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Sample records for 1h larmor frequency

  1. Noninvasive measurement of conductivity anisotropy at larmor frequency using MRI.

    PubMed

    Lee, Joonsung; Song, Yizhuang; Choi, Narae; Cho, Sungmin; Seo, Jin Keun; Kim, Dong-Hyun

    2013-01-01

    Anisotropic electrical properties can be found in biological tissues such as muscles and nerves. Conductivity tensor is a simplified model to express the effective electrical anisotropic information and depends on the imaging resolution. The determination of the conductivity tensor should be based on Ohm's law. In other words, the measurement of partial information of current density and the electric fields should be made. Since the direct measurements of the electric field and the current density are difficult, we use MRI to measure their partial information such as B1 map; it measures circulating current density and circulating electric field. In this work, the ratio of the two circulating fields, termed circulating admittivity, is proposed as measures of the conductivity anisotropy at Larmor frequency. Given eigenvectors of the conductivity tensor, quantitative measurement of the eigenvalues can be achieved from circulating admittivity for special tissue models. Without eigenvectors, qualitative information of anisotropy still can be acquired from circulating admittivity. The limitation of the circulating admittivity is that at least two components of the magnetic fields should be measured to capture anisotropic information.

  2. Direct CW - NMR observation of forbidden transitions at double larmor frequency in hydrogen

    NASA Astrophysics Data System (ADS)

    Skrbek, L.; Sebek, J.; Safrata, R. S.

    1990-08-01

    By means of the classical transverse continuous wave nuclear magnetic resonance (NMR) the forbidden transitions at double Larmor frequency for hydrogen have been observed. The NMR spectra have been measured directly by scanning the external magnetic field up to 10 mT at temperatures about 30 mK. The intensity of the forbidden transition at double Larmor frequency I 2 is of the same order of magnitude as the intensity I 1 of the main Larmor line under these conditions. The intensity ratio I 1/I 2 depends on the external magnetic field in accordance with Cheng theory and NMR-SQUID measurements of Kohl and coworkers.

  3. Larmor frequency dressing by a nonharmonic transverse magnetic field

    NASA Astrophysics Data System (ADS)

    Bevilacqua, G.; Biancalana, V.; Dancheva, Y.; Moi, L.

    2012-04-01

    We present a theoretical and experimental study of spin precession in the presence of both a static and an orthogonal oscillating magnetic field, which is nonresonant, not harmonically related to the Larmor precession, and of arbitrary strength. Due to the intrinsic nonlinearity of the system, previous models that account only for the simple sinusoidal case cannot be applied. We suggest an alternative approach and develop a model that closely agrees with experimental data produced by an optical-pumping atomic magnetometer. We demonstrate that an appropriately designed nonharmonic field makes it possible to extract a linear response to a weak dc transverse field, despite the scalar nature of the magnetometer, which normally causes a much weaker, second-order response.

  4. Comments on finite Larmor radius models for ion cyclotron range of frequencies heating in tokamaks

    SciTech Connect

    Phillips, C.K.; Wilson, J.R.; Hosea, J.C.; Majeski, R.; Smithe, D.N.

    1994-06-01

    The accuracy of standard finite Larmor radius (FLR) models for wave propagation in the ion cyclotron range of frequencies (ICRF) is compared against full hot plasma models. For multiple ion species plasmas, the FLR model is shown to predict the presence of a spurious second harmonic ion-ion type resonance between the second harmonic cyclotron layers of two ion species. It is shown explicitly here that the spurious resonance is an artifact of the FLR models and that no absorption occurs in the plasma as a result of this ``resonance.``

  5. Neutron intensity modulation and time-focusing with integrated Larmor and resonant frequency techniques

    SciTech Connect

    Zhao, Jinkui Hamilton, William A.; Robertson, J. L.; Crow, Lowell; Lee, Sung-Woo; Kang, Yoon W.

    2015-09-14

    The analysis of neutron diffraction experiments often assumes that neutrons are elastically scattered from the sample. However, there is growing evidence that a significant fraction of the detected neutrons is in fact inelastically scattered, especially from soft materials and aqueous samples. Ignoring these inelastic contributions gives rise to inaccurate experimental results. To date, there has been no simple method with broad applicability for inelastic signal separation in neutron diffraction experiments. Here, we present a simple and robust method that we believe could be suited for this purpose. We use two radio frequency resonant spin flippers integrated with a Larmor precession field to modulate the neutron intensity and to encode the inelastic scattering information into the neutron data. All three components contribute to the spin encoding. The Larmor field serves several additional purposes. Its usage facilitates neutron time-focusing, eliminates the need for stringent magnetic shielding, and allows for compact setups. The scheme is robust, simple, and flexible. We believe that, with further improvements, it has the potential of adding inelastic signal discrimination capabilities to many existing diffraction instruments in the future.

  6. Neutron intensity modulation and time-focusing with integrated Larmor and resonant frequency techniques

    NASA Astrophysics Data System (ADS)

    Zhao, Jinkui; Hamilton, William A.; Lee, Sung-Woo; Robertson, J. L.; Crow, Lowell; Kang, Yoon W.

    2015-09-01

    The analysis of neutron diffraction experiments often assumes that neutrons are elastically scattered from the sample. However, there is growing evidence that a significant fraction of the detected neutrons is in fact inelastically scattered, especially from soft materials and aqueous samples. Ignoring these inelastic contributions gives rise to inaccurate experimental results. To date, there has been no simple method with broad applicability for inelastic signal separation in neutron diffraction experiments. Here, we present a simple and robust method that we believe could be suited for this purpose. We use two radio frequency resonant spin flippers integrated with a Larmor precession field to modulate the neutron intensity and to encode the inelastic scattering information into the neutron data. All three components contribute to the spin encoding. The Larmor field serves several additional purposes. Its usage facilitates neutron time-focusing, eliminates the need for stringent magnetic shielding, and allows for compact setups. The scheme is robust, simple, and flexible. We believe that, with further improvements, it has the potential of adding inelastic signal discrimination capabilities to many existing diffraction instruments in the future.

  7. Magnetic relaxation for Mn-based compounds exhibiting the Larmor precession at THz wave range frequencies

    NASA Astrophysics Data System (ADS)

    Mizukami, S.; Iihama, S.; Sasaki, Y.; Sugihara, A.; Ranjbar, R.; Suzuki, K. Z.

    2016-10-01

    Mn-based hard magnets are potentially suitable for advanced ultra-high frequency spintronics applications because they exhibit the Larmor precession of magnetization at THz wave-range frequencies with low magnetic relaxation. However, the low magnetic relaxation properties are not well understood; thus, a more detailed study is necessary. In this study, magnetization precessions in L10 Mn1.54Ga, D022 Mn2.12Ga, and C38 MnAlGe epitaxial films grown on MgO substrates were investigated using an all-optical pump-probe method under a magnetic field of ˜20 kOe. The coherent magnetization precessions at frequencies of more than 0.1, 0.2, and 0.3 THz for the C38 MnAlGe, L10 Mn1.54Ga, and D022 Mn2.12Ga films, respectively, were clearly measured. The effective damping constant for the C38 MnAlGe film was smaller than the previously reported value measured at 10 kOe by a factor of 2, whereas those showed a large angular dependence. The effective damping constants for the L10 Mn1.54Ga and D022 Mn2.12Ga films were independent of the field angle and approximately identical to the values measured at 10 kOe. Thus, it was concluded that the values for the Gilbert damping constant, α, were 0.008 and 0.012 for the L10 Mn1.54Ga and D022 Mn2.12Ga films, respectively. The possible origin of the discrepancy between the experimental and theoretical α values for these films is discussed.

  8. Electrical tissue property imaging using MRI at dc and Larmor frequency

    NASA Astrophysics Data System (ADS)

    Seo, Jin Keun; Kim, Dong-Hyun; Lee, Joonsung; In Kwon, Oh; Sajib, Saurav Z. K.; Woo, Eung Je

    2012-08-01

    Cross-sectional imaging of conductivity and permittivity distributions inside the human body has been actively investigated in impedance imaging areas such as electrical impedance tomography (EIT) and magnetic induction tomography (MIT). Since the conductivity and permittivity values exhibit frequency-dependent changes, it is worthwhile to perform spectroscopic imaging from almost dc to hundreds of MHz. To probe the human body, we may inject current using surface electrodes or induce current using external coils. In EIT and MIT, measured data are only available on the boundary or exterior of the body unless we invasively place sensors inside the body. Their image reconstruction problems are nonlinear and ill-posed to result in images with a relatively low spatial resolution. Noting that an MRI scanner can noninvasively measure magnetic fields inside the human body, electrical tissue property imaging methods using MRI have lately been proposed. Magnetic resonance EIT (MREIT) performs conductivity imaging at dc or below 1 kHz by externally injecting current into the human body and measuring induced internal magnetic flux density data using an MRI scanner. Magnetic resonance electrical property tomography (MREPT) produces both conductivity and permittivity images at the Larmor frequency of an MRI scanner based on B1-mapping techniques. Since internal data are only available in MREIT and MREPT, we may formulate well-posed inverse problems for image reconstructions. To develop related imaging techniques, we should clearly understand the basic principles of MREIT and MREPT, which are based on coupled physics of bioelectromagnetism and MRI as well as associated mathematical methods. In this paper, we describe the physical principles of MREIT and MREPT in a unified way and associate measurable quantities with the conductivity and permittivity. Clarifying the key relations among them, we examine existing image reconstruction algorithms to reveal their capabilities and

  9. Decoupling a spin qubit from high-frequency Larmor dynamics of a GaAs nuclear spin bath

    NASA Astrophysics Data System (ADS)

    Malinowski, Filip K.; Martins, Frederico; Nissen, Peter D.; Rudner, Mark S.; Marcus, Charles M.; Kuemmeth, Ferdinand; Barnes, Edwin; Fallahi, Saeed; Gardner, Geoffrey C.; Manfra, Michael J.

    We present a technique of decoupling a spin qubit in a GaAs/AlGaAs heterostructure from low- and high-frequency noise arising from hyperfine interaction of electrons with nuclear spins. We use Carr-Purcell-Meiboom-Gill sequences in which we synchronize the repetition rate of π pulses to difference Larmor frequencies of 69Ga, 71Ga and 75As nuclei. This decouples the qubit both from low-frequency noise due to diffusion of nuclear spins and from noise at selected high frequencies, allowing us to apply more than a thousand π pulses in a sequence. We demonstrate a coherence time of a singlet-triplet qubit of 0.87 ms, i.e. five orders of magnitude longer than the inhomogeneous dephasing time intrinsic to GaAs. Support through IARPA-MQCO, Army Research Office, LPS-MPO-CMTC, the Villum Foundation and the Danish National Research Foundation is acknowledged.

  10. Finite-pulse radio frequency driven recoupling with phase cycling for 2D 1H/1H correlation at ultrafast MAS frequencies

    NASA Astrophysics Data System (ADS)

    Nishiyama, Yusuke; Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2014-06-01

    The first-order recoupling sequence radio frequency driven dipolar recoupling (RFDR) is commonly used in single-quantum/single-quantum homonuclear correlation 2D experiments under magic angle spinning (MAS) to determine homonuclear proximities. From previously reported analysis of the use of XY-based super-cycling schemes to enhance the efficiency of the finite-pulse-RFDR (fp-RFDR) pulse sequence, XY814 phase cycling was found to provide the optimum performance for 2D correlation experiments on low-γ nuclei. In this study, we analyze the efficiency of different phase cycling schemes for proton-based fp-RFDR experiments. We demonstrate the advantages of using a short phase cycle, XY4, and its super-cycle XY414 that only recouples the zero-quantum homonuclear dipolar coupling, for the fp-RFDR sequence in 2D 1H/1H correlation experiments at ultrafast MAS frequencies. The dipolar recoupling efficiencies of XY4, XY414 and XY814 phase cycling schemes are compared based on results obtained from 2D 1H/1H correlation experiments, utilizing the fp-RFDR pulse sequence, on powder samples of U-13C,15N-L-alanine, N-acetyl-15N-L-valyl-15N-L-leucine, and glycine. Experimental results and spin dynamics simulations show that XY414 performs the best when a high RF power is used for the 180° pulse, whereas XY4 renders the best performance when a low RF power is used. The effects of RF field inhomogeneity and chemical shift offsets are also examined. Overall, our results suggest that a combination of fp-RFDR-XY414 employed in the recycle delay with a large RF-field to decrease the recycle delay, and fp-RFDR-XY4 in the mixing period with a moderate RF-field, is a robust and efficient method for 2D single-quantum/single-quantum 1H/1H correlation experiments at ultrafast MAS frequencies.

  11. Protein-induced water 1H MR frequency shifts: Contributions from magnetic susceptibility and exchange effects

    NASA Astrophysics Data System (ADS)

    Luo, Jie; He, Xiang; d'Avignon, D. Andre'; Ackerman, Joseph J. H.; Yablonskiy, Dmitriy A.

    2010-01-01

    Defining the biophysics underlying the remarkable MRI phase contrast reported in high field MRI studies of human brain would lead to more quantitative image analysis and more informed pulse sequence development. Toward this end, the dependence of water 1H resonance frequency on protein concentration was investigated using bovine serum albumin (BSA) as a model system. Two distinct mechanisms were found to underlie a water 1H resonance frequency shift: (i) a protein-concentration-induced change in bulk magnetic susceptibility, causing a shift to lower frequency, and (ii) exchange of water between chemical-shift distinct environments, i.e., free (bulk water) and protein-associated ("bound") water, including freely exchangeable 1H sites on proteins, causing a shift to higher frequency. At 37 °C the amplitude of the exchange effect is roughly half that of the susceptibility effect.

  12. Rapid measurement of multidimensional 1H solid-state NMR spectra at ultra-fast MAS frequencies

    NASA Astrophysics Data System (ADS)

    Ye, Yue Qi; Malon, Michal; Martineau, Charlotte; Taulelle, Francis; Nishiyama, Yusuke

    2014-02-01

    A novel method to realize rapid repetition of 1H NMR experiments at ultra-fast MAS frequencies is demonstrated. The ultra-fast MAS at 110 kHz slows the 1H-1H spin diffusion, leading to variations of 1H T1 relaxation times from atom to atom within a molecule. The different relaxation behavior is averaged by applying 1H-1H recoupling during relaxation delay even at ultra-fast MAS, reducing the optimal relaxation delay to maximize the signal to noise ratio. The way to determine optimal relaxation delay for arbitrary relaxation curve is shown. The reduction of optimal relaxation delay by radio-frequency driven recoupling (RFDR) was demonstrated on powder samples of glycine and ethenzamide with one and multi-dimensional NMR measurements.

  13. Quantum Larmor radiation in de Sitter spacetime

    NASA Astrophysics Data System (ADS)

    Blaga, Robert; Busuioc, Sergiu

    2016-09-01

    We study the radiation emitted by inertial charge evolving on the expanding de Sitter spacetime. Performing a perturbative calculation, within scalar quantum electrodynamics (sQED), we obtain the transition amplitude for the process and using this we define the energy radiated by the source. In the non-relativistic limit we find that the leading term is compatible with the classical result (Larmor formula). The first quantum correction is found to be negative, a result which is in line with a number of similar quantum field theory results. For the ultra-relativistic case we find a logarithmic divergence of the emitted energy for large frequencies, which we link to the nature of the spacetime. We compare our results with that of Nomura et al. (JCAP 11:013, 2006), where the authors make a similar calculation for a general conformally flat spacetime.

  14. Visualizing brain inflammation with a shingled-leg radio-frequency head probe for 19F/1H MRI.

    PubMed

    Waiczies, Helmar; Lepore, Stefano; Drechsler, Susanne; Qadri, Fatimunnisa; Purfürst, Bettina; Sydow, Karl; Dathe, Margitta; Kühne, André; Lindel, Tomasz; Hoffmann, Werner; Pohlmann, Andreas; Niendorf, Thoralf; Waiczies, Sonia

    2013-01-01

    Magnetic resonance imaging (MRI) provides the opportunity of tracking cells in vivo. Major challenges in dissecting cells from the recipient tissue and signal sensitivity constraints albeit exist. In this study, we aimed to tackle these limitations in order to study inflammation in autoimmune encephalomyelitis. We constructed a very small dual-tunable radio frequency (RF) birdcage probe tailored for (19)F (fluorine) and (1)H (proton) MR mouse neuroimaging. The novel design eliminated the need for extra electrical components on the probe structure and afforded a uniform -field as well as good SNR. We employed fluorescently-tagged (19)F nanoparticles and could study the dynamics of inflammatory cells between CNS and lymphatic system during development of encephalomyelitis, even within regions of the brain that are otherwise not easily visualized by conventional probes. (19)F/(1)H MR Neuroimaging will allow us to study the nature of immune cell infiltration during brain inflammation over an extensive period of time. PMID:23412352

  15. Visualizing Brain Inflammation with a Shingled-Leg Radio-Frequency Head Probe for 19F/1H MRI

    PubMed Central

    Waiczies, Helmar; Lepore, Stefano; Drechsler, Susanne; Qadri, Fatimunnisa; Purfürst, Bettina; Sydow, Karl; Dathe, Margitta; Kühne, André; Lindel, Tomasz; Hoffmann, Werner; Pohlmann, Andreas; Niendorf, Thoralf; Waiczies, Sonia

    2013-01-01

    Magnetic resonance imaging (MRI) provides the opportunity of tracking cells in vivo. Major challenges in dissecting cells from the recipient tissue and signal sensitivity constraints albeit exist. In this study, we aimed to tackle these limitations in order to study inflammation in autoimmune encephalomyelitis. We constructed a very small dual-tunable radio frequency (RF) birdcage probe tailored for 19F (fluorine) and 1H (proton) MR mouse neuroimaging. The novel design eliminated the need for extra electrical components on the probe structure and afforded a uniform -field as well as good SNR. We employed fluorescently-tagged 19F nanoparticles and could study the dynamics of inflammatory cells between CNS and lymphatic system during development of encephalomyelitis, even within regions of the brain that are otherwise not easily visualized by conventional probes. 19F/1H MR Neuroimaging will allow us to study the nature of immune cell infiltration during brain inflammation over an extensive period of time. PMID:23412352

  16. Finite Larmor radius modification of the Mercier criterion

    SciTech Connect

    Connor, J.W.; Tang, W.M.; Allen, L.

    1984-04-01

    The finite Larmor radius modification of the Suydam criterion involves a competition between stabilizing finite Larmor radius effects and destabilizing curvature. In the case of the toroidal calculation, corresponding to the Mercier criterion, ballooning effects from regions of unfavorable curvature must be taken into account. In the case of a model equilibrium, valid near the magnetic axis, a complete solution is obtained. Results indicate that the amount of finite Larmor radius stabilization needed to overcome the effects of unfavorable average curvature increases as a function of the toroidal ballooning parameter.

  17. Experimental study of finite Larmor radius effects

    SciTech Connect

    Struve, K.W.

    1980-08-01

    Linear Z-pinches in Ar, Kr, Xe, N/sub 2/, and He are experimentally studied in regimes where strong finite Larmor radius effects could provide a significant stabilizing effect. Scaling arguments show that for deuterium such a pinch has an electron line density of order 2 x 10/sup 15//cm. For higher Z plasmas a higher line density is allowed, the exact value of which depends on the average ion charge. The pinch is formed by puffing gas axially through the cathode towards the anode of an evacuated pinch chamber. When the gas reaches the anode, the pinch bank is fired. The pinch current rises in 2 to 3 ..mu..sec to a maximum of 100 to 200 kA. The pinch bank capacitance is 900 ..mu..F, and the external inductance is 100 nH. Additionally, the bank is fused to increase dI/dt. The primary diagnostics are a framing camera, a spatially resolved Mach-Zehnder interferometer, and X-ray absorption.

  18. Calibration of a Larmor clock for tunneling time experiments

    NASA Astrophysics Data System (ADS)

    Ramos, Jesus; Potnis, Shreyas; Spierings, David; Ebadi, Sapehr; Steinberg, Aephraim

    2016-05-01

    How much time does it take for a particle to tunnel? This has been a controversial question since the early times of quantum mechanics. The debate stems mainly from the inability to measure time directly. One proposal to measure the tunnelling time is the Larmor clock, in which the spin degree of freedom of the tunneling particle is used as a clock. This clock only ``ticks'' inside the forbidden region due to the precession of the spin about a magnetic field localized within the barrier. Here, we report the calibration of a Larmor clock to measure tunneling times of a 87 Rb Bose Einstein condensate. We use the Zeeman sublevels of the ground-state F = 2 manifold and Raman beams for the implementation of a Larmor clock. Experimental progress towards measuring the tunneling time and the challenges involved in this measurement will also be discussed.

  19. Finite Larmor radius flute mode theory with end loss

    SciTech Connect

    Kotelnikov, I.A.; Berk, H.L.

    1993-08-01

    The theory of flute mode stability is developed for a two-energy- component plasma partially terminated by a conducting limiter. The formalism is developed as a preliminary study of the effect of end-loss in open-ended mirror machines where large Larmor radius effects are important.

  20. Flute waves at the ion Larmor radius scales

    SciTech Connect

    Onishchenko, O. G.

    2010-12-14

    The theory of the magnetic Rayleigh-Taylor instability (RTI) is discussed. Modified linear kinetic theory allows us to investigate RTI and flute waves with arbitrary perpendicular spatial scales compared to the ion Larmor radius. It is shown that in the linear limit a Fourier transform of these equations yields the dispersion relation which in the so-called Pade approximation corresponds to results of the kinetic theory. This analysis represents an extension of the previous study of the magnetic RTI obtained in the large wave scale approximation. It is shown that incorporation of the effects associated with wave scales of the order of the ion Larmor radius leads to a broader wave number range of the magnetic RTI.

  1. Larmor labeling of neutron spin using superconducting Wollaston prisms

    NASA Astrophysics Data System (ADS)

    Li, Fankang

    Neutron spin Larmor labeling using magnetic Wollaston prisms (WP) provides a way to overcome some of the limitations arising from the nature of neutron beams: low flux and divergence. Using superconducting films and tapes, a series of strong, well-defined shaped magnetic fields can be produced due to both the zero-resistance and Meissner effect in superconductors. Using finite element simulations, the criterion to build a superconducting magnetic Wollaston prism with high encoding efficiency and low Larmor phase aberrations are presented. To achieve a high magnetic field and simplify the maintenance, we optimize the design using careful thermal analysis. The measured neutron spin flipping efficiency is measured to be independent of both the neutron wavelength and energizing current, which is a significant improvement over other devices with similar functions. A highly linear variation of the Larmor phase is measured across the device, which ensures a highly uniform encoding of scattering angles into the neutron spin Larmor phase. Using two WPs, the correlation function for a colloidal silica sample was measured by spin echo modulated small angle neutron scattering (SEMSANS) and agrees well with other techniques. Using Monte Carlo code (McStas), we further investigated the SEMSANS setup and showed the requirements to improve its performance. We have proposed a new technique to implement neutron spin echo on a triple axis neutron spectrometer to achieve high resolution measurements of the lifetime of dispersive phonon excitations. The spin echo is tuned by appropriate choice of magnetic fields instead of physically tilting the coils used in traditional methods. This new approach allows a higher energy resolution and a larger effective tilting angle and hence larger group velocity to be measured.

  2. Quantum Larmor radiation in a conformally flat universe

    SciTech Connect

    Kimura, Rampei; Nakamura, Gen; Yamamoto, Kazuhiro

    2011-02-15

    We investigate the quantum effect on the Larmor radiation from a moving charge in an expanding universe based on the framework of the scalar quantum electrodynamics. A theoretical formula for the radiation energy is derived at the lowest order of the perturbation theory with respect to the coupling constant of the scalar quantum electrodynamics. We evaluate the radiation energy on the background universe so that the Minkowski spacetime transits to the Milne universe, in which the equation of motion for the mode function of the free complex scalar field can be exactly solved in an analytic way. Then, the result is compared with the WKB approach, in which the equation of motion of the mode function is constructed with the WKB approximation which is valid as long as the Compton wavelength is shorter than the Hubble horizon length. This demonstrates that the quantum effect on the Larmor radiation of the order e{sup 2}({h_bar}/2{pi}) is determined by a nonlocal integration in time depending on the background expansion. We also compare our result with a recent work by Higuchi and Walker [Phys. Rev. D 80, 105019 (2009)], which investigated the quantum correction to the Larmor radiation from a charged particle in a nonrelativistic motion in a homogeneous electric field.

  3. Finite Larmor radii effects in fast ion measurements with neutron emission spectrometry

    NASA Astrophysics Data System (ADS)

    Eriksson, J.; Hellesen, C.; Andersson Sundén, E.; Cecconello, M.; Conroy, S.; Ericsson, G.; Gatu Johnson, M.; Pinches, S. D.; Sharapov, S. E.; Weiszflog, M.; EFDA contributors, JET

    2013-01-01

    When analysing data from fast ion measurements it is normally assumed that the gyro-phase distribution of the ions is isotropic within the field of view of the measuring instrument. This assumption is not valid if the Larmor radii of the fast ions are comparable to—or larger than—the gradient scale length in the spatial distribution of the ions, and if this scale length is comparable to—or smaller than—the width of the field of view of the measuring instrument. In this paper the effect of such an anisotropy is demonstrated by analysing neutron emission spectrometry data from a JET experiment with deuterium neutral beams together with radiofrequency heating at the third harmonic of the deuterium cyclotron frequency. In the experiment, the neutron time-of-flight spectrometer TOFOR was used to measure the neutrons from the d(d,n)3He-reaction. Comparison of the experimental data with Monte Carlo calculations shows that the finite Larmor radii of the fast ions need to be included in the modelling to get a good description of the data. Similar effects are likely to be important for other fast ion diagnostics, such as γ-ray spectroscopy and neutral particle analysis, as well.

  4. FTIR and 1H MAS NMR investigations on the correlation between the frequency of stretching vibration and the chemical shift of surface OH groups of solids

    NASA Astrophysics Data System (ADS)

    Brunner, Eike; Karge, H. G.; Pfeifer, H.

    1992-03-01

    The study of surface hydroxyl groups of solids, especially of zeolites, belongs to the 'classical' topics of IR spectroscopy since physico-chemical information may be derived from the wavenumber (nu) OH of the stretching vibration of the different hydroxyls. On the other hand, the last decade has seen the development of high resolution solid-state NMR spectroscopy and through the use of the so-called magic-angle-spinning technique (MAS) the signals of different hydroxyl species can be resolved in the 1H NMR spectra of solids. The chemical shift (delta) H describing the position of these lines may be used as well as (nu) OH to characterize quantitatively the strength of acidity of surface OH groups of solids. In a first comparison of (nu) OH with (delta) H for several types of surface OH groups, a linear correlation between them could be found. The aim of this paper was to prove the validity of this correlation for a wide variety of hydroxyls. The IR measurements were carried out on a Perkin-Elmer FTIR spectrometer 1800 at the Fritz Haber Institute of the Max Planck Society, Berlin, and the 1H MAS NMR spectra were recorded on a Bruker MSL- 300 at the University of Leipzig.

  5. Finite Larmor radius effect on ion pickup at Venus

    NASA Technical Reports Server (NTRS)

    Phillips, J. L.; Luhmann, J. G.; Russell, C. T.; Moore, K. R.

    1987-01-01

    The interaction of the solar wind with Venus is influenced by the pickup of newly born exospheric oxygen ions by the convecting magnetosheath plasma. The flow and field configuration of the magnetosheath plasma, together with the large gyroradius of the pickup ions, cause mass loading to occur preferentially on one side of the magnetosheath. The observed hemispherical asymmetry in the magnetic field in the near-planet magnetosheath, attributed to this pickup process, is confirmed by direct observation of the picked-up planetary particles. Test particle calculations show that a current system created by ion pickup has the appropriate location and magnitude to account for the magnetic field asymmetry. The results indicate that a fluid treatment of the Venus mass-loading problem is not entirely appropriate; a hybrid or kinetic model is necessary to incorporate the finite Larmor radius of the pickup particles which produces the observed asymmetry.

  6. Increased component isotropy and plasma magnetic compression at sub-ion Larmor scale turbulence in the solar wind as seen by Cluster

    NASA Astrophysics Data System (ADS)

    Kiyani, K.; Sahraoui, F.; Hnat, B.; Chapman, S. C.; Fauvarque, O.; Khotyaintsev, Y. V.

    2012-12-01

    The anisotropic nature of solar wind magnetic turbulence fluctuations is investigated scale-by-scale using high cadence in-situ magnetic field measurements from the Cluster and ACE spacecraft missions. The data span five decades in scales from the inertial range to the electron Larmor radius. In contrast to the inertial range, there is a successive increase towards isotropy between parallel and transverse power at scales below the ion Larmor radius, with isotropy being achieved at the electron Larmor radius. In the context of wave-mediated theories of turbulence, we show that this enhancement in magnetic fluctuations parallel to the local mean background field is qualitatively consistent with the magnetic compressibility signature of kinetic Alfvén wave solutions of the linearized Vlasov equation. More generally, we discuss how these results may arise naturally due to the prominent role of the Hall term at sub-ion Larmor scales. Furthermore, computing higher-order statistics, we show that the full statistical signature of the fluctuations at scales below the ion Larmor radius is that of a single isotropic globally scale-invariant process distinct from the anisotropic statistics of the inertial range.(Upper panel) PSD (from Cluster) of the transverse and parallel components spanning the inertial and dissipation ranges. (Lower panel) Ratio of parallel over transverse PSD. Horizontal dot-dashed line indicates a ratio of 1/3 where isotropy in power occurs. Vertical dashed and dashed-dotted lines indicate the ion and electron gyro-radii respectively, Doppler-shifted to spacecraft frequency using the Taylor hypothesis.

  7. Control and Detection of the Larmor Precession of F = 2 87Rb Bose-Einstein Condensates by Ramsey Interferometry and Spin-Echo

    NASA Astrophysics Data System (ADS)

    Eto, Yujiro; Sekine, Sawako; Hasegawa, Sho; Sadgrove, Mark; Saito, Hiroki; Hirano, Takuya

    2013-05-01

    Radio-frequency pulses are applied to probe and control the Larmor precession of a spin-2 Bose-Einstein condensate subject to a magnetic field gradient. Using the techniques of Ramsey interferometry and Stern-Gerlach absorption imaging, a helical spin pattern was clearly observed as spatial variations in the atomic density distribution. We experimentally show that the spin echo technique reduces the effects of spatially inhomogeneous and temporally fluctuating spin evolution, and improves the repeatability of the interferometry.

  8. U1h Superstructure

    SciTech Connect

    Glen Sykes

    2000-11-01

    The U1H Shaft Project is a design build subcontract to supply the U. S. Department of Energy (DOE) a 1,045 ft. deep, 20 ft. diameter, concrete lined shaft for unspecified purposes. The subcontract awarded to Atkinson Construction by Bechtel Nevada to design and construct the shaft for the DOE has been split into phases with portions of the work being released as dictated by available funding. The first portion released included the design for the shaft, permanent hoist, headframe, and collar arrangement. The second release consisted of constructing the shaft collar to a depth of 110 ft., the service entry, utility trenches, and installation of the temporary sinking plant. The temporary sinking plant included the installation of the sinking headframe, the sinking hoist, two deck winches, the shaft form, the sinking work deck, and temporary utilities required to sink the shaft. Both the design and collar construction were completed on schedule. The third release consisted of excavating and lining the shaft to the station depth of approximately 950 feet. Work is currently proceeding on this production sinking phase. At a depth of approximately 600 feet, Atkinson has surpassed production expectation and is more than 3 months ahead of schedule. Atkinson has employed the use of a Bobcat 331 excavator as the primary means of excavation. the shaft is being excavated entirely in an alluvial deposit with varying degrees of calcium carbonate cementation. Several more work packages are expected to be released in the near future. The remaining work packages include, construction of the shaft station a depth of 975 ft. and construction of the shaft sump to a depth of 1,045 ft., installation of the loading pocket and station steel and equipment, installation of the shaft steel and guides, installation of the shaft utilities, and installation of the permanent headframe, hoist, collar utilities, and facilities.

  9. Effects of a Guide Field on the Larmor Electric Field in Collisionless Asymmetric Reconnection

    NASA Astrophysics Data System (ADS)

    Ruffolo, D. J.; Malakit, K.; Ek-In, S.; Shay, M. A.; Cassak, P.

    2014-12-01

    Recently it has been pointed out that when the inflow conditions of magnetic reconnection are asymmetric, a new in-plane electric field can arise from the physics of finite ion Larmor radius, called the Larmor electric field. It is located next to the Hall electric field structure, making it a potential indicator of proximity to the diffusion region. However, the properties of the Larmor electric field have not previously been explored for the case of a nonzero guide field, which could occur for many reconnection sites, including the day-side magnetopause. In this study, we therefore further explore the properties of the Larmor electric field by adding guide fields with different strengths into our simulations. The results show that the width of the Larmor electric field structure will be smaller, but the strength of the field will be stronger as the guide field increases, consistent with what we expect from the existing theory. Moreover, we show that in the region where the Larmor electric field occurs, there also appears an electron anisotropy. The widths of the electron anisotropy and Larmor electric field structures are found to be similar, suggesting that observing the combination of these two signatures provides a useful indicator of proximity to a reconnection site. Partially supported by a Mahidol University Postdoctoral Fellowship and the Thailand Research Fund. This research was supported by the postdoctoral research sponsorship of Mahidol University (K. M.), the Thailand Research Fund (D. R.), NSF Grants No. ATM-0645271 (M. A. S.) and No. AGS-0953463 (P.A. C.), NASA Grants No. NNX08A083G—MMS IDS, No. NNX11AD69G, and No. NNX13AD72G(M. A. S.).

  10. Larmor electric field observed at the Earth's magnetopause by Polar satellite

    SciTech Connect

    Koga, D. Gonzalez, W. D.; Silveira, M. V. D.; Mozer, F. S.; Cardoso, F. R.

    2014-10-15

    We present, for the first time, observational evidence of a kinetic electric field near the X-line associated with asymmetric reconnection at the Earth's dayside magnetopause using Polar observations. On March 29, 2003, Polar satellite detected an asymmetric collisionless reconnection event. This event shows a unipolar Hall electric field signature and a simple deviation from the guide field during the magnetopause crossing, with the absence of an ion plasma jet outflow indicating that the magnetopause crossing was near the X-line. As expected from particle-in-cell simulations by Malakit et al. (Phys. Rev. Lett. 111, 135001 (2013)), an earthward pointing normal electric field appears in the magnetospheric side of the ion diffusion region. The electric field satisfies two necessary conditions for the existence of the finite ion Larmor radius effect: (1) the ion Larmor radius (r{sub g2}) is larger than the distance between the stagnation point and the edge of the ion diffusion region in the strong magnetic field side (δ{sub S2}) and (2) the spatial extent of the kinetic electric field (δ{sub EL}) is of the order of the ion Larmor radius. Furthermore, it is shown that the peak value of the Larmor electric field is comparable to the predicted value. The observation of the Larmor electric field can be valuable in other analyses to show that the crossing occurred near the X-line.

  11. The modulational instability in the extended Hasegawa-Mima equation with a finite Larmor radius

    SciTech Connect

    Gallagher, S.; Hnat, B.; Rowlands, G.; Connaughton, C.; Nazarenko, S.

    2012-12-15

    The effects of the finite Larmor radius on the generation of zonal flows by the four-wave modulational instability are investigated using an extended form of the Hasegawa-Mima equation. Growth rates of the zonal mode are quantified using analytical predictions from a four-mode truncated model, as well as from direct numerical simulation of the nonlinear extended Hasegawa-Mima equation. We not only consider purely zonal flows but also examine the generic oblique case and show that, for small Larmor radii, off-axis modes may become dominant. We find a key parameter M{sub {rho}} which characterises the behaviour of the system due to changes in the Larmor radius. We find that, similarly to previous results obtained by changing the driving wave amplitude, two separate dynamical regimes can be accessed. These correspond to oscillatory energy transfer between zonal flows and a driving wave and the fully saturated zonal flow.

  12. The modulational instability in the extended Hasegawa-Mima equation with a finite Larmor radius

    NASA Astrophysics Data System (ADS)

    Gallagher, S.; Hnat, B.; Connaughton, C.; Nazarenko, S.; Rowlands, G.

    2012-12-01

    The effects of the finite Larmor radius on the generation of zonal flows by the four-wave modulational instability are investigated using an extended form of the Hasegawa-Mima equation. Growth rates of the zonal mode are quantified using analytical predictions from a four-mode truncated model, as well as from direct numerical simulation of the nonlinear extended Hasegawa-Mima equation. We not only consider purely zonal flows but also examine the generic oblique case and show that, for small Larmor radii, off-axis modes may become dominant. We find a key parameter Mρ which characterises the behaviour of the system due to changes in the Larmor radius. We find that, similarly to previous results obtained by changing the driving wave amplitude, two separate dynamical regimes can be accessed. These correspond to oscillatory energy transfer between zonal flows and a driving wave and the fully saturated zonal flow.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  14. Simultaneous (19)F-(1)H medium resolution NMR spectroscopy for online reaction monitoring.

    PubMed

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

    2014-10-18

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

  15. Quantum Larmor Radiation from a Moving Charge in AN Electromagnetic Plane Wave Background

    NASA Astrophysics Data System (ADS)

    Nakamura, Gen; Yamamoto, Kazuhiro

    2012-09-01

    We extend our previous work [Phys. Rev. D83, 045030 (2011)], which investigated the first-order quantum effect in the Larmor radiation from a moving charge in a spatially homogeneous time-dependent electric field. Specifically, we investigate the quantum Larmor radiation from a moving charge in a monochromatic electromagnetic plane wave background based on the scalar quantum electrodynamics at the lowest order of the perturbation theory. Using the in-in formalism, we derive the theoretical formula of the total radiation energy from a charged particle in the initial states being at rest and being in a relativistic motion. Expanding the theoretical formula in terms of the Planck constant ℏ, we obtain the first-order quantum effect on the Larmor radiation. The quantum effect generally suppresses the total radiation energy compared with the prediction of the classical Larmor formula, which is a contrast to the previous work. The reason is explained by the fact that the radiation from a moving charge in a monochromatic electromagnetic plane wave is expressed in terms of the inelastic collisions between an electron and photons of the background electromagnetic waves.

  16. Finite Larmor radius assisted velocity shear stabilization of the interchange instability in magnetized plasmas

    SciTech Connect

    Ng Sheungwah; Hassam, A.B.

    2005-06-15

    Finite Larmor radius (FLR) effects, originally shown to stabilize magnetized plasma interchange modes at short wavelength, are shown to assist velocity shear stabilization of long wavelength interchanges. It is shown that the FLR effects result in stabilization with roughly the same efficacy as the stabilization from dissipative (resistive and viscous) effects found earlier.

  17. The magnetic Rayleigh-Taylor instability and flute waves at the ion Larmor radius scales

    SciTech Connect

    Onishchenko, O. G.; Pokhotelov, O. A.; Stenflo, L.; Shukla, P. K.

    2011-02-15

    The theory of flute waves (with arbitrary spatial scales compared to the ion Larmor radius) driven by the Rayleigh-Taylor instability (RTI) is developed. Both the kinetic and hydrodynamic models are considered. In this way we have extended the previous analysis of RTI carried out in the long wavelength limit. It is found that complete finite ion Larmor radius stabilization is absent when the ion diamagnetic velocity attains the ion gravitation drift velocity. The hydrodynamic approach allowed us to deduce a new set of nonlinear equations for flute waves with arbitrary spatial scales. It is shown that the previously deduced equations are inadequate when the wavelength becomes of the order of the ion Larmor radius. In the linear limit a Fourier transform of these equations yields the dispersion relation which in the so-called Pade approximation corresponds to the results of the fully kinetic treatment. The development of such a theory gives us enough grounds for an adequate description of the RTI stabilization by the finite ion Larmor radius effect.

  18. Interchange and Flow Velocity Shear Instabilities in the Presence of Finite Larmor Radius Effects

    NASA Astrophysics Data System (ADS)

    Sotnikov, V.; Kim, T.; Mishin, E.; Genoni, T.; Rose, D.; Mehlhorn, T.

    2014-09-01

    Ionospheric irregularities cause scintillations of electromagnetic signals that can severely affect navigation and transionospheric communication, in particular during Equatorial Plasma Bubbles (EPBs) events. However, the existing ionospheric models do not describe density irregularities with typical scales of several ion Larmor radii that affect UHF and L bands. These irregularities can be produced in the process of nonlinear evolution of interchange or flow velocity shear instabilities. The model of nonlinear development of these instabilities based on two-fluid hydrodynamic description with inclusion of finite Larmor radius effects will be presented. The derived nonlinear equations will be numerically solved by using the code Flute, which was originally developed for High Energy Density applications and modified to describe interchange and flow velocity shear instabilities in the ionosphere. The high-resolution simulations will be driven by the ambient conditions corresponding to the AFRL C/NOFS satellite low-resolution data during EPBs.

  19. Finite ion Larmor radius effects and wall effects on m = 1 instabilities

    SciTech Connect

    Cayton, T.E.

    1980-12-01

    A set of fluid-like equations that simultaneously includes effects due to geometry and finite ion gyroradii is used to examine the stability of a straight, radially diffuse screw pinch in the regime where the poloidal magnetic field is very small compared with the axial magnetic field. It is shown that this pinch may be rendered completely stable through a combination of finite Larmor radius effects and wall effects. Many of the m = 1 modes of the diffuse pinch can be stabilized by finite ion Larmor radius effects, just as all flute modes can be stabilized. Because of the special nature of the m = 1 eigenfunctions, finite ion gyroradius effects are negligible for the kink modes of very large wavelength. This special nature of the eigenfunctions, however, makes these modes good candidates for wall stabilization. The finite Larmor radius stabilization of m = 1 modes of a diffuse pinch is contrary to the conventional wisdom that has evolved from studies of sharp-boundary, skin-current models of the pinch.

  20. Finite Larmor radius effects on the (m = 2, n = 1) cylindrical tearing mode

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Chowdhury, J.; Parker, S. E.; Wan, W.

    2015-04-01

    New field solvers are developed in the gyrokinetic code GEM [Chen and Parker, J. Comput. Phys. 220, 839 (2007)] to simulate low-n modes. A novel discretization is developed for the ion polarization term in the gyrokinetic vorticity equation. An eigenmode analysis with finite Larmor radius effects is developed to study the linear resistive tearing mode. The mode growth rate is shown to scale with resistivity as γ ˜ η1/3, the same as the semi-collisional regime in previous kinetic treatments [Drake and Lee, Phys. Fluids 20, 1341 (1977)]. Tearing mode simulations with gyrokinetic ions are verified with the eigenmode calculation.

  1. Jeans instability of magnetized quantum plasma: Effect of viscosity, rotation and finite Larmor radius corrections

    SciTech Connect

    Jain, Shweta Sharma, Prerana; Chhajlani, R. K.

    2015-07-31

    The Jeans instability of self-gravitating quantum plasma is examined considering the effects of viscosity, finite Larmor radius (FLR) corrections and rotation. The analysis is done by normal mode analysis theory with the help of relevant linearized perturbation equations of the problem. The general dispersion relation is obtained using the quantum magneto hydrodynamic model. The modified condition of Jeans instability is obtained and the numerical calculations have been performed to show the effects of various parameters on the growth rate of Jeans instability.

  2. Finite Larmor radius effects on the coupled trapped electron and ion temperature gradient modes

    SciTech Connect

    Sandberg, I.; Isliker, H.; Pavlenko, V. P.

    2007-09-15

    The properties of the coupled trapped electron and toroidal ion temperature gradient modes are investigated using the standard reactive fluid model and taking rigorously into account the effects attributed to the ion polarization drift and to the drifts associated with the lowest-order finite ion Larmor radius effects. In the flat density regime, where the coupling between the modes is relatively weak, the properties of the unstable modes are slightly modified through these effects. For the peak density regions, where the coupling of the modes is rather strong, these second-order drifts determine the spectra of the unstable modes near the marginal conditions.

  3. 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.

  4. ENHANCED MAGNETIC COMPRESSIBILITY AND ISOTROPIC SCALE INVARIANCE AT SUB-ION LARMOR SCALES IN SOLAR WIND TURBULENCE

    SciTech Connect

    Kiyani, K. H.; Fauvarque, O.; Chapman, S. C.; Hnat, B.; Sahraoui, F.; Khotyaintsev, Yu. V.

    2013-01-20

    The anisotropic nature of solar wind magnetic turbulence fluctuations is investigated scale by scale using high cadence in situ magnetic field measurements from the Cluster and ACE spacecraft missions. The data span five decades in scales from the inertial range to the electron Larmor radius. In contrast to the inertial range, there is a successive increase toward isotropy between parallel and transverse power at scales below the ion Larmor radius, with isotropy being achieved at the electron Larmor radius. In the context of wave-mediated theories of turbulence, we show that this enhancement in magnetic fluctuations parallel to the local mean background field is qualitatively consistent with the magnetic compressibility signature of kinetic Alfven wave solutions of the linearized Vlasov equation. More generally, we discuss how these results may arise naturally due to the prominent role of the Hall term at sub-ion Larmor scales. Furthermore, computing higher-order statistics, we show that the full statistical signature of the fluctuations at scales below the ion Larmor radius is that of a single isotropic globally scale-invariant process distinct from the anisotropic statistics of the inertial range.

  5. A fluid finite ion Larmor radius model of the magnetopause layer

    SciTech Connect

    Stasiewicz, K. )

    1989-07-01

    A model of the magnetopause current layer is constructed on the basis of fluid equations for collision-free plasmas with finite ion Larmor radius (FLR). The model provides self-consistent solutions for the plasma flow vector, magnetic field, and electric currents inside the magnetopause layer. This is the first fluid model that offers explanations for some observations at the terrestrial magnetopause that are inexplicable by earlier models. In particular, it is shown that the erosion of the dayside magnetosphere can be explained by the normal component of the gyroviscous stress tensor that is related to the intensity of field-aligned currents inside the magnetopause layer. It is found that the sense of rotation of the magnetic field across the magnetopause is determined by the ratio of the normal component of the Alfven velocity to the normal flow velocity {xi}={ital B}{sub {ital n}}/({mu}{sub 0}{rho}){sup 1/2}{ital V}{sub {ital n}}. For {vert bar} {xi} {vert bar}{gt}1 the sense of rotation corresponds to electron polarization, and {vert bar} {xi} {vert bar}{lt}1 yields proton polarization. It is argued that the case {vert bar} {xi} {vert bar}=1 corresponds to the formation of transient flux transfer events. The observed departures from MHD jump conditions across the magnetopause are explained by additional, finite Larmor radius terms in the moment equations. An expression is also derived for the characteristic thickness of the magnetopause layer. {copyright} American Geophysical Union 1989

  6. Linear vs. nonlinear acceleration in plasma turbulence. II. Hall–finite-Larmor-radius magnetohydrodynamics

    SciTech Connect

    Ghosh, Sanjoy; Parashar, Tulasi N.

    2015-04-15

    The local k-space ratio of linear and nonlinear accelerations associated with a variety of initial conditions undergoing steady relaxation is investigated for the Hall–finite-Larmor-radius magnetohydrodynamics (MHD) system in the presence of a mean magnetic field. Building on a related study (Paper I) where it was shown that discrepancies exist between describing the global and local characterizations of the pure MHD system with mean magnetic field, we find regions of the Fourier space that are consistently dominated by linear acceleration and other regions that are consistently dominated by nonlinear acceleration, independent of the overall system's description as linear, weakly nonlinear, or turbulent. In general, dynamics within a certain angular range of the mean magnetic field direction are predominantly linear, while dynamics adjacent the Hall scales along the field-parallel direction and dynamics adjacent the finite Larmor radius scales in the field-perpendicular direction can become strongly nonlinear. The nonlinear influences are particularly significant as the plasma beta increases from unity to higher values.

  7. Transport of and radiation production by transrelativistic and nonrelativistic particles moving through sub-Larmor-scale electromagnetic turbulence.

    PubMed

    Keenan, Brett D; Ford, Alexander L; Medvedev, Mikhail V

    2015-09-01

    Plasmas with electromagnetic fields turbulent at sub-Larmor scales are a feature of a wide variety of high-energy-density environments and are essential to the description of many astrophysical and laboratory plasma phenomena. Radiation from particles, whether they are relativistic or nonrelativistic, moving through small-scale magnetic turbulence has spectral characteristics distinct from both synchrotron and cyclotron radiation. The radiation, carrying information on the statistical properties of the magnetic turbulence, is also intimately related to the particle diffusive transport. We have investigated, both theoretically and numerically, the transport of nonrelativistic and trans-relativistic particles in plasmas with high-amplitude isotropic sub-Larmor-scale magnetic turbulence, and its relation to the spectra of radiation simultaneously produced by these particles. Consequently, the diffusive and radiative properties of plasmas turbulent on sub-Larmor scales may serve as a powerful tool to diagnosis laboratory and astrophysical plasmas.

  8. Generalized power-spectrum Larmor formula for an extended charged particle embedded in a harmonic oscillator

    NASA Astrophysics Data System (ADS)

    Marengo, Edwin A.; Khodja, Mohamed R.

    2006-09-01

    The nonrelativistic Larmor radiation formula, giving the power radiated by an accelerated charged point particle, is generalized for a spatially extended particle in the context of the classical charged harmonic oscillator. The particle is modeled as a spherically symmetric rigid charge distribution that possesses both translational and spinning degrees of freedom. The power spectrum obtained exhibits a structure that depends on the form factor of the particle, but reduces, in the limit of an infinitesimally small particle and for the charge distributions considered, to Larmor’s familiar result. It is found that for finite-duration small-enough accelerations as well as perpetual uniform accelerations the power spectrum of the spatially extended particle reduces to that of a point particle. It is also found that when the acceleration is violent or the size parameter of the particle is very large compared to the wavelength of the emitted radiation the power spectrum is highly suppressed. Possible applications are discussed.

  9. Ion finite Larmor radius effects on the interchange instability in an open system

    SciTech Connect

    Katanuma, I.; Sato, S.; Okuyama, Y.; Kato, S.; Kubota, R.

    2013-11-15

    A particle simulation of an interchange instability was performed by taking into account the ion finite Larmor radius (FLR) effects. It is found that the interchange instability with large FLR grows in two phases, that is, linearly growing phase and the nonlinear phase subsequent to the linear phase, where the instability grows exponentially in both phases. The linear growth rates observed in the simulation agree well with the theoretical calculation. The effects of FLR are usually taken in the fluid simulation through the gyroviscosity, the effects of which are verified in the particle simulation with large FLR regime. The gyroviscous cancellation phenomenon observed in the particle simulation causes the drifts in the direction of ion diamagnetic drifts.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-01

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

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

    PubMed

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-28

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

  12. Determination of relative orientation between (1)H CSA tensors from a 3D solid-state NMR experiment mediated through (1)H/(1)H RFDR mixing under ultrafast MAS.

    PubMed

    Pandey, Manoj Kumar; Nishiyama, Yusuke

    2015-09-01

    To obtain piercing insights into inter and intramolecular H-bonding, and π-electron interactions measurement of (1)H chemical shift anisotropy (CSA) tensors is gradually becoming an obvious choice. While the magnitude of CSA tensors provides unique information about the local electronic environment surrounding the nucleus, the relative orientation between these tensors can offer further insights into the spatial arrangement of interacting nuclei in their respective three-dimensional (3D) space. In this regard, we present a 3D anisotropic/anisotropic/isotropic proton chemical shift (CSA/CSA/CS) correlation experiment mediated through (1)H/(1)H radio frequency-driven recoupling (RFDR) which enhances spin diffusion through recoupled (1)H-(1)H dipolar couplings under ultrafast magic angle spinning (MAS) frequency (70kHz). Relative orientation between two interacting 1H CSA tensors is obtained by fitting two-interacting (1)H CSA tensors by fitting two-dimensional (2D) (1)H/(1)H CSA/CSA spectral slices through extensive numerical simulations. To recouple (1)H CSAs in the indirect frequency dimensions of a 3D experiment we have employed γ-encoded radio frequency (RF) pulse sequence based on R-symmetry (R188(7)) with a series of phase-alternated 2700(°)-90180(°) composite-180° pulses on citric acid sample. Due to robustness of applied (1)H CSA recoupling sequence towards the presence of RF field inhomogeneity, we have successfully achieved an excellent (1)H/(1)H CSA/CSA cross-correlation efficiency between H-bonded sites of citric acid. PMID:26065628

  13. 1H DNP at 1.4 T of water doped with a triarylmethyl-based radical.

    PubMed

    Wind, R A; Ardenkjaer-Larsen, J H

    1999-12-01

    Recently a triarylmethyl-based (TAM) radical has been developed for research in biological and other aqueous systems, and in low magnetic fields, 10 mT or less, large (1)H dynamic nuclear polarization (DNP) enhancements have been reported. In this paper the DNP properties of this radical have been investigated in a considerably larger field of 1.4 T, corresponding to proton and electron Larmor frequencies of 60 MHz and 40 GHz, respectively. To avoid excessive microwave heating of the sample, an existing DNP NMR probe was modified with a screening coil, wound around the sample capillary and with its axis perpendicular to the electric component of the microwave field. It was found that with this probe the temperature increase in the sample after 4 s of microwave irradiation with an incident power of 10 W was only 16 degrees C. For the investigations, 10 mM of the TAM radical was dissolved in deionized, but not degassed, water and put into a 1-mm i.d. and 6-mm long capillary tube. At 26 degrees C the following results were obtained: (I) The relaxivity of the radical is 0.07 (mMs)(-1), in accordance with the value extrapolated from low-field results; (II) The leakage factor is 0.63, the saturation factor at maximum power is 0.85, and the coupling factor is -0.0187. It is shown that these results agree very well with an analysis where the electron-dipolar interactions are the dominant DNP mechanism, and where the relaxation transitions resulting from these interactions are governed by translational diffusion of the water molecules. Finally, the possibilities of combining DNP with magnetic resonance microscopy (MRM) are discussed. It is shown that at 26 degrees C the overall DNP-enhanced proton polarization should become maximal in an external field of 0.3 T and become comparable to the thermal equilibrium polarization in a field of 30 T, considerably larger than the largest high-resolution magnet available to date. It is concluded that DNP MRM in this field, which

  14. Radiation from plasmas with sub-Larmor scale magnetic fields -- generalized jitter radiation

    NASA Astrophysics Data System (ADS)

    Medvedev, Mikhail

    2009-11-01

    Radiation produced by relativistic electrons in random magnetic fields of a sub-Larmor scale is referred to as the jitter radiation. It has been predicted to be produced from high- energy density environments which naturally generate such fields via Weibel-type (e.g., streaming) instabilities. Thus, it was argued to be a new diagnostic of Weibel turbulence in relativistic collisionless shocks, in reconnection in electron- positron plasmas and in laser-produced plasmas, the latter is of interest to both laser-plasma applications (e.g., Fast Ignition) and to Laboratory Astrophysics. The spectral characteristics of jitter radiation are markedly different from those of synchrotron and carry information about the magnetic fields structure (e.g., its spatial spectrum). Conventional treatment of jitter radiation assumes negligibly small deflections of particles in the magnetic fields, which is not always the case. Here we relax this assumption and discuss the transition between jitter and synchrotron regimes. Although the full treatment is model-dependent, certain important conclusions can be drawn. We will also address applications to both laboratory studies of the Weibel turbulence and astrophysical phenomena.

  15. Two-fluid and finite Larmor radius effects on helicity evolution in a plasma pinch

    NASA Astrophysics Data System (ADS)

    Sauppe, J. P.; Sovinec, C. R.

    2016-03-01

    The evolution of magnetic energy, helicity, and hybrid helicity during nonlinear relaxation of a driven-damped plasma pinch is compared in visco-resistive magnetohydrodynamics and two-fluid models with and without the ion gyroviscous stress tensor. Magnetic energy and helicity are supplied via a boundary electric field which initially balances the resistive dissipation, and the plasma undergoes multiple relaxation events during the nonlinear evolution. The magnetic helicity is well conserved relative to the magnetic energy over each event, which is short compared with the global resistive diffusion time. The magnetic energy decreases by roughly 1.5% of its initial value over a relaxation event, while the magnetic helicity changes by at most 0.2% of the initial value. The hybrid helicity is dominated by magnetic helicity in low-β pinch conditions and is also well conserved. Differences of less than 1% between magnetic helicity and hybrid helicity are observed with two-fluid modeling and result from cross helicity evolution. The cross helicity is found to change appreciably due to the first-order finite Larmor radius effects which have not been included in contemporary relaxation theories. The plasma current evolves towards the flat parallel current state predicted by Taylor relaxation theory but does not achieve it. Plasma flow develops significant structure for two-fluid models, and the flow perpendicular to the magnetic field is much more substantial than the flow along it.

  16. Kohn's theorem, Larmor's equivalence principle and the Newton-Hooke group

    SciTech Connect

    Gibbons, G.W.; Pope, C.N.

    2011-07-15

    Highlights: > We show that non-relativistic electrons moving in a magnetic field with trapping potential admits as relativity group the Newton-Hooke group. > We use this fact to give a group theoretic interpretation of Kohn's theorem and to obtain the spectrum. > We obtain the lightlike lift of the system exhibiting showing it coincides with the Nappi-Witten spacetime. - Abstract: We consider non-relativistic electrons, each of the same charge to mass ratio, moving in an external magnetic field with an interaction potential depending only on the mutual separations, possibly confined by a harmonic trapping potential. We show that the system admits a 'relativity group' which is a one-parameter family of deformations of the standard Galilei group to the Newton-Hooke group which is a Wigner-Inoenue contraction of the de Sitter group. This allows a group-theoretic interpretation of Kohn's theorem and related results. Larmor's theorem is used to show that the one-parameter family of deformations are all isomorphic. We study the 'Eisenhart' or 'lightlike' lift of the system, exhibiting it as a pp-wave. In the planar case, the Eisenhart lift is the Brdicka-Eardley-Nappi-Witten pp-wave solution of Einstein-Maxwell theory, which may also be regarded as a bi-invariant metric on the Cangemi-Jackiw group.

  17. Kinetic-Scale Magnetic Turbulence and Finite Larmor Radius Effects at Mercury

    NASA Technical Reports Server (NTRS)

    Uritsky, V. M.; Slavin, J. A.; Khazanov, G. V.; Donovan, E. F.; Boardsen, S. A.; Anderson, B. J.; Korth, H.

    2011-01-01

    We use a nonstationary generalization of the higher-order structure function technique to investigate statistical properties of the magnetic field fluctuations recorded by MESSENGER spacecraft during its first flyby (01/14/2008) through the near-Mercury space environment, with the emphasis on key boundary regions participating in the solar wind - magnetosphere interaction. Our analysis shows, for the first time, that kinetic-scale fluctuations play a significant role in the Mercury's magnetosphere up to the largest resolvable timescale (approx.20 s) imposed by the signal nonstationariry, suggesting that turbulence at this plane I is largely controlled by finite Larmor radius effects. In particular, we report the presence of a highly turbulent and extended foreshock system filled with packets of ULF oscillations, broad-band intermittent fluctuations in the magnetosheath, ion-kinetic turbulence in the central plasma sheet of Mercury's magnetotail, and kinetic-scale fluctuations in the inner current sheet encountered at the outbound (dawn-side) magnetopause. Overall, our measurements indicate that the Hermean magnetosphere, as well as the surrounding region, are strongly affected by non-MHD effects introduced by finite sizes of cyclotron orbits of the constituting ion species. Physical mechanisms of these effects and their potentially critical impact on the structure and dynamics of Mercury's magnetic field remain to be understood.

  18. A VISTA on PD-1H.

    PubMed

    Liu, Yang

    2014-05-01

    Three years ago, two research groups independently identified a previously undescribed T cell cosignaling molecule; one referred to it as V-domain Ig suppressor of T cell activation (VISTA), and the other used the term programmed death-1 homolog (PD-1H). Recombinant and ectopically expressed PD-1H functions as a coinhibitory ligand for T cell responses. However, the function of endogenous PD-1H is not clear. In this issue of the JCI, Flies and colleagues demonstrate that endogenous PD-1H on both T cells and APCs serves as a coinhibitory molecule for T cell activation and provide further support for targeting PD-1H as a therapeutic strategy for transplantation and cancers.

  19. Formation of the muonic helium atom /alpha particle-muon-electron/ and observation of its Larmor precession

    NASA Technical Reports Server (NTRS)

    Souder, P. A.; Casperson, D. E.; Crane, T. W.; Hughes, V. W.; Lu, D. C.; Yam, M. H.; Orth, H.; Reist, H. W.; Zu Putlitz, G.

    1975-01-01

    Experiments are described in which it proved possible to form the muonic helium atom by stopping polarized negative muons in a helium gas with a 2% xenon admixture at a pressure of 14 atm. The observed Larmor precession amplitudes are plotted against the gyromagnetic ratio for both muons and antimuons stopped in He + 2% Xe. In addition, a non-zero residual polarization of 0.06 plus or minus 0.01 was measured for muons stopped in pure helium gas, which corresponds to a depolarization factor of 18 plus or minus 3.

  20. Finite Larmor radius effects on the (m = 2, n = 1) cylindrical tearing mode

    SciTech Connect

    Chen, Y.; Chowdhury, J.; Parker, S. E.; Wan, W.

    2015-04-15

    New field solvers are developed in the gyrokinetic code GEM [Chen and Parker, J. Comput. Phys. 220, 839 (2007)] to simulate low-n modes. A novel discretization is developed for the ion polarization term in the gyrokinetic vorticity equation. An eigenmode analysis with finite Larmor radius effects is developed to study the linear resistive tearing mode. The mode growth rate is shown to scale with resistivity as γ ∼ η{sup 1∕3}, the same as the semi-collisional regime in previous kinetic treatments [Drake and Lee, Phys. Fluids 20, 1341 (1977)]. Tearing mode simulations with gyrokinetic ions are verified with the eigenmode calculation.

  1. Enhanced Y1H Assays for Arabidopis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Transcription regulation plays a key role in development and response to environment. To understand this mechanism, we need to know which transcription factor (TFs) would bind to which promoter, thus regulate their target gene expression. Yeast one-hybrid (Y1H) technique can be used to map this kind...

  2. Alfvén Eigenmode Induced Fast Ion Transport in DIII-D Resulting From Finite Larmor Radius Effects

    NASA Astrophysics Data System (ADS)

    Kramer, G. J.; Fu, G. Y.; Nazikian, R.; van Zeeland, M. A.; Fisher, R. K.; Pace, D. C.; Chen, L.; Chen, X.; Heidbrink, W. W.

    2013-10-01

    Alfvén Eigenmode (AE) induced fast-ion redistribution and loss are commonly observed in DIII-D. In those experiments the perpendicular wave vector times the fast-ion Larmor radius is of order unity (k⊥ρi ~ 1), which allows fast ion orbits to traverse the AE mode structures asymmetrically causing a significant change in magnetic moment. Full-orbit simulations of the expected transport in DIII-D plasmas show that this effect can lead to fast-ion radial diffusion constants of 5 m2/s at the measured mode amplitudes. This level of diffusion is not captured with a guiding center approximation and is in agreement with that deduced in DIII-D experiments when AE activity was present. Work supported by the US Department of Energy under DE-AC02-09CH11466, DE-FC02-04ER54698, and SC-G903402.

  3. Finite Larmor Radius and Three-Dimensional Effects on the Blobs in the Scrape-Off Layer

    SciTech Connect

    Jovanovic, D.; Shukla, P. K.; Pegoraro, F.

    2008-10-15

    The nonlinear processes in the tokamak core edge and in the scrape-off layer are studied within the electrostatic interchange paradigm, with the collisions among the plasma particles and with the neutras, including the effects of the finite ion Larmor radius and of fully three-dimensional electron dynamics. These new three-dimensional model equations are solved numerically, to study the propagation of plasma blobs in the scrape-off layer. It is shown that the coupling with the resistive drift mode causes the transverse contraction and the rotation of the blob. The parallel resistivity and the finite ion temperature give rise to the symmetry breaking and the poloidal propagation of the blobs, while their stability is only weakly affected.

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

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2015-10-28

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

  5. Gyro-gauge-independent formulation of the guiding-center reduction to arbitrary order in the Larmor radius

    NASA Astrophysics Data System (ADS)

    de Guillebon, L.; Vittot, M.

    2013-10-01

    Guiding-center reduction is studied using gyro-gauge-independent coordinates. The Lagrangian 1-form of charged particle dynamics is Lie transformed without introducing a gyro-gauge, but using directly the unit vector of the component of the velocity perpendicular to the magnetic field as the coordinate corresponding to Larmor gyration. The reduction is shown to provide a maximal reduction for the Lagrangian and to work for all orders in the Larmor radius, following exactly the same procedure as when working with the standard gauge-dependent coordinate. The gauge-dependence is removed from the coordinate system by using a constrained variable for the gyro-angle. The closed 1-form dθ is replaced by a more general non-closed 1-form, which is equal to dθ in the gauge-dependent case. The gauge vector is replaced by a more general connection in the definition of the gradient, which behaves as a covariant derivative, in perfect agreement with the circle-bundle picture. This explains some results of previous works, whose gauge-independent expressions did not correspond to gauge fixing but did indeed correspond to connection fixing. In addition, some general results are obtained for the guiding-center reduction. The expansion is polynomial in the cotangent of the pitch-angle as an effect of the structure of the Lagrangian, preserved by Lie derivatives. The induction for the reduction is shown to rely on the inversion of a matrix, which is the same for all orders higher than three. It is inverted and explicit induction relations are obtained to go to an arbitrary order in the perturbation expansion. The Hamiltonian and symplectic representations of the guiding-center reduction are recovered, but conditions for the symplectic representation at each order are emphasized.

  6. Dynamics-based selective 2D 1H/1H chemical shift correlation spectroscopy under ultrafast MAS conditions

    PubMed Central

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-01-01

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of 1H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of 1H/1H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials. PMID:26026440

  7. Proton-detected 3D (15)N/(1)H/(1)H isotropic/anisotropic/isotropic chemical shift correlation solid-state NMR at 70kHz MAS.

    PubMed

    Pandey, Manoj Kumar; Yarava, Jayasubba Reddy; Zhang, Rongchun; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2016-01-01

    Chemical shift anisotropy (CSA) tensors offer a wealth of information for structural and dynamics studies of a variety of chemical and biological systems. In particular, CSA of amide protons can provide piercing insights into hydrogen-bonding interactions that vary with the backbone conformation of a protein and dynamics. However, the narrow span of amide proton resonances makes it very difficult to measure (1)H CSAs of proteins even by using the recently proposed 2D (1)H/(1)H anisotropic/isotropic chemical shift (CSA/CS) correlation technique. Such difficulties due to overlapping proton resonances can in general be overcome by utilizing the broad span of isotropic chemical shifts of low-gamma nuclei like (15)N. In this context, we demonstrate a proton-detected 3D (15)N/(1)H/(1)H CS/CSA/CS correlation experiment at fast MAS frequency (70kHz) to measure (1)H CSA values of unresolved amide protons of N-acetyl-(15)N-l-valyl-(15)N-l-leucine (NAVL).

  8. Star formation through thermal instability of radiative plasma with finite electron inertia and finite Larmor radius corrections

    NASA Astrophysics Data System (ADS)

    Kaothekar, Sachin

    2016-08-01

    I have studied the effects of finite electron inertia, finite ion Larmor radius (FLR) corrections, and radiative heat-loss function on the thermal instability of an infinite homogeneous, viscous plasma incorporating the effect of thermal conductivity for star formation in interstellar medium (ISM). A general dispersion relation is derived using the normal mode analysis method with the help of relevant linearized perturbation equations of the problem. The wave propagation is discussed for longitudinal and transverse directions to the external magnetic field and the conditions of modified thermal instabilities and stabilities are discussed in different cases. We find that the thermal instability criterion is get modified into radiative instability criterion by inclusion of radiative heat-loss functions with thermal conductivity. The viscosity of medium removes the effect of FLR corrections from the condition of radiative instability. Numerical calculation shows stabilizing effect of heat-loss function, viscosity and FLR corrections, and destabilizing effect of finite electron inertia on the thermal instability. Results carried out in this paper shows that stars are formed in interstellar medium mainly due to thermal instability.

  9. Finite Larmor radius magnetohydrodynamic analysis of the Rayleigh-Taylor instability in Z pinches with sheared axial flow

    SciTech Connect

    Qiu, X. M.; Huang, L.; Jian, G. D.

    2007-03-15

    The Rayleigh-Taylor (RT) instability in Z pinches with sheared axial flow (SAF) is analyzed using finite Larmor radius (FLR) magnetohydrodynamic theory, in whose momentum equation the FLR effect (also referred to as the effect of gyroviscosity) is introduced through an anisotropic ion (FLR) stress tensor. A dispersion relation is derived for the linear RT instability. Both analytical and numerical solutions of the dispersion equation are given. The results indicate that the short-wavelength modes of the RT instability can be stabilized by a sufficient FLR, whereas the long-wavelength modes can be stabilized by a sufficient SAF. In the small-wavenumber region, for normalized wavenumber K<2.4, the hybrid RT/KH (Kelvin-Helmholtz) instability is shown to be the most difficult to stabilize. However the synergistic effect of the SAF and gyroviscosity can mitigate both the RT instability in the large-wavenumber region (K>2.4) and the hybrid RT/KH instability in the small-wavenumber region. In addition, this synergistic effect can compress the RT instability to a narrow wavenumber region. Even the thorough stabilization of the RT instability in the large-wavenumber region is possible with a sufficient SAF and a sufficient gyroviscosity.

  10. Stereospecificity of (1) H, (13) C and (15) N shielding constants in the isomers of methylglyoxal bisdimethylhydrazone: problem with configurational assignment based on (1) H chemical shifts.

    PubMed

    Afonin, Andrei V; Pavlov, Dmitry V; Ushakov, Igor A; Keiko, Natalia A

    2012-07-01

    In the (13) C NMR spectra of methylglyoxal bisdimethylhydrazone, the (13) C-5 signal is shifted to higher frequencies, while the (13) C-6 signal is shifted to lower frequencies on going from the EE to ZE isomer following the trend found previously. Surprisingly, the (1) H-6 chemical shift and (1) J(C-6,H-6) coupling constant are noticeably larger in the ZE isomer than in the EE isomer, although the configuration around the -CH═N- bond does not change. This paradox can be rationalized by the C-H⋯N intramolecular hydrogen bond in the ZE isomer, which is found from the quantum-chemical calculations including Bader's quantum theory of atoms in molecules analysis. This hydrogen bond results in the increase of δ((1) H-6) and (1) J(C-6,H-6) parameters. The effect of the C-H⋯N hydrogen bond on the (1) H shielding and one-bond (13) C-(1) H coupling complicates the configurational assignment of the considered compound because of these spectral parameters. The (1) H, (13) C and (15) N chemical shifts of the 2- and 8-(CH(3) )(2) N groups attached to the -C(CH(3) )═N- and -CH═N- moieties, respectively, reveal pronounced difference. The ab initio calculations show that the 8-(CH(3) )(2) N group conjugate effectively with the π-framework, and the 2-(CH(3) )(2) N group twisted out from the plane of the backbone and loses conjugation. As a result, the degree of charge transfer from the N-2- and N-8- nitrogen lone pairs to the π-framework varies, which affects the (1) H, (13) C and (15) N shieldings. PMID:22615146

  11. First-order finite-Larmor-radius fluid modeling of tearing and relaxation in a plasma pincha)

    NASA Astrophysics Data System (ADS)

    King, J. R.; Sovinec, C. R.; Mirnov, V. V.

    2012-05-01

    Drift and Hall effects on magnetic tearing, island evolution, and relaxation in pinch configurations are investigated using a non-reduced first-order finite-Larmor-radius (FLR) fluid model with the nonideal magnetohydrodynamics (MHD) with rotation, open discussion (NIMROD) code [C.R. Sovinec and J. R. King, J. Comput. Phys. 229, 5803 (2010)]. An unexpected result with a uniform pressure profile is a drift effect that reduces the growth rate when the ion sound gyroradius (ρs) is smaller than the tearing-layer width. This drift is present only with warm-ion FLR modeling, and analytics show that it arises from ∇B and poloidal curvature represented in the Braginskii gyroviscous stress. Nonlinear single-helicity computations with experimentally relevant ρs values show that the warm-ion gyroviscous effects reduce saturated-island widths. Computations with multiple nonlinearly interacting tearing fluctuations find that m = 1 core-resonant-fluctuation amplitudes are reduced by a factor of two relative to single-fluid modeling by the warm-ion effects. These reduced core-resonant-fluctuation amplitudes compare favorably to edge coil measurements in the Madison Symmetric Torus (MST) reversed-field pinch [R. N. Dexter et al., Fusion Technol. 19, 131 (1991)]. The computations demonstrate that fluctuations induce both MHD- and Hall-dynamo emfs during relaxation events. The presence of a Hall-dynamo emf implies a fluctuation-induced Maxwell stress, and the simulation results show net transport of parallel momentum. The computed magnitude of force densities from the Maxwell and competing Reynolds stresses, and changes in the parallel flow profile, are qualitatively and semi-quantitatively similar to measurements during relaxation in MST.

  12. 1H NMR spectra part 31: 1H chemical shifts of amides in DMSO solvent.

    PubMed

    Abraham, Raymond J; Griffiths, Lee; Perez, Manuel

    2014-07-01

    The (1)H chemical shifts of 48 amides in DMSO solvent are assigned and presented. The solvent shifts Δδ (DMSO-CDCl3 ) are large (1-2 ppm) for the NH protons but smaller and negative (-0.1 to -0.2 ppm) for close range protons. A selection of the observed solvent shifts is compared with calculated shifts from the present model and from GIAO calculations. Those for the NH protons agree with both calculations, but other solvent shifts such as Δδ(CHO) are not well reproduced by the GIAO calculations. The (1)H chemical shifts of the amides in DMSO were analysed using a functional approach for near ( ≤ 3 bonds removed) protons and the electric field, magnetic anisotropy and steric effect of the amide group for more distant protons. The chemical shifts of the NH protons of acetanilide and benzamide vary linearly with the π density on the αN and βC atoms, respectively. The C=O anisotropy and steric effect are in general little changed from the values in CDCl3. The effects of substituents F, Cl, Me on the NH proton shifts are reproduced. The electric field coefficient for the protons in DMSO is 90% of that in CDCl3. There is no steric effect of the C=O oxygen on the NH proton in an NH…O=C hydrogen bond. The observed deshielding is due to the electric field effect. The calculated chemical shifts agree well with the observed shifts (RMS error of 0.106 ppm for the data set of 257 entries). PMID:24824670

  13. 1H homonuclear editing of rat brain using semiselective pulses

    SciTech Connect

    Hetherington, H.P.; Avison, M.J.; Shulman, R.G.

    1985-05-01

    The authors have used a semiselective Hahn spin-echo sequence of the form (1331)-tau-(2662)-tau-AQ, delivered by a surface coil to obtain high-resolution 1H NMR spectra from the brains of intact dead rats. This sequence gave suppression of the tissue water resonance by a factor of 80,000 when tau = 68 ms. Delivery of a frequency-selective Dante pulse train to the alpha-CH resonance of lactate at 4.11 ppm, simultaneously with the 2662 refocusing pulse, altered the j-modulation in the spin-coupled beta-CH3 protons. Subtraction of this spectrum from one in which the Dante was ineffective gave an edited spectrum containing only the beta-CH3 resonance of lactate at 1.31 ppm. When the position of the Dante was shifted to 3.78 ppm to selectively invert the alpha-CH protons of alanine, an edited spectrum of alanine was obtained.

  14. Inductive sustainment of oblate field-reversed configurations with the assistance of magnetic diffusion, shaping, and finite-Larmor radius stabilization

    SciTech Connect

    Gerhardt, S. P.; Belova, E. V.; Yamada, M.; Ji, H.; Jacobson, C. M.; McGeehan, B.; Ren, Y.; Inomoto, M.; Maqueda, R.

    2008-02-15

    Oblate field-reversed configurations (FRCs) have been sustained for >300 {mu}s, or >15 magnetic diffusion times, through the use of an inductive solenoid. These argon FRCs can have their poloidal flux sustained or increased, depending on the timing and strength of the induction. An inward pinch is observed during sustainment, leading to a peaking of the pressure profile and maintenance of the FRC equilibrium. The good stability observed in argon (and krypton) does not transfer to lighter gases, which develop terminal co-interchange instabilities. The stability in argon and krypton is attributed to a combination of external field shaping, magnetic diffusion, and finite-Larmor radius effects.

  15. First-order quantum correction to the Larmor radiation from a moving charge in a spatially homogeneous time-dependent electric field

    SciTech Connect

    Yamamoto, Kazuhiro; Nakamura, Gen

    2011-02-15

    First-order quantum correction to the Larmor radiation is investigated on the basis of the scalar QED on a homogeneous background of a time-dependent electric field, which is a generalization of a recent work by Higuchi and Walker so as to be extended for an accelerated charged particle in a relativistic motion. We obtain a simple approximate formula for the quantum correction in the limit of the relativistic motion when the direction of the particle motion is parallel to that of the electric field.

  16. Synthesis, characterization and theoretical studies of 5-(benzylthio)-1-cylopentyl-1H-tetrazole.

    PubMed

    Saglam, S; Disli, A; Erdogdu, Y; Marchewka, M K; Kanagathara, N; Bay, B; Güllüoğlu, M T

    2015-01-25

    In this study, 5-(benzylthio)-1-cylopentyl-1H-tetrazole (5B1C1HT) have been synthesized. Boiling points of the obtained compound have been determined and it has been characterized by FT-IR, (1)H NMR, (13)C-APT and LC-MS spectroscopy techniques. The FT-IR, (1)H NMR and (13)C-APT spectral measurements of the 5B1C1HT compound and complete assignment of the vibrational bands observed in spectra has been discussed. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on Density Functional Theory (DFT) at 6-311++G(**), cc-pVDZ and cc-pVTZ basis sets. The optimized geometry with 6-311++G(**) basis sets were used to determine the total energy distribution, harmonic vibrational frequencies, IR intensities. PMID:25171051

  17. 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.

  18. Efficient dipolar double quantum filtering under magic angle spinning without a (1)H decoupling field.

    PubMed

    Courtney, Joseph M; Rienstra, Chad M

    2016-08-01

    We present a systematic study of dipolar double quantum (DQ) filtering in (13)C-labeled organic solids over a range of magic-angle spinning rates, using the SPC-n recoupling sequence element with a range of n symmetry values from 3 to 11. We find that efficient recoupling can be achieved for values n⩾7, provided that the (13)C nutation frequency is on the order of 100kHz or greater. The decoupling-field dependence was investigated and explicit heteronuclear decoupling interference conditions identified. The major determinant of DQ filtering efficiency is the decoupling interference between (13)C and (1)H fields. For (13)C nutation frequencies greater than 75kHz, optimal performance is observed without an applied (1)H field. At spinning rates exceeding 20kHz, symmetry conditions as low as n=3 were found to perform adequately.

  19. Efficient dipolar double quantum filtering under magic angle spinning without a 1H decoupling field

    NASA Astrophysics Data System (ADS)

    Courtney, Joseph M.; Rienstra, Chad M.

    2016-08-01

    We present a systematic study of dipolar double quantum (DQ) filtering in 13C-labeled organic solids over a range of magic-angle spinning rates, using the SPC-n recoupling sequence element with a range of n symmetry values from 3 to 11. We find that efficient recoupling can be achieved for values n ⩾ 7, provided that the 13C nutation frequency is on the order of 100 kHz or greater. The decoupling-field dependence was investigated and explicit heteronuclear decoupling interference conditions identified. The major determinant of DQ filtering efficiency is the decoupling interference between 13C and 1H fields. For 13C nutation frequencies greater than 75 kHz, optimal performance is observed without an applied 1H field. At spinning rates exceeding 20 kHz, symmetry conditions as low as n = 3 were found to perform adequately.

  20. Efficient dipolar double quantum filtering under magic angle spinning without a (1)H decoupling field.

    PubMed

    Courtney, Joseph M; Rienstra, Chad M

    2016-08-01

    We present a systematic study of dipolar double quantum (DQ) filtering in (13)C-labeled organic solids over a range of magic-angle spinning rates, using the SPC-n recoupling sequence element with a range of n symmetry values from 3 to 11. We find that efficient recoupling can be achieved for values n⩾7, provided that the (13)C nutation frequency is on the order of 100kHz or greater. The decoupling-field dependence was investigated and explicit heteronuclear decoupling interference conditions identified. The major determinant of DQ filtering efficiency is the decoupling interference between (13)C and (1)H fields. For (13)C nutation frequencies greater than 75kHz, optimal performance is observed without an applied (1)H field. At spinning rates exceeding 20kHz, symmetry conditions as low as n=3 were found to perform adequately. PMID:27314744

  1. Teaching 1H NMR Spectrometry Using Computer Modeling.

    ERIC Educational Resources Information Center

    Habata, Yoichi; Akabori, Sadatoshi

    2001-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  3. Extension of the Rorschach-Hazlewood Theoretical Model for Spin-Lattice Relaxation in Biological Systems to Low Frequencies

    NASA Astrophysics Data System (ADS)

    Hackmann, Andreas; Ailion, David C.; Ganesan, Krishnamurthy; Laicher, Gernot; Goodrich, K. Craig; Cutillo, Antonio G.

    1996-02-01

    The water-biopolymer cross-relaxation model, proposed by H. E. Rorschach and C. F. Hazlewood (RH) [J. Magn. Reson.70,79 (1986)], explains the Larmor frequency dependence ofT1in many biological systems. However, the RH theory fails at low Larmor frequencies. In this paper, a more general version of the RH theory has been developed. This theory is valid at all frequencies. Use of the new expression for the spin-lattice relaxation rate (1/T1), earlier published experimental data in H2O/D2O bovine serum albumin, which had been measured over a wide frequency range (10 kHz to 100 MHz), were fitted over the entire frequency range. The agreement between theory and the experimental data is excellent. Theoretical expressions for the rotating-frame spin-lattice relaxation rate (1/T1ρ) were also obtained.

  4. Following Metabolism in Living Microorganisms by Hyperpolarized (1)H NMR.

    PubMed

    Dzien, Piotr; Fages, Anne; Jona, Ghil; Brindle, Kevin M; Schwaiger, Markus; Frydman, Lucio

    2016-09-21

    Dissolution dynamic nuclear polarization (dDNP) is used to enhance the sensitivity of nuclear magnetic resonance (NMR), enabling monitoring of metabolism and specific enzymatic reactions in vivo. dDNP involves rapid sample dissolution and transfer to a spectrometer/scanner for subsequent signal detection. So far, most biologically oriented dDNP studies have relied on hyperpolarizing long-lived nuclear spin species such as (13)C in small molecules. While advantages could also arise from observing hyperpolarized (1)H, short relaxation times limit the utility of prepolarizing this sensitive but fast relaxing nucleus. Recently, it has been reported that (1)H NMR peaks in solution-phase experiments could be hyperpolarized by spontaneous magnetization transfers from bound (13)C nuclei following dDNP. This work demonstrates the potential of this sensitivity-enhancing approach to probe the enzymatic process that could not be suitably resolved by (13)C dDNP MR. Here we measured, in microorganisms, the action of pyruvate decarboxylase (PDC) and pyruvate formate lyase (PFL)-enzymes that catalyze the decarboxylation of pyruvate to form acetaldehyde and formate, respectively. While (13)C NMR did not possess the resolution to distinguish the starting pyruvate precursor from the carbonyl resonances in the resulting products, these processes could be monitored by (1)H NMR at 500 MHz. These observations were possible in both yeast and bacteria in minute-long kinetic measurements where the hyperpolarized (13)C enhanced, via (13)C → (1)H cross-relaxation, the signals of protons binding to the (13)C over the course of enzymatic reactions. In addition to these spontaneous heteronuclear enhancement experiments, single-shot acquisitions based on J-driven (13)C → (1)H polarization transfers were also carried out. These resulted in higher signal enhancements of the (1)H resonances but were not suitable for multishot kinetic studies. The potential of these (1)H-based approaches for

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

    DOE PAGES

    Lichtscheidl, Alejandro G.; Janicke, Michael T.; Scott, Brian L.; Nelson, Andrew T.; Kiplinger, Jaqueline L.

    2015-08-21

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

  6. Effect of Finite Larmor Radius Corrections on the Thermal Instability of Thermally Conducting Viscous Plasma with Hall Current and Electron Inertia

    NASA Astrophysics Data System (ADS)

    Jain, Shweta; Sharma, Prerana; Kaothekar, Sachin; Chhajlani, R. K.

    2016-10-01

    The thermal instability of an infinite homogeneous, thermally conducting, and rotating plasma, incorporating finite electrical resistivity, finite electron inertia, and an arbitrary radiative heat-loss function in the presence of finite Larmor radius corrections and Hall current, has been studied. Analysis has been made with the help of linearized magnetohydrodynamics (MHD) equations. A general dispersion relation is obtained using the normal mode analysis method, and the dispersion relation is discussed for longitudinal propagation and transverse propagation separately. The dispersion relation has been solved numerically to obtain the dependence of the growth rate on the various parameters involved. The conditions of modified thermal instability and stability are discussed in the different cases of interest.

  7. Higher-order harmonic effect of a three-dimensional helical wiggler on the Larmor rotation of the equilibrium electrons in a free-electron laser with a positive or a reversed guide magnetic field

    SciTech Connect

    Zhang, Shi-Chang

    2013-10-15

    Analytical formulas of the Larmor rotation are derived in detail for the equilibrium electrons motion in a free-electron laser with combination of a three-dimensional (3-D) helical wiggler and a positive or a reversed guide magnetic field. Generally, the Larmor radius in the configuration of a reversed guide field is much smaller than that in a positive guide field. At non-resonance, a helical orbit governed by the zero-order component of a 3-D wiggler field could hold; meanwhile, the higher-harmonic effect definitely influences those electrons with off-axis guiding centers and induces the electron-beam spreads. At resonance, the Larmor radius in the configuration of a positive guide field has a singularity with a limit tending to infinite, which causes all the electrons to hit the waveguide wall before the exit of the wiggler. Although Larmor-radius singularity does not exist in the configuration of a reversed guide field, at anti-resonance, the first-order harmonic of a 3-D wiggler field induces a transverse displacement which rapidly grows in proportion to a square of time, and leads part of the electron beam to hit the waveguide wall before reaching the wiggler exit, which depends on the specific parameters of the individual electrons. The analytical conclusions derived in the present paper are examined by the nonlinear simulations and the experimental observation. Disagreement with the previous literatures is discussed in detail.

  8. 27Al-->1H cross-polarization in aluminosilicates.

    PubMed

    Kolodziejski, W; Corma, A

    1994-06-01

    Solid-state nuclear magnetic resonance (NMR) cross-polarization (CP) from 27Al to 1H was set on kaolinite, verified by a variable-contact time experiment and applied to ultrastable zeolite Y. The technique is useful for the selective NMR observation of AlOH sites in aluminosilicates, especially those from extraframework species in zeolites.

  9. Nuclear receptor NR1H3 in familial multiple sclerosis

    PubMed Central

    Wang, Zhe; Sadovnick, A. Dessa; Traboulsee, Anthony L.; Ross, Jay P.; Bernales, Cecily Q.; Encarnacion, Mary; Yee, Irene M.; de Lemos, Madonna; Greenwood, Talitha; Lee, Joshua D.; Wright, Galen; Ross, Colin J.; Zhang, Si; Song, Weihong; Vilariño-Güell, Carles

    2016-01-01

    SUMMARY Multiple sclerosis (MS) is an inflammatory disease characterized by myelin loss and neuronal dysfunction. Despite the aggregation observed in some families, pathogenic mutations have remained elusive. In this study we describe the identification of NR1H3 p.Arg415Gln in seven MS patients from two multi-incident families presenting severe and progressive disease, with an average age at onset of 34 years. Additionally, association analysis of common variants in NR1H3 identified rs2279238 conferring a 1.35-fold increased risk of developing progressive MS. The p.Arg415Gln position is highly conserved in orthologs and paralogs, and disrupts NR1H3 heterodimerization and transcriptional activation of target genes. Protein expression analysis revealed that mutant NR1H3 (LXRA) alters gene expression profiles, suggesting a disruption in transcriptional regulation as one of the mechanisms underlying MS pathogenesis. Our study indicates that pharmacological activation of LXRA or its targets may lead to effective treatments for the highly debilitating and currently untreatable progressive phase of MS. PMID:27253448

  10. Study on 1H-NMR fingerprinting of Rhodiolae Crenulatae Radix et Rhizoma.

    PubMed

    Wen, Shi-yuan; Zhou, Jiang-tao; Chen, Yan-yan; Ding, Li-qin; Jiang, Miao-miao

    2015-07-01

    Nuclear magnetic resonance (1H-NMR) fingerprint of Rhodiola rosea medicinal materials was established, and used to distinguish the quality of raw materials from different sources. Pulse sequence for water peak inhibition was employed to acquire 1H-NMR spectra with the temperature at 298 K and spectrometer frequency of 400.13 MHz. Through subsection integral method, the obtained NMR data was subjected to similarity analysis and principal component analysis (PCA). 10 batches raw materials of Rhodiola rosea from different origins were successfully distinguished by PCA. The statistical results indicated that rhodiola glucoside, butyl alcohol, maleic acid and alanine were the main differential ingredients. This method provides an auxiliary method of Chinese quality approach to evaluate the quality of Rhodiola crenulata without using natural reference substances. PMID:26697690

  11. High resolution 1H nuclear magnetic resonance of a transmembrane peptide.

    PubMed Central

    Davis, J. H.; Auger, M.; Hodges, R. S.

    1995-01-01

    Although the strong 1H-1H dipolar interaction is known to result in severe homogeneous broadening of the 1H nuclear magnetic resonance (NMR) spectra of ordered systems, in the fluid phase of biological and model membranes the rapid, axially symmetric reorientation of the molecules about the local bilayer normal projects the dipolar interaction onto the motional symmetry axis. Because the linewidth then scales as (3 cos2 theta-1)/2, where theta is the angle between the local bilayer normal and the magnetic field, the dipolar broadening has been reduced to an "inhomogeneous" broadening by the rapid axial reorientation. It is then possible to obtain high resolution 1H-NMR spectra of membrane components by using magic angle spinning (MAS). Although the rapid axial reorientation effectively eliminates the homogeneous dipolar broadening, including that due to n = 0 rotational resonances, the linewidths observed in both lipids and peptides are dominated by low frequency motions. For small peptides the most likely slow motions are either a "wobble" or reorientation of the molecular diffusion axis relative to the local bilayer normal, or the reorientation of the local bilayer normal itself through surface undulations or lateral diffusion over the curved surface. These motions render the peptide 1H-NMR lines too broad to be observed at low spinning speeds. However, the linewidths due to these slow motions are very sensitive to spinning rate, so that at higher speeds the lines become readily visible. The synthetic amphiphilic peptide K2GL20K2A-amide (peptide-20) has been incorporated into bilayers of 1,2-di-d 27-myristoyl-sn-glycero-3-phosphocholine (DMPC-d54) and studied by high speed 1H-MAS-NMR. The linewidths observed for this transbilayer peptide, although too broad to be observable at spinning rates below -5 kHz, are reduced to 68 Hz at a spinning speed of 14 kHz (at 500C). Further improvements in spinning speed and modifications in sample composition designed to reduce

  12. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids. PMID:26203019

  13. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  14. Selective excitation enables assignment of proton resonances and {sup 1}H-{sup 1}H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of {sup 1}H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as {sup 13}C or {sup 15}N. In this method, after the initial preparation of proton magnetization and cross-polarization to {sup 13}C nuclei, transverse magnetization of desired {sup 13}C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific {sup 13}C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of {sup 1}H-{sup 1}H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  15. Selective excitation enables assignment of proton resonances and 1H-1H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-01

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of 1H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as 13C or 15N. In this method, after the initial preparation of proton magnetization and cross-polarization to 13C nuclei, transverse magnetization of desired 13C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific 13C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of 1H-1H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  16. Dynamics-based selective 2D {sup 1}H/{sup 1}H chemical shift correlation spectroscopy under ultrafast MAS conditions

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-28

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of {sup 1}H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of {sup 1}H/{sup 1}H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

  17. Quantitative produced water analysis using mobile 1H NMR

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  18. {sup 1}H nuclear magnetic resonance study of hydrated water dynamics in perfluorosulfonic acid ionomer Nafion

    SciTech Connect

    Han, Jun Hee; Lee, Kyu Won; Jeon, G. W.; Lee, Cheol Eui; Park, W. K.; Choi, E. H.

    2015-01-12

    We have studied the dynamics of hydrated water molecules in the proton exchange membrane of Nafion by means of high-resolution {sup 1}H nuclear magnetic resonance (NMR) measurements. “Bound” and “free” states of hydrated water clusters as well as the exchange protons were identified from the NMR chemical shift measurements, and their activation energies were obtained from the temperature-dependent laboratory- and rotating-frame spin-lattice relaxation measurements. Besides, a peculiar motional transition in the ultralow frequency region was observed at 373 K for the “free” hydrated water from the rotating-frame NMR spin-lattice relaxation time measurements.

  19. Dynamic 1H NMR Studies of Schiff Base Derivatives

    NASA Astrophysics Data System (ADS)

    Köylü, M. Z.; Ekinci, A.; Böyükata, M.; Temel, H.

    2016-01-01

    The spin-lattice relaxation time T 1 and the spin-spin relaxation time T 2 of two Schiff base derivatives, N,N'-ethylenebis(salicylidene)-1,2-diaminoethane (H2L1) and N,N'-ethylenebis (salicylidene)-1,3-diaminopropane (H2L2), in DMSO-d6 solvent were studied as a function of temperature in the range of 20-50°C using a Bruker Avance 400.132 MHz 1H NMR spectrometer. Based on the activation energy ( E a) and correlation time (τc), we believe that the Schiff base derivatives perform a molecular tumbling motion.

  20. Effect of Hall Current and Finite Larmor Radius Corrections on Thermal Instability of Radiative Plasma for Star Formation in Interstellar Medium (ISM)

    NASA Astrophysics Data System (ADS)

    Kaothekar, Sachin

    2016-09-01

    The effects of finite ion Larmor radius (FLR) corrections, Hall current and radiative heat-loss function on the thermal instability of an infinite homogeneous, viscous plasma incorporating the effects of finite electrical resistivity, thermal conductivity and permeability for star formation in interstellar medium have been investigated. A general dispersion relation is derived using the normal mode analysis method with the help of relevant linearized perturbation equations of the problem. The wave propagation is discussed for longitudinal and transverse directions to the external magnetic field and the conditions of modified thermal instabilities and stabilities are discussed in different cases. We find that the thermal instability criterion gets modified into radiative instability criterion. The finite electrical resistivity removes the effect of magnetic field and the viscosity of the medium removes the effect of FLR from the condition of radiative instability. The Hall parameter affects only the longitudinal mode of propagation and it has no effect on the transverse mode of propagation. Numerical calculation shows stabilizing effect of viscosity, heat-loss function and FLR corrections, and destabilizing effect of finite resistivity and permeability on the thermal instability. The outcome of the problem discussed the formation of star in the interstellar medium.

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

    PubMed Central

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

    2013-01-01

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

  2. 23Na and 1H NMR Microimaging of Intact Plants

    NASA Astrophysics Data System (ADS)

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

    2000-06-01

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

  3. Crystal structure of 1H,1'H-[2,2'-biimid-azol]-3-ium hydrogen tartrate hemi-hydrate.

    PubMed

    Gao, Xiao-Li; Bian, Li-Fang; Guo, Shao-Wei

    2014-11-01

    In the crystal of the title hydrated salt, C6H7N4 (+)·C4H5O6 (-)·0.5H2O, the bi-imidazole monocation, 1H,1'H-[2,2'-biimidazol]-3-ium, is hydrogen bonded, via N-H⋯O, O-H⋯O and O-H⋯N hydrogen bonds, to the hydrogen tartrate anion and the water mol-ecule, which is located on a twofold rotation axis, forming sheets parallel to (001). The sheets are linked via C-H⋯O hydrogen bonds, forming a three-dimensional structure. There are also C=O⋯π inter-actions present [O⋯π distances are 3.00 (9) and 3.21 (7) Å], involving the carbonyl O atoms and the imidazolium ring, which may help to consolidate the structure. In the cation, the dihedral angle between the rings is 11.6 (2)°.

  4. In vivo 1H chemical shift imaging of silicone implants.

    PubMed

    Pfleiderer, B; Ackerman, J L; Garrido, L

    1993-05-01

    In order to study the aging process (i.e., silicone migration, fat infiltration) of silicone (polydimethylsiloxane, PDMS) based biomaterials in living subjects by NMR imaging, a hybrid 1H selective excitation and saturation chemical shift imaging technique (IR/CHESS-CSSE) has been developed. This sequence allows selective mapping of the distribution of silicone protons in vivo, while suppressing the contributions of fat and water. Our results indicate that a combined inversion recovery and CHESS pulse, followed by a spoiler gradient, must be applied to suppress all contributions of fat protons to the NMR signal. The sensitivity of our experiments allows the detection of a chemically unchanged silicone concentration of 5% in a voxel of 0.9 mm3 at a signal/noise ratio of 2.

  5. One dimensional 1H, 2H and 3H

    NASA Astrophysics Data System (ADS)

    Vidal, A. J.; Astrakharchik, G. E.; Vranješ Markić, L.; Boronat, J.

    2016-05-01

    The ground-state properties of one-dimensional electron-spin-polarized hydrogen 1H, deuterium 2H, and tritium 3H are obtained by means of quantum Monte Carlo methods. The equations of state of the three isotopes are calculated for a wide range of linear densities. The pair correlation function and the static structure factor are obtained and interpreted within the framework of the Luttinger liquid theory. We report the density dependence of the Luttinger parameter and use it to identify different physical regimes: Bogoliubov Bose gas, super-Tonks-Girardeau gas, and quasi-crystal regimes for bosons; repulsive, attractive Fermi gas, and quasi-crystal regimes for fermions. We find that the tritium isotope is the one with the richest behavior. Our results show unambiguously the relevant role of the isotope mass in the properties of this quantum system.

  6. Study of aqueous humour by 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Tkadlecová, Marcela; Havlíček, Jaroslav; Volka, Karel; Souček, Petr; Karel, Ivan

    1999-05-01

    The aim of this work was to study the composition of the samples of human aqueous humour including the protein content. Using 1H NMR spectroscopy many compounds (proteins, glucose, lactate, citrate and other metabolites) can be identified and their concentrations evaluated using the internal standard. While the concentrations of non-proteins in aqueous humour were relatively stable, the amount of proteins differed much more. In most of the spectra, the signals of proteins were hardly distinguishable from the baseline. For some samples a significantly higher protein content (more than 1 mg/ml) was found. The total protein concentration expressed in albumin equivalents can be determined by comparing the spectra measured by S2PUL (standard measurement) and CPMG (protein suppression) pulse sequentions. For comparison, the spectra of rabbit and bovine aqueous humour are also given.

  7. 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.

  8. 3-hydroxy-2(1H)-pyridinone chelating agents

    DOEpatents

    Raymond, Kenneth N.; Xu, Jide

    1997-01-01

    Disclosed is a series of improved metal chelating agents, which are highly effective upon both injection and oral administration; several of the most effective are of low toxicity. These chelating agents incorporate within their structure 1-hydroxy-2-pyridinone (1,2-HOPO) and 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy or oxo groups of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity of the hydroxypyridinones. In the metal complexes of said chelating agents, the amide protons form very strong hydrogen bonds with its adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provides a certain degree of lipophilicity to said 3,2-HOPO, increasing oral activity. Also disclosed is a method of making the chelating agents and a method of producing a known compound, 3-hydroxy-1-alkyl-2(1H)pyridinone, used as a precursor to the chelating agent, safely and in large quantities.

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

    PubMed

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

    2005-01-01

    Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood. PMID:16485652

  10. 3-hydroxy-2(1H)-pyridinone chelating agents

    DOEpatents

    Raymond, K.N.; Xu, J.

    1997-04-29

    Disclosed is a series of improved metal chelating agents, which are highly effective upon both injection and oral administration; several of the most effective are of low toxicity. These chelating agents incorporate within their structure 1-hydroxy-2-pyridinone (1,2-HOPO) and 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy or oxo groups of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity of the hydroxypyridinones. In the metal complexes of the chelating agents, the amide protons form very strong hydrogen bonds with its adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provides a certain degree of lipophilicity to the 3,2-HOPO, increasing oral activity. Also disclosed is a method of making the chelating agents and a method of producing a known compound, 3-hydroxy-1-alkyl-2(1H)pyridinone, used as a precursor to the chelating agent, safely and in large quantities. 2 figs.

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

    PubMed

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

    2005-01-01

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

  12. Tacrine derivatives-acetylcholinesterase interaction: 1H NMR relaxation study.

    PubMed

    Delfini, Maurizio; Di Cocco, Maria Enrica; Piccioni, Fabiana; Porcelli, Fernando; Borioni, Anna; Rodomonte, Andrea; Del Giudice, Maria Rosaria

    2007-06-01

    Two acetylcholinesterase (AChE) inhibitors structurally related to Tacrine, 6-methoxytacrine (1a) and 9-heptylamino-6-methoxytacrine (1b), and their interaction with Electrophorus Electricus AChE were investigated. The complete assignment of the 1H and 13C NMR spectra of 1a and 1b was performed by mono-dimensional and homo- and hetero-correlated two-dimensional NMR experiments. This study was undertaken to elucidate the interaction modes between AChE and 1a and 1b in solution, using NMR. The interaction between the two inhibitors and AChE was studied by the analysis of the motional parameters non-selective and selective spin-lattice relaxation times, thereby allowing the motional state of 1a and 1b, both free and bound with AChE, to be defined. The relaxation data pointed out the ligands molecular moiety most involved in the binding with AChE. The relevant ligand/enzyme interaction constants were also evaluated for both compounds and resulted to be 859 and 5412M(-1) for 1a and1b, respectively.

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

    SciTech Connect

    Cort, John R.; Cho, Herman M.

    2009-10-01

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

  14. Larmor, Joseph (1857-1942)

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    Physicist, born in Magheragall, County Antrim, Ireland, became Lucasian professor in Cambridge, working on electricity, dynamics and thermodynamics, and especially the ether, the postulated material which pervades space and in which electromagnetic radiation travels. Finding no evidence that the ether existed, he was led to some of the results inherent in EINSTEIN's theory of relativity, giving a...

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  16. A large volume double channel 1H-X RF probe for hyperpolarized magnetic resonance at 0.0475 T.

    PubMed

    Coffey, Aaron M; Shchepin, Roman V; Wilkens, Ken; Waddell, Kevin W; Chekmenev, Eduard Y

    2012-07-01

    In this work we describe a large volume 340 mL (1)H-X magnetic resonance (MR) probe for studies of hyperpolarized compounds at 0.0475 T. (1)H/(13)C and (1)H/(15)N probe configurations are demonstrated with the potential for extension to (1)H/(129)Xe. The primary applications of this probe are preparation and quality assurance of (13)C and (15)N hyperpolarized contrast agents using PASADENA (parahydrogen and synthesis allow dramatically enhanced nuclear alignment) and other parahydrogen-based methods of hyperpolarization. The probe is efficient and permits 62 μs (13)C excitation pulses at 5.3 W, making it suitable for portable operation. The sensitivity and detection limits of this probe, tuned to (13)C, are compared with a commercial radio frequency (RF) coil operating at 4.7 T. We demonstrate that low field MR of hyperpolarized contrast agents could be as sensitive as conventional high field detection and outline potential improvements and optimization of the probe design for preclinical in vivo MRI. PASADENA application of this low-power probe is exemplified with (13)C hyperpolarized 2-hydroxyethyl propionate-1-(13)C,2,3,3-d(3).

  17. Focusing effect and modulation mechanism of the beam self-fields on the electronʼs Larmor rotation in a free-electron laser with an axial guide magnetic field

    NASA Astrophysics Data System (ADS)

    Zhang, Shi-Chang

    2013-01-01

    It is revealed that at anti-resonance in a free-electron laser with a reversed guide magnetic field, the beam self-fields can act to focus the beam transport and prevent the electrons from striking on the waveguide wall before the wiggler exit. It is found that the focusing function results from the modulation of the periodically-varying self-field tangential and normal components on the electron's Larmor rotation. As a potential application, substantial improvement of the wave gain and output power at anti-resonance could be expected, since the beam current loss can be obviated by using this modulation mechanism.

  18. Simple Approaches for Estimating Vicinal 1H- 1H Coupling-Constants and for Obtaining Stereospecific Resonance Assignments in Leucine Side Chains

    NASA Astrophysics Data System (ADS)

    Constantine, K. L.; Friedrichs, M. S.; Mueller, L.

    An approach for deriving stereospecific δ-methyl assignments and χ 2 dihedral angle constraints for leucine residues, based on easily recognized patterns of 1H- 1H spin-spin coupling constants and intraresidue nuclear-Overhauser-effect spectroscopy (NOESY) cross-peak intensities, is described. The approach depends on resolved H γ and/or δ-methyl resonances and on initially obtaining stereospecific assignments for H β2 and H β3. As part of the overall strategy, a method is presented for obtaining qualitative or, in favorable cases, semiquantitative estimates of vicinal 1H- 1H coupling constants from peak intensities measured in a short-mixing-time 1H- 1H total correlation spectroscopy (TOCSY) experiment. This method of estimating 1H- 1H spin-spin coupling constants is generally applicable to all side-chain types. The approach is illustrated for several leucine residues within uniformly 15N-labeled and 15N/ 13C-double-labeled isolated light-chain variable domain of the anti-digoxin antibody 26-10. Estimates of 3Jαβ and 3Jβγ coupling constants are derived from a three-dimensional (3D) 13C-edited TOCSY-heteronuclear multiple-quantum coherence (HMQC) spectrum. These data are combined with information from 3D 15N-edited NOESY and 3D 13C-edited NOESY spectra to yield stereospecific H β2, H β3, and δ-methyl assignments, as well as constraints on χ (1) and χ 2 dihedral angles. Although the overall approach is illustrated using 3D 15N-edited and 13C-edited data, it is equally applicable to analysis of two-dimensional 1H- 1H NOESY and TOCSY spectra.

  19. 40 CFR 721.10373 - 1H-Imidazole, 1-(1-methylethyl)-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 1H-Imidazole, 1-(1-methylethyl)-. 721... Substances § 721.10373 1H-Imidazole, 1-(1-methylethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1H-imidazole, 1-(1-methylethyl)- (PMN...

  20. 40 CFR 721.10373 - 1H-Imidazole, 1-(1-methylethyl)-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 1H-Imidazole, 1-(1-methylethyl)-. 721... Substances § 721.10373 1H-Imidazole, 1-(1-methylethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1H-imidazole, 1-(1-methylethyl)- (PMN...

  1. 40 CFR 721.10373 - 1H-Imidazole, 1-(1-methylethyl)-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false 1H-Imidazole, 1-(1-methylethyl)-. 721... Substances § 721.10373 1H-Imidazole, 1-(1-methylethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1H-imidazole, 1-(1-methylethyl)- (PMN...

  2. Complete assignments of 1H and 13C NMR data for ten phenylpiperazine derivatives.

    PubMed

    Xiao, Zhihui; Yuan, Mu; Zhang, Si; Wu, Jun; Qi, Shuhua; Li, Qingxin

    2005-10-01

    Ten phenylpiperazine derivatives were designed and synthesized. The first complete assignments of (1)H and (13)C NMR chemical shifts for these phenylpiperazine derivatives were achieved by means of 1D and 2D NMR techniques, including (1)H-(1)H COSY, HSQC and HMBC spectra.

  3. Complete assignments of 1H and 13C NMR data for 10 phenylethanoid glycosides.

    PubMed

    Wu, Jun; Huang, Jianshe; Xiao, Qiang; Zhang, Si; Xiao, Zhihui; Li, Qingxin; Long, Lijuan; Huang, Liangmin

    2004-07-01

    Ten phenylethanoid glycosides, including two new ones, isolated from the aerial parts of the mangrove plant Acanthus ilicifolius were identified. The first complete assignments of the 1H and 13C NMR chemical shifts for these glycosides were achieved by means of 2D NMR techniques, including 1H-1H COSY, TOCSY, HSQC and HMBC spectra.

  4. 1H NMR-based protocol for the detection of adulterations of refined olive oil with refined hazelnut oil.

    PubMed

    Mannina, Luisa; D'Imperio, Marco; Capitani, Donatella; Rezzi, Serge; Guillou, Claude; Mavromoustakos, Thomas; Vilchez, María Dolores Molero; Fernández, Antonio Herrera; Thomas, Freddy; Aparicio, Ramon

    2009-12-23

    A (1)H NMR analytical protocol for the detection of refined hazelnut oils in admixtures with refined olive oils is reported according to ISO format. The main purpose of this research activity is to suggest a novel analytical methodology easily usable by operators with a basic knowledge of NMR spectroscopy. The protocol, developed on 92 oil samples of different origins within the European MEDEO project, is based on (1)H NMR measurements combined with a suitable statistical analysis. It was developed using a 600 MHz instrument and was tested by two independent laboratories on 600 MHz spectrometers, allowing detection down to 10% adulteration of olive oils with refined hazelnut oils. Finally, the potential and limitations of the protocol applied on spectrometers operating at different magnetic fields, that is, at the proton frequencies of 500 and 400 MHz, were investigated.

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

    PubMed Central

    2015-01-01

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

  6. Complete 1H NMR spectral analysis of ten chemical markers of Ginkgo biloba

    PubMed Central

    Napolitano, José G.; Lankin, David C.; Chen, Shao-Nong; Pauli, Guido F.

    2013-01-01

    The complete and unambiguous 1H NMR assignments of ten marker constituents of Ginkgo biloba are described. The comprehensive 1H NMR profiles (fingerprints) of ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J, bilobalide, quercetin, kaempferol, isorhamnetin, isoquercetin, and rutin in DMSO-d6 were obtained through the examination of 1D 1H NMR and 2D 1H,1H-COSY data, in combination with 1H iterative Full Spin Analysis (HiFSA). The computational analysis of discrete spin systems allowed a detailed characterization of all the 1H NMR signals in terms of chemical shifts (δH) and spin-spin coupling constants (JHH), regardless of signal overlap and higher order coupling effects. The capability of the HiFSA-generated 1H fingerprints to reproduce experimental 1H NMR spectra at different field strengths was also evaluated. As a result of this analysis, a revised set of 1H NMR parameters for all ten phytoconstituents was assembled. Furthermore, precise 1H NMR assignments of the sugar moieties of isoquercetin and rutin are reported for the first time. PMID:22730238

  7. Formation of large-scale structures with sharp density gradient through Rayleigh-Taylor growth in a two-dimensional slab under the two-fluid and finite Larmor radius effects

    SciTech Connect

    Goto, R.; Hatori, T.; Miura, H. Ito, A.; Sato, M.

    2015-03-15

    Two-fluid and the finite Larmor effects on linear and nonlinear growth of the Rayleigh-Taylor instability in a two-dimensional slab are studied numerically with special attention to high-wave-number dynamics and nonlinear structure formation at a low β-value. The two effects stabilize the unstable high wave number modes for a certain range of the β-value. In nonlinear simulations, the absence of the high wave number modes in the linear stage leads to the formation of the density field structure much larger than that in the single-fluid magnetohydrodynamic simulation, together with a sharp density gradient as well as a large velocity difference. The formation of the sharp velocity difference leads to a subsequent Kelvin-Helmholtz-type instability only when both the two-fluid and finite Larmor radius terms are incorporated, whereas it is not observed otherwise. It is shown that the emergence of the secondary instability can modify the outline of the turbulent structures associated with the primary Rayleigh-Taylor instability.

  8. 1H-13C/1H-15N Heteronuclear Dipolar Recoupling by R-Symmetry Sequences Under Fast Magic Angle Spinning for Dynamics Analysis of Biological and Organic Solids

    PubMed Central

    Hou, Guangjin; Byeon, In-Ja L.; Ahn, Jinwoo; Gronenborn, Angela M.; Polenova, Tatyana

    2011-01-01

    Fast magic angle spinning (MAS) NMR spectroscopy is becoming increasingly important in structural and dynamics studies of biological systems and inorganic materials. Superior spectral resolution due to the efficient averaging of the dipolar couplings can be attained at MAS frequencies of 40 kHz and higher with appropriate decoupling techniques, while proton detection gives rise to significant sensitivity gains, therefore making fast MAS conditions advantageous across the board compared with the conventional slow- and moderate-MAS approaches. At the same time, many of the dipolar recoupling approaches that currently constitute the basis for structural and dynamics studies of solid materials and that are designed for MAS frequencies of 20 kHz and below, fail above 30 kHz. In this report, we present an approach for 1H-13C/1H-15N heteronuclear dipolar recoupling under fast MAS conditions using R-type symmetry sequences, which is suitable even for fully protonated systems. A series of rotor-synchronized R-type symmetry pulse schemes are explored for the determination of structure and dynamics in biological and organic systems. The investigations of the performance of the various RNnv-symmetry sequences at the MAS frequency of 40 kHz experimentally and by numerical simulations on [U-13C,15N]-alanine and [U-13C,15N]-N-acetyl-valine, revealed excellent performance for sequences with high symmetry number ratio (N/2n > 2.5). Further applications of this approach are presented for two proteins, sparsely 13C/uniformly 15N enriched CAP-Gly domain of dynactin and U-13C,15N-Tyr enriched C-terminal domain of HIV-1 CA protein. 2D and 3D R1632-based DIPSHIFT experiments carried out at the MAS frequency of 40 kHz, yielded site-specific 1H-13C/1H-15N heteronuclear dipolar coupling constants for CAP-Gly and CTD CA, reporting on the dynamic behavior of these proteins on time scales of nano- to microseconds. The R-symmetry based dipolar recoupling under fast MAS is expected to find

  9. Unique Backbone-Water Interaction Detected in Sphingomyelin Bilayers with 1H/31P and 1H/13C HETCOR MAS NMR Spectroscopy

    PubMed Central

    Holland, Gregory P.; Alam, Todd M.

    2008-01-01

    Two-dimensional 1H/31P dipolar heteronuclear correlation (HETCOR) magic-angle spinning nuclear magnetic resonance (NMR) is used to investigate the correlation of the lipid headgroup with various intra- and intermolecular proton environments. Cross-polarization NMR techniques involving 31P have not been previously pursued to a great extent in lipid bilayers due to the long 1H-31P distances and high degree of headgroup mobility that averages the dipolar coupling in the liquid crystalline phase. The results presented herein show that this approach is very promising and yields information not readily available with other experimental methods. Of particular interest is the detection of a unique lipid backbone-water intermolecular interaction in egg sphingomyelin (SM) that is not observed in lipids with glycerol backbones like phosphatidylcholines. This backbone-water interaction in SM is probed when a mixing period allowing magnetization exchange between different 1H environments via the nuclear Overhauser effect (NOE) is included in the NMR pulse sequence. The molecular information provided by these 1H/31P dipolar HETCOR experiments with NOE mixing differ from those previously obtained by conventional NOE spectroscopy and heteronuclear NOE spectroscopy NMR experiments. In addition, two-dimensional 1H/13C INEPT HETCOR experiments with NOE mixing support the 1H/31P dipolar HETCOR results and confirm the presence of a H2O environment that has nonvanishing dipolar interactions with the SM backbone. PMID:18390621

  10. Mechanistic Assessment of PD-1H Coinhibitory Receptor-Induced T Cell Tolerance to Allogeneic Antigens.

    PubMed

    Flies, Dallas B; Higuchi, Tomoe; Chen, Lieping

    2015-06-01

    PD-1H is a recently identified cell surface coinhibitory molecule of the B7/CD28 immune modulatory gene family. We showed previously that single injection of a PD-1H agonistic mAb protected mice from graft-versus-host disease (GVHD). In this study, we report two distinct mechanisms operate in PD-1H-induced T cell tolerance. First, signaling via PD-1H coinhibitory receptor potently arrests alloreactive donor T cells from activation and expansion in the initiation phase. Second, donor regulatory T cells are subsequently expanded to maintain long-term tolerance and GVHD suppression. Our study reveals the crucial function of PD-1H as a coinhibitory receptor on alloreactive T cells and its function in the regulation of T cell tolerance. Therefore, PD-1H may be a target for the modulation of alloreactive T cells in GVHD and transplantation. PMID:25917101

  11. Visual stimulation, 1H MR spectroscopy and fMRI of the human visual pathways.

    PubMed

    Boucard, Christine C; Mostert, Jop P; Cornelissen, Frans W; De Keyser, Jacques; Oudkerk, Matthijs; Sijens, Paul E

    2005-01-01

    The purpose was to assess changes in lactate content and other brain metabolites under visual stimulation in optical chiasm, optic radiations and occipital cortex using multiple voxel MR spectroscopy (MRS). 1H chemical shift imaging (CSI) examinations of transverse planes centered to include the above structures were performed in four subjects at an echo time of 135 ms. Functional MRI (fMRI) was used to confirm the presence of activity in the visual cortex during the visual stimulation. Spectral maps of optical chiasm were of poor quality due to field disturbances caused by nearby large blood vessels and/or eye movements. The optic radiations and the occipital lobe did not show any significant MR spectral change upon visual stimulation, i.e., the peak areas of inositol, choline, creatine, glutamate and N-acetylaspartate were not affected. Reproducible lactate signals were not observed. fMRI confirmed the presence of strong activations in stimulated visual cortex. Prolonged visual stimulation did not cause significant changes in MR spectra. Any signal observed near the 1.33 ppm resonance frequency of the lactate methyl-group was artifactual, originating from lipid signals from outside the volume of interest (VOI). Previous claims about changes in lactate levels in the visual cortex upon visual stimulation may have been based on such erroneous observations. PMID:15480690

  12. Organometallic 3-(1H-Benzimidazol-2-yl)-1H-pyrazolo[3,4-b]pyridines as Potential Anticancer Agents

    PubMed Central

    2011-01-01

    Six organometallic complexes of the general formula [MIICl(η6-p-cymene)(L)]Cl, where M = Ru (11a, 12a, 13a) or Os (11b, 12b, 13b) and L = 3-(1H-benzimidazol-2-yl)-1H-pyrazolo[3,4-b]pyridines (L1–L3) have been synthesized. The latter are known as potential cyclin-dependent kinase (Cdk) inhibitors. All compounds have been comprehensively characterized by elemental analysis, one- and two-dimensional NMR spectroscopy, UV–vis spectroscopy, ESI mass spectrometry, and X-ray crystallography (11b and 12b). The multistep synthesis of 3-(1H-benzimidazol-2-yl)-1H-pyrazolo[3,4-b]pyridines (L1–L3), which was reported by other researchers, has been modified by us essentially (e.g., the synthesis of 5-bromo-1H-pyrazolo[3,4-b]pyridine-3-carboxylic acid (3) via 5-bromo-3-methyl-1H-pyrazolo[3,4-b]pyridine (2); the synthesis of 1-methoxymethyl-2,3-diaminobenzene (5) by avoiding the use of unstable 2,3-diaminobenzyl alcohol; and the activation of 1H-pyrazolo[3,4-b]pyridine-3-carboxylic acids (1, 3) through the use of an inexpensive coupling reagent, N,N′-carbonyldiimidazole (CDI)). Stabilization of the 7b tautomer of methoxymethyl-substituted L3 by coordination to a metal(II) center, as well as the NMR spectroscopic characterization of two tautomers 7b-L3 and 4b′-L3 in a metal-free state are described. Structure–activity relationships with regard to cytotoxicity and cell cycle effects in human cancer cells, as well as Cdk inhibitory activity, are also reported. PMID:22032295

  13. 1H and 13C NMR studies of glycine in anisotropic media: Double-quantum transitions and the effects of chiral interactions

    NASA Astrophysics Data System (ADS)

    Naumann, Christoph; Kuchel, Philip W.

    2011-07-01

    The 1H NMR spectrum of glycine in stretched gelatin gel and in cromolyn liquid crystal displays a well-resolved doublet due to 1H- 1H dipolar interaction. Multiple spectra were obtained within a wide range of offset frequencies of partially saturating radio-frequency (RF) radiation to generate steady-state irradiation envelopes or z-spectra of glycine. Maximal suppression of the doublet occurred when the irradiation was applied exactly at the centre frequency, between the two glycine peaks. This phenomenon is due to double-quantum transitions and is similar to our previous work on quadrupolar nuclei 2H (HDO) and 23Na +. When the 13C isotopomer glycine-2- 13C was used, the same effect was found in twice, split by 1JCH + 2 DCH. Additional signals in 1H and 13C NMR due to prochiral-chiral interactions were found when glycine-2- 13C was dissolved in chiral anisotropic gelatin and κ-carrageenan gels. The NMR spectra were successfully simulated assuming a 2JHH coupling constant of -16.5 Hz and two distinct dipolar coupling constants for the - 13CH 2- group ( DC,HA, and DC,HB).

  14. Electronic states and molecular dynamics of single-component molecular conductors [M (tmdt) 2] (M =Ni , Pt) studied by 13C and 1H NMR

    NASA Astrophysics Data System (ADS)

    Takagi, Rina; Miyagawa, Kazuya; Yoshimura, Masahide; Gangi, Hiro; Kanoda, Kazushi; Zhou, Biao; Idobata, Yuki; Kobayashi, Akiko

    2016-01-01

    The molecular conductors [M(tmdt) 2] (M =Ni , Pt) consisting of single molecular species are investigated with 13C NMR and 1H NMR. The temperature dependences of the 13C NMR shift and relaxation rate provide microscopic evidence for the metallic nature with appreciable electron correlations. Both compounds exhibit an anomalous frequency-dependent enhancement in the 1H nuclear spin-lattice relaxation rate in a wide temperature range. These observations signify the presence of extraordinary molecular motions with low energy excitations.

  15. A classical approach in simple nuclear fusion reaction {sub 1}H{sup 2}+{sub 1}H{sup 3} using two-dimension granular molecular dynamics model

    SciTech Connect

    Viridi, S.; Kurniadi, R.; Waris, A.; Perkasa, Y. S.

    2012-06-06

    Molecular dynamics in 2-D accompanied by granular model provides an opportunity to investigate binding between nuclei particles and its properties that arises during collision in a fusion reaction. A fully classical approach is used to observe the influence of initial angle of nucleus orientation to the product yielded by the reaction. As an example, a simplest fusion reaction between {sub 1}H{sup 2} and {sub 1}H{sup 3} is observed. Several products of the fusion reaction have been obtained, even the unreported ones, including temporary {sub 2}He{sup 4} nucleus.

  16. Molecular structure studies of (1S,2S)-2-benzyl-2,3-dihydro-2-(1H-inden-2-yl)-1H-inden-1-ol

    PubMed Central

    Zhang, Tao; Paluch, Krzysztof; Scalabrino, Gaia; Frankish, Neil; Healy, Anne-Marie; Sheridan, Helen

    2015-01-01

    The single enantiomer (1S,2S)-2-benzyl-2,3-dihydro-2-(1H-inden-2-yl)-1H-inden-1-ol (2), has recently been synthesized and isolated from its corresponding diastereoisomer (1). The molecular and crystal structures of this novel compound have been fully analyzed. The relative and absolute configurations have been determined by using a combination of analytical tools including X-ray crystallography, X-ray Powder Diffraction (XRPD) analysis and Nuclear Magnetic Resonance (NMR) spectroscopy. PMID:25750458

  17. A study of the molecular conformations and the vibrational, 1H and 13C NMR spectra of the anticancer drug tamoxifen and triphenylethylene

    NASA Astrophysics Data System (ADS)

    Badawi, Hassan M.; Khan, Ibrahim

    2016-08-01

    The structural stability and the vibrational spectra of the anticancer drug tamoxifen and triphenylethylene were investigated by the DFT B3LYP/6-311G (d,p) calculations. Tamoxifen and triphenylethylene were predicted to exist predominantly as non-planar structures. The vibrational frequencies and the 1H and 13C NMR chemical shifts of the low energy structures of tamoxifen and triphenylethylene were computed at the DFT B3LYP level of theory. Complete vibrational assignments were provided by combined theoretical and experimental data of tamoxifen and triphenylethylene. The 1H and 13C NMR spectra of both molecules were interpreted by experimental and DFT calculated chemical shifts of the two molecules. The RMSD between experimental and theoretical 1H and 13C chemical shifts for tamoxifen is 0.29 and 4.72 ppm, whereas for triphenylethylene, it is 0.16 and 2.70 ppm, respectively.

  18. Magnetoreception in the wood mouse (Apodemus sylvaticus): influence of weak frequency-modulated radio frequency fields

    PubMed Central

    Malkemper, E. Pascal; Eder, Stephan H. K.; Begall, Sabine; Phillips, John B.; Winklhofer, Michael; Hart, Vlastimil; Burda, Hynek

    2015-01-01

    The mammalian magnetic sense is predominantly studied in species with reduced vision such as mole-rats and bats. Far less is known about surface-dwelling (epigeic) rodents with well-developed eyes. Here, we tested the wood mouse Apodemus sylvaticus for magnetoreception using a simple behavioural assay in which mice are allowed to build nests overnight in a visually symmetrical, circular arena. The tests were performed in the ambient magnetic field or in a field rotated by 90°. When plotted with respect to magnetic north, the nests were bimodally clustered in the northern and southern sectors, clearly indicating that the animals used magnetic cues. Additionally, mice were tested in the ambient magnetic field with a superimposed radio frequency magnetic field of the order of 100 nT. Wood mice exposed to a 0.9 to 5 MHz frequency sweep changed their preference from north-south to east-west. In contrast to birds, however, a constant frequency field tuned to the Larmor frequency (1.33 MHz) had no effect on mouse orientation. In sum, we demonstrated magnetoreception in wood mice and provide first evidence for a radical-pair mechanism in a mammal. PMID:25923312

  19. Classification of brain tumours using short echo time 1H MR spectra

    NASA Astrophysics Data System (ADS)

    Devos, A.; Lukas, L.; Suykens, J. A. K.; Vanhamme, L.; Tate, A. R.; Howe, F. A.; Majós, C.; Moreno-Torres, A.; van der Graaf, M.; Arús, C.; Van Huffel, S.

    2004-09-01

    The purpose was to objectively compare the application of several techniques and the use of several input features for brain tumour classification using Magnetic Resonance Spectroscopy (MRS). Short echo time 1H MRS signals from patients with glioblastomas ( n = 87), meningiomas ( n = 57), metastases ( n = 39), and astrocytomas grade II ( n = 22) were provided by six centres in the European Union funded INTERPRET project. Linear discriminant analysis, least squares support vector machines (LS-SVM) with a linear kernel and LS-SVM with radial basis function kernel were applied and evaluated over 100 stratified random splittings of the dataset into training and test sets. The area under the receiver operating characteristic curve (AUC) was used to measure the performance of binary classifiers, while the percentage of correct classifications was used to evaluate the multiclass classifiers. The influence of several factors on the classification performance has been tested: L2- vs. water normalization, magnitude vs. real spectra and baseline correction. The effect of input feature reduction was also investigated by using only the selected frequency regions containing the most discriminatory information, and peak integrated values. Using L2-normalized complete spectra the automated binary classifiers reached a mean test AUC of more than 0.95, except for glioblastomas vs. metastases. Similar results were obtained for all classification techniques and input features except for water normalized spectra, where classification performance was lower. This indicates that data acquisition and processing can be simplified for classification purposes, excluding the need for separate water signal acquisition, baseline correction or phasing.

  20. 2D 1H and 3D 1H-15N NMR of zinc-rubredoxins: contributions of the beta-sheet to thermostability.

    PubMed Central

    Richie, K. A.; Teng, Q.; Elkin, C. J.; Kurtz, D. M.

    1996-01-01

    Based on 2D 1H-1H and 2D and 3D 1H-15N NMR spectroscopies, complete 1H NMR assignments are reported for zinc-containing Clostridium pasteurianum rubredoxin (Cp ZnRd). Complete 1H NMR assignments are also reported for a mutated Cp ZnRd, in which residues near the N-terminus, namely, Met 1, Lys 2, and Pro 15, have been changed to their counterparts, (-), Ala and Glu, respectively, in rubredoxin from the hyperthermophilic archaeon, Pyrococcus furiosus (Pf Rd). The secondary structure of both wild-type and mutated Cp ZnRds, as determined by NMR methods, is essentially the same. However, the NMR data indicate an extension of the three-stranded beta-sheet in the mutated Cp ZnRd to include the N-terminal Ala residue and Glu 15, as occurs in Pf Rd. The mutated Cp Rd also shows more intense NOE cross peaks, indicating stronger interactions between the strands of the beta-sheet and, in fact, throughout the mutated Rd. However, these stronger interactions do not lead to any significant increase in thermostability, and both the mutated and wild-type Cp Rds are much less thermostable than Pf Rd. These correlations strongly suggest that, contrary to a previous proposal [Blake PR et al., 1992, Protein Sci 1:1508-1521], the thermostabilization mechanism of Pf Rd is not dominated by a unique set of hydrogen bonds or electrostatic interactions involving the N-terminal strand of the beta-sheet. The NMR results also suggest that an overall tighter protein structure does not necessarily lead to increased thermostability. PMID:8732760

  1. A common polymorphism in NR1H2 (LXRbeta) is associated with preeclampsia

    PubMed Central

    2011-01-01

    Background Preeclampsia is a frequent complication of pregnancy and a leading cause of perinatal mortality. Both genetic and environmental risk factors have been identified. Lipid metabolism, particularly cholesterol metabolism, is associated with this disease. Liver X receptors alpha (NR1H3, also known as LXRalpha) and beta (NR1H2, also known as LXRbeta) play a key role in lipid metabolism. They belong to the nuclear receptor superfamily and are activated by cholesterol derivatives. They have been implicated in preeclampsia because they modulate trophoblast invasion and regulate the expression of the endoglin (CD105) gene, a marker of preeclampsia. The aim of this study was to investigate associations between the NR1H3 and NR1H2 genes and preeclampsia. Methods We assessed associations between single nucleotide polymorphisms of NR1H3 (rs2279238 and rs7120118) and NR1H2 (rs35463555 and rs2695121) and the disease in 155 individuals with preeclampsia and 305 controls. Genotypes were determined by high-resolution melting analysis. We then used a logistic regression model to analyze the different alleles and genotypes for those polymorphisms as a function of case/control status. Results We found no association between NR1H3 SNPs and the disease, but the NR1H2 polymorphism rs2695121 was found to be strongly associated with preeclampsia (genotype C/C: adjusted odds ratio, 2.05; 95% CI, 1.04-4.05; p = 0.039 and genotype T/C: adjusted odds ratio, 1.85; 95% CI, 1.01-3.42; p = 0.049). Conclusions This study provides the first evidence of an association between the NR1H2 gene and preeclampsia, adding to our understanding of the links between cholesterol metabolism and this disease. PMID:22029530

  2. The Frequency-Dependence of the NMR Longitudinal Relaxation Rate, T(1)(-1), of Water in Cysts of the Brine Shrimp

    NASA Astrophysics Data System (ADS)

    Egan, Thomas F.

    The NMR spin-lattice relaxation rate, T(,1)(' -1), of water is independent of the Larmor frequency, (omega)/2(pi), in the normal rf range. However, T(,1)('-1) of intracellular water in biological systems, which accounts for as much as 80% of the cell mass, is frequency-dependent. This indicates that the NMR properties of water in the cellular environment are influenced by long-correlation time processes due to the interaction of water with proteins and other macromolecular constituents of the cell. In this research, the relaxation rate T(,1)(' -1) of water in the Artemia (brine shrimp) cyst is examined as a function of: (1) the proton NMR Larmor frequency for .01 <= (omega)/2(pi) <= 500 MHz, (2) different cyst hydration levels from 0.12 to 1.25 grams water/gram dry solid, (3) temperatures of 22C and 5C. The frequency-dependence of T(,1)('-1) is interpreted in terms of a two-phase exchange model. One water phase is similar to pure water and contributes a small constant relaxation rate. The second phase is water closely associated with the surfaces of large molecules and termed "hydration water". A polymer-dynamics relaxation mechanism, which treats fluctuations of long-chain molecules in aqueous solution, has been proposed by Rorschach and Hazlewood to explain the relaxation in this second water phase. In one limit, this mechanism predicts a frequency-dependent relaxation rate proportional to (omega)('- 1/2). This particular dependence has previously been observed in other NMR studies on biological systems and is also observed in this study for Artemia cysts between 10 and 500 MHz. At lower Larmor frequencies, below 1 MHz, the relaxation rates of water in brine shrimp cysts are influenced by additional relexation mechanisms; translational diffusion of hydration water is one possibility.

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2013-12-31

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

  5. Preparation and dielectric properties of core-shell structural composites of poly(1H,1H,2H,2H-perfluorooctyl methacrylate)@BaTiO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhang, Xianhong; Chen, Haochuan; Ma, Yuhong; Zhao, Changwen; Yang, Wantai

    2013-07-01

    Polymer nanocomposite films, poly(1H,1H,2H,2H-perfluorooctyl methacrylate)@BaTiO3 (PPFOMA@BaTiO3), with enhanced dielectric permittivity was fabricated via a two-step processes, consisting of BaTiO3 nanoparticle surface modification and surface initiated atom transfer radical grafting polymerization (SI-ATRP). At first, BaTiO3 nanoparticles were treated by hydroxylation, silylation and amidation to offer their SI-ATRP capability. Then PPFOMA chains were grafted from the modified BaTiO3 nanoparticles by SI-ATRP at 70 °C to form core-shell composites. The effects of polymer structure and polymer/BaTiO3 ratios on dielectric properties were measured over a broad frequency from 40 Hz to 30 MHz at room temperature. The results showed that the dielectric constant (k) increased and dielectric loss reduced significantly with the addition of BaTiO3. The k of the composite was up to 7.4 at 100 kHz at room temperature when the BaTiO3 loading was up to 70.70 wt% which is almost three time of pure PPFOMA (k = 2.6). While the dielectric loss (tan δ) of PPFOMA@BaTiO3 composite was about 0.01, which was much lower than that of the pure PPFOMA (tan δ = 0.04).

  6. Potential role of body fluid 1H NMR metabonomics as a prognostic and diagnostic tool.

    PubMed

    Ala-Korpela, Mika

    2007-11-01

    This review briefly handles the use of (1)H NMR spectroscopy in lipoprotein subclass analytics. Potential diagnostic uses of (1)H NMR metabonomics of human serum for coronary heart disease, diabetic nephropathy and cancer are also discussed. In addition, miscellaneous recent applications of NMR metabonomics (e.g., a pharmacometabonomic tactic to personalize drug treatment) as well as multi-organ, multispecies and multi-omics approaches to molecular systems biology are featured. Some related experimental and data analysis methodologies are briefly introduced with respect to the biochemical rationales. Critical considerations on the potential diagnostic value of in vitro (1)H NMR are presented together with optimism toward the usage of body fluid (1)H NMR metabonomics in disease risk assessment and as an aid for personalized medicine.

  7. One-Pot Synthesis of Substituted Trifluoromethylated 2,3-Dihydro-1H-imidazoles.

    PubMed

    Deutsch, Amrei; Jessen, Christoph; Deutsch, Carl; Karaghiosoff, Konstantin; Hoffmann-Röder, Anja

    2016-07-15

    An operationally simple one-pot reaction for the preparation of a novel class of racemic trifluoromethylated 2,3-dihydro-1H-imidazoles derived from electron-poor N,O-acetals and aryl Grignard reagents is described. In addition, access to highly functionalized 2-trifluoromethyl-2,3-dihydro-1H-imidazoles was accomplished by reaction of N-aryl hemiaminal ethers and N-aryl trifluoroethylamines in the presence of an excess of n-butyllithium. PMID:27359260

  8. Measurements of heavy-atom isotope effects using 1H NMR spectroscopy.

    PubMed

    Pabis, Anna; Kamiński, Rafał; Ciepielowski, Grzegorz; Jankowski, Stefan; Paneth, Piotr

    2011-10-01

    A novel method for measuring heavy-atom KIEs for magnetically active isotopes using (1)H NMR is presented. It takes advantage of the resonance split of the protons coupled with the heavy atom in the (1)H spectrum. The method is validated by the example of the (13)C-KIE on the hydroamination of styrene with aniline, catalyzed by phosphine-ligated palladium triflates.

  9. Complete 1H, 15N and 13C assignment of trappin-2 and 1H assignment of its two domains, elafin and cementoin.

    PubMed

    Loth, Karine; Alami, Soha Abou Ibrahim; Habès, Chahrazed; Garrido, Solène; Aucagne, Vincent; Delmas, Agnès F; Moreau, Thierry; Zani, Marie-Louise; Landon, Céline

    2016-04-01

    Trappin-2 is a serine protease inhibitor with a very narrow inhibitory spectrum and has significant anti-microbial activities. It is a 10 kDa cationic protein composed of two distinct domains. The N-terminal domain (38 residues) named cementoin is known to be intrinsically disordered when it is not linked to the elafin. The C-terminal domain (57 residues), corresponding to elafin, is a cysteine-rich domain stabilized by four disulfide bridges and is characterized by a flat core and a flexible N-terminal part. To our knowledge, there is no structural data available on trappin-2. We report here the complete (1)H, (15)N and (13)C resonance assignment of the recombinant trappin-2 and the (1)H assignments of cementoin and elafin, under the same experimental conditions. This is the first step towards the 3D structure determination of the trappin-2.

  10. Magnesium Silicate Dissolution Investigated by 29Si MAS, 1H-29Si CP MAS, 25Mg QCPMG, and 1H-25Mg CP QCPMG NMR

    SciTech Connect

    Davis, Michael C.; Brouwer, William J.; Wesolowski, David J.; Anovitz, Lawrence M.; Lipton, Andrew S.; Mueller, Karl T.

    2009-08-01

    Olivine has been the subject of frequent investigation in the earth sciences because of its simple structure and rapid dissolution kinetics. Several studies have observed a preferential release of magnesium with respect to silica during weathering under acidic conditions, which has been correlated to the formation of a silicon rich leached layer. While leached layer formation has been inferred through the changing solution chemistry, a thorough spectroscopic investigation of olivine reacted under acidic conditions has not been conducted. In particular, the fate of magnesium in the system is not understood and spectroscopic interrogations through nuclear magnetic resonance can elucidate the changing magnesium coordination and bonding environment. In this study, we combine analysis of the changing solution chemistry with advanced spectroscopic techniques (29Si MAS, 1H-29Si CP MAS, 25Mg QCPMG, and 1H-25Mg 2 CP QCPMG NMR) to probe leached layer formation and possible secondary phase precipitation during the dissolution of forsterite at 150 oC.

  11. Determination of glucan phosphorylation using heteronuclear 1H, 13C double and 1H, 13C, 31P triple-resonance NMR spectra.

    PubMed

    Schmieder, Peter; Nitschke, Felix; Steup, Martin; Mallow, Keven; Specker, Edgar

    2013-10-01

    Phosphorylation and dephosphorylation of starch and glycogen are important for their physicochemical properties and also their physiological functions. It is therefore desirable to reliably determine the phosphorylation sites. Heteronuclear multidimensional NMR-spectroscopy is in principle a straightforward analytical approach even for complex carbohydrate molecules. With heterogeneous samples from natural sources, however, the task becomes more difficult because a full assignment of the resonances of the carbohydrates is impossible to obtain. Here, we show that the combination of heteronuclear (1) H,(13) C and (1) H,(13) C,(31) P techniques and information derived from spectra of a set of reference compounds can lead to an unambiguous determination of the phosphorylation sites even in heterogeneous samples. PMID:23913630

  12. Bioinspired, cysteamine-catalyzed co-silicification of (1H, 1H, 2H, 2HPerfluorooctyl) triethoxysilane and tetraethyl orthosilicate: formation of superhydrophobic surfaces.

    PubMed

    Park, Ji Hun; Kim, Ji Yup; Cho, Woo Kyung; Choi, Insung S

    2014-03-01

    Bioinspired silicification attracts a great deal of interest because of its physiologically relevant, mild conditions for hydrolysis and condensation of silica precursors, which makes the bioinspired approach superior to the conventional sol–gel process, particularly when dealing with biological entities. However, the morphological control of silica structures with incorporation of functional groups in the bioinspired silicilication has been unexplored. In this work, we co-silicificated (1H, 1H, 2H, 2H-perfluorooctyl)triethoxysilane and tetraethyl orthosilicate to investigate the morphological evolution of fluorinated silica structures in the cetyltrimethylammonium bromide-mediated, cysteamine-catalyzed silicification. The generated micrometer-long wormlike and spherical silica structures display superhydrophobicity after film formation. Interestingly, the measurement of dynamic water contact angles shows that the morphological difference leads to a different wetting state, either the self-cleaning or the pinning state of the superhydrophobic surface.

  13. Determination of glucan phosphorylation using heteronuclear 1H, 13C double and 1H, 13C, 31P triple-resonance NMR spectra.

    PubMed

    Schmieder, Peter; Nitschke, Felix; Steup, Martin; Mallow, Keven; Specker, Edgar

    2013-10-01

    Phosphorylation and dephosphorylation of starch and glycogen are important for their physicochemical properties and also their physiological functions. It is therefore desirable to reliably determine the phosphorylation sites. Heteronuclear multidimensional NMR-spectroscopy is in principle a straightforward analytical approach even for complex carbohydrate molecules. With heterogeneous samples from natural sources, however, the task becomes more difficult because a full assignment of the resonances of the carbohydrates is impossible to obtain. Here, we show that the combination of heteronuclear (1) H,(13) C and (1) H,(13) C,(31) P techniques and information derived from spectra of a set of reference compounds can lead to an unambiguous determination of the phosphorylation sites even in heterogeneous samples.

  14. Coinhibitory receptor PD-1H preferentially suppresses CD4+ T cell–mediated immunity

    PubMed Central

    Flies, Dallas B.; Han, Xue; Higuchi, Tomoe; Zheng, Linghua; Sun, Jingwei; Ye, Jessica Jane; Chen, Lieping

    2014-01-01

    T cell activation is regulated by the interactions of surface receptors with stimulatory and inhibitory ligands. Programmed death-1 homolog (PD-1H, also called VISTA) is a member of the CD28 family of proteins and has been shown to act as a coinhibitory ligand on APCs that suppress T cell responses. Here, we determined that PD-1H functions as a coinhibitory receptor for CD4+ T cells. CD4+ T cells in mice lacking PD-1H exhibited a dramatically increased response to antigen stimulation. Furthermore, delivery of a PD-1H–specific agonist mAb directly inhibited CD4+ T cell activation both in vitro and in vivo, validating a coinhibitory function of PD-1H. In a murine model of acute hepatitis, administration of a PD-1H agonist mAb suppressed CD4+ T cell–mediated acute inflammation. PD-1H–deficient animals were highly resistant to tumor induction in a murine brain glioma model, and depletion of CD4+ T cells, but not CD8+ T cells, promoted tumor formation. Together, our findings suggest that PD-1H has potential as a target of immune modulation in the treatment of human inflammation and malignancies. PMID:24743150

  15. Analysis of the electronic, IR, and 1H NMR spectra of conjugated oligomers based on 4,4'-triphenylamine vinylene

    NASA Astrophysics Data System (ADS)

    Baryshnikov, G. V.; Minaeva, V. A.; Minaev, B. F.; Sun, V.-H.; Grigoras, M.

    2016-09-01

    Two types of conjugated oligomers based on 4,4'-triphenylamine vinylene have been synthesized and characterized by the methods of IR, UV-visible, and 1H NMR spectroscopy. The corresponding spectra have also been simulated theoretically at the density functional theory level with application of the B3LYP and BMK hybrid exchange-correlation functionals. A comparative analysis of the experimental and theoretical spectra of polymers and oligomers has revealed regularities of the manifestation of spectral signals depending on the conjugation chain length and the presence of a substituent in the triphenylamine core. It has been established, in particular, that the absolute intensity of IR bands satisfies a linear dependence with increase in the degree of polymerization; however, no frequency shift is observed at the same time. The position of the main peak in electron absorption spectra demonstrates the bathochromic shift with an increase in the oligomeric chain length due to the narrowing of the energy gap between the boundary molecular orbitals. Based on the theoretical estimation of the hydrogen atoms chemical shifts, the signals of various protons types in the strongly broadened experimental 1H NMR spectra of the bis-(4-iodine phenyl)-phenylamine and N,N-bis-(4-iodine phenyl)-4'-(phenylethynyl)-phenylamine polymerization products have also been identified.

  16. Reaction of (chloro carbonyl) phenyl ketene with 5-amino pyrazolones: Synthesis, characterization and theoretical studies of 7-hydroxy-6-phenyl-3-(phenyldiazenyl)pyrazolo[1,5-a]pyrimidine-2,5(1H,4H)-dione derivatives

    NASA Astrophysics Data System (ADS)

    Zahedifar, Mahboobeh; Razavi, Razieh; Sheibani, Hassan

    2016-12-01

    New 7-hydroxy-6-phenyl-3-(phenyldiazenyl)pyrazolo[1,5-a]pyrimidine-2,5(1H,4H)-dione derivatives were synthesized from the reaction of (chlorocarbonyl)phenyl ketene and 5-amino pyrazolones in high to excellent yields and short reaction times. Structures of the new compounds were fully characterized by their spectral data IR, 1H NMR, and 13C NMR and by the theoretical results. Density Functional Theory (DFT) was used to optimize the structures, compute the energies and vibrational frequencies IR and 1H NMR shielding tensors of the desired products. The theoretical results excellent are compared with the experimental data.

  17. Oscillating two stream instability of electromagnetic pump in the ion cyclotron range of frequency in a plasma

    SciTech Connect

    Ahmad, Nafis; Tripathi, V. K.; Rafat, M.; Husain, Mudassir M.

    2009-06-15

    An analytical formalism of oscillating two stream instability of a large amplitude electromagnetic wave in the ion cyclotron range of frequency in a plasma is developed. The instability produces electrostatic ion cyclotron sidebands and a driven low frequency mode. The nonlinear coupling arises primarily due to the motion of ions and is strong when the pump frequency is close to ion cyclotron frequency and the oscillatory ion velocity is a significant fraction of acoustic speed. For propagation perpendicular to the ambient magnetic field, the X-mode pump wave produces flute type perturbation with maximum growth rate at some specific wavelengths, which are three to four times larger than the ion Larmor radius. For propagation at oblique angles to ambient magnetic field, the ion cyclotron O-mode, the growth rate increases with the wave number of the low frequency mode.

  18. Design of a sup 13 C (1H) RF probe for monitoring the in vivo metabolism of (1- sup 13 C)glucose in primate brain

    SciTech Connect

    Hammer, B.E.; Sacks, W.; Bigler, R.E.; Hennessy, M.J.; Sacks, S.; Fleischer, A.; Zanzonico, P.B. )

    1990-01-01

    The design of an RF probe suitable for obtaining proton-decoupled {sup 13}C spectra from a subhuman primate brain is described. Two orthogonal saddle coils, one tuned to the resonant frequency of {sup 13}C and the other to the resonant frequency of 1H, were used to monitor the in vivo metabolism of (1-{sup 13}C)glucose in rhesus monkey brain at 2.1 T. Difference spectra showed the appearance of {sup 13}C-enriched glutamate and glutamine 30 to 40 min after a bolus injection of (1-{sup 13}C)glucose.

  19. High-Resolution Solid-State NMR of Anisotropically Mobile Molecules Under Very Low Power 1H Decoupling and Moderate Magic-Angle Spinning

    PubMed Central

    Doherty, Tim; Hong, Mei

    2011-01-01

    We show that for observing high-resolution heteronuclear NMR spectra of anisotropically mobile systems with order parameters less than 0.25, moderate magic-angle spinning (MAS) rates of ∼11 kHz combined with 1H decoupling at 1-2 kHz are sufficient. Broadband decoupling at this low 1H nutation frequency is achieved by composite pulse sequences such as WALTZ-16. We demonstrate this moderate MAS low-power decoupling technique on hydrated POPC lipid membranes, and show that 1 kHz 1H decoupling yields spectra with the same resolution and sensitivity as spectra measured under 50 kHz 1H decoupling when the same acquisition times (∼ 50 ms) are used, but the low-power decoupled spectra give higher resolution and sensitivity when longer acquisition times (> 150 ms) are used, which are not possible with high-power decoupling. The limits of validity of this approach are explored for a range of spinning rates and molecular mobilities using more rigid membrane systems such as POPC/cholesterol mixed bilayers. Finally, we show 15N and 13C spectra of a uniaxially diffusing membrane peptide assembly, the influenza A M2 transmembrane domain, under 11 kHz MAS and 2 kHz 1H decoupling. The peptide 15N and 13C intensities at low power decoupling are 70-80% of the high-power decoupled intensities. Therefore, it is possible to study anisotropically mobile lipids and membrane peptides using liquid-state NMR equipment, relatively large rotors, and moderate MAS frequencies. PMID:19501003

  20. Transformation of 1H-benzotriazole by ozone in aqueous solution.

    PubMed

    Mawhinney, Douglas B; Vanderford, Brett J; Snyder, Shane A

    2012-07-01

    Recent studies have shown that 1H-benzotriazole is a widespread contaminant of wastewater and surface water. Although disinfection by ozone has been shown to efficiently remove this compound, the transformation products have not been identified. To that end, the reaction of ozone with 1H-benzotriazole in aqueous solution has been studied in real time employing quadrupole time-of-flight mass spectrometry (Q-TOF MS) and negative electrospray ionization. The transformation products have been identified by calculating their empirical formulas using accurate mass measurements, and further confirmed by performing the reaction with stable isotope-labeled 1H-benzotriazole and measuring product ion spectra. Stable reaction products were distinguished from transient species by plotting their extracted mass profiles. The products that resulted from ozone and hydroxyl radicals in the reaction were qualitatively identified by modifying the conditions to either promote the formation of hydroxyl radicals, or to scavenge them. Based on experimental evidence, a mechanism for the direct reaction between ozone and 1H-benzotriazole is proposed that results in the formation of 1H-1,2,3-triazole-4,5-dicarbaldehyde, which has an empirical formula of C(4)H(3)O(2)N(3). Lastly, it was confirmed that the same transformation products formed in surface water and tertiary-treated wastewater, although they were observed to degrade at higher ozone doses.

  1. Synthesis and preliminary evaluation of 3-thiocyanato-1H-indoles as potential anticancer agents.

    PubMed

    Fortes, Margiani P; da Silva, Paulo B N; da Silva, Teresinha G; Kaufman, Teodoro S; Militão, Gardenia C G; Silveira, Claudio C

    2016-08-01

    A novel series of twenty 3-thiocyanato-1H-indoles, carrying diversification at positions N-1, C-2 and C-5 of the heterocyclic core, were synthesized; their antiproliferative activity against four human cancer cell lines (HL60, HEP-2, NCI-H292 and MCF-7) was evaluated, employing doxorubicin as positive control. Indole, N-methylindole and 2-(4-chlorophenyl)-N-methylindole demonstrated to be essentially inactive, whereas several of their congener 3-thiocyanato-1H-indoles displayed good to excellent levels of potency (IC50 ≤ 6 μM), while being non-hemolytic. N-Phenyl-3-thiocyanato-1H-indole and 1-methyl-2-(4-chlorophenyl)-3-thiocyanato-1H-indole showed good to high potency against all the cell lines. On the other side, the N-(4-chlorophenyl)-, 2-(4-chlorophenyl)- and 2-phenyl- 3-thiocyanato-1H-indole derivatives were slightly less active against the test cell lines. Overall, these results suggest that the indole-3-thiocyanate motif can be suitably decorated to afford highly cytotoxic compounds and that the substituted indole can be employed as a useful scaffold toward more potent compounds.

  2. Urinary metabolic fingerprint of acute intermittent porphyria analyzed by (1)H NMR spectroscopy.

    PubMed

    Carichon, Mickael; Pallet, Nicolas; Schmitt, Caroline; Lefebvre, Thibaud; Gouya, Laurent; Talbi, Neila; Deybach, Jean Charles; Beaune, Philippe; Vasos, Paul; Puy, Hervé; Bertho, Gildas

    2014-02-18

    (1)H NMR is a nonbiased technique for the quantification of small molecules that could result in the identification and characterization of potential biomarkers with prognostic value and contribute to better understand pathophysiology of diseases. In this study, we used (1)H NMR spectroscopy to analyze the urinary metabolome of patients with acute intermittent porphyria (AIP), an inherited metabolic disorder of heme biosynthesis in which an accumulation of the heme precursors 5-aminolaevulinic acid (ALA) and porphobilinogen (PBG) promotes sudden neurovisceral attacks, which can be life-threatening. Our objectives were (1) to demonstrate the usefulness of (1)H NMR to identify and quantify ALA and PBG in urines from AIP patients and (2) to identify metabolites that would predict the response to AIP crisis treatment and reflect differential metabolic reprogramming. Our results indicate that (1)H NMR can help to diagnose AIP attacks based on the identification of ALA and PBG. We also show that glycin concentration increases in urines from patients with frequent recurrences at the end of the treatment, after an initial decrease, whereas PBG concentration remains low. Although the reasons for this altered are elusive, these findings indicate that a glycin metabolic reprogramming occurs in AIPr patients and is associated with recurrence. Our results validate the proof of concept of the usefulness of (1)H NMR spectroscopy in clinical chemistry for the diagnosis of acute attack of AIP and identify urinary glycin as a potential marker of recurrence of AIP acute attacks. PMID:24437734

  3. A disc wind interpretation of the strong Fe Kα features in 1H 0707-495

    NASA Astrophysics Data System (ADS)

    Hagino, Kouichi; Odaka, Hirokazu; Done, Chris; Tomaru, Ryota; Watanabe, Shin; Takahashi, Tadayuki

    2016-10-01

    1H 0707-495 is the most convincing example of a supermassive black hole with an X-ray spectrum being dominated by extremely smeared, relativistic reflection, with the additional requirement of strongly supersolar iron abundance. However, here we show that the iron features in its 2-10 keV spectrum are rather similar to the archetypal wind dominated source, PDS 456. We fit all the 2-10 keV spectra from 1H 0707-495 using the same wind model as used for PDS 456, but viewed at higher inclination so that the iron absorption line is broader but not so blueshifted. This gives a good overall fit to the data from 1H 0707-495, and an extrapolation of this model to higher energies also gives a good match to the NuSTAR data. Small remaining residuals indicate that the iron line emission is stronger than in PDS 456. This is consistent with the wider angle wind expected from a continuum-driven wind from the super-Eddington mass accretion rate in 1H 0707-495, and/or the presence of residual reflection from the underlying disc though the presence of the absorption line in the model removes the requirement for highly relativistic smearing, and highly supersolar iron abundance. We suggest that the spectrum of 1H 0707-495 is sculpted more by absorption in a wind than by extreme relativistic effects in strong gravity.

  4. Inhibition of monoamine oxidase by 3,4-dihydro-2(1H)-quinolinone derivatives.

    PubMed

    Meiring, Letitia; Petzer, Jacobus P; Petzer, Anél

    2013-10-15

    In the present study, a series of 3,4-dihydro-2(1H)-quinolinone derivatives were synthesized and evaluated as inhibitors of recombinant human monoamine oxidase (MAO) A and B. The 3,4-dihydro-2(1H)-quinolinone derivatives are structurally related to a series of coumarin (1-benzopyran-2-one) derivatives which have been reported to act as MAO-B inhibitors. The results document that the quinolinones are highly potent and selective MAO-B inhibitors with most homologues exhibiting IC50 values in the nanomolar range. The most potent MAO-B inhibitor, 7-(3-bromobenzyloxy)-3,4-dihydro-2(1H)-quinolinone, exhibits an IC50 value of 2.9 nM with a 2750-fold selectivity for MAO-B over the MAO-A isoform. An analysis of the structure-activity relationships for MAO-B inhibition shows that substitution on the C7 position of the 3,4-dihydro-2(1H)-quinolinone scaffold leads to significantly more potent inhibition compared to substitution on C6. In this regard, a benzyloxy substituent on C7 is more favourable than phenylethoxy and phenylpropoxy substitution on this position. It may be concluded that C7-substituted 3,4-dihydro-2(1H)-quinolinones are promising leads for the therapy of Parkinson's disease.

  5. The structure and properties of 5,6-dinitro-1H-benzotriazole

    NASA Astrophysics Data System (ADS)

    Santa María, Dolores; Claramunt, Rosa M.; Torralba, M. Carmen; Torres, M. Rosario; Alkorta, Ibon; Elguero, José

    2016-06-01

    5,6-Dinitro-1H-benzotriazole crystallizes in the monoclinic system, space group P21/c. The asymmetric unit contains the planar 1H-tautomer together with a water molecule of crystallization. Each water molecule is hydrogen bonded to three adjacent 5,6-dinitrobenzotriazoles forming a tape along the b-axis of the crystal. These tapes stack along the c-axis through hydrogen bonds involving the water molecules and one of the nitro groups leading to a bidimensional structure. Solid-state 13C and 15N CPMAS NMR allow to confirm that the tautomer present is the 1H one. In DMSO-d6 solution the results are quite different and, based on GIAO/B3LYP/6-311++G(d,p) calculations, lead us to conclude that the major tautomer is the 5,6-dinitro-2H-benzotriazole, a surprising result that contradicts the rule that the major tautomer in solution coincides with the one present in the crystal. An anhydrous pseudopolymorph of 5,6-dinitro-1H-benzotriazole has been obtained as a non-crystalline form and from solid-state NMR and theoretical calculations, we conclude that it is an 1H-tautomer.

  6. Noise figure characterization of preamplifiers at NMR frequencies.

    PubMed

    Nordmeyer-Massner, J A; De Zanche, N; Pruessmann, K P

    2011-05-01

    A method for characterizing the noise figure of preamplifiers at NMR frequencies is presented. The noise figure of preamplifiers as used for NMR and MRI detection varies with source impedance and with the operating frequency. Therefore, to characterize a preamplifier's noise behavior, it is necessary to perform noise measurements at the targeted frequency while varying the source impedance with high accuracy. At high radiofrequencies, such impedance variation is typically achieved with transmission-line tuners, which however are not available for the relatively low range of typical NMR frequencies. To solve this issue, this work describes an alternative approach that relies on lumped-element circuits for impedance manipulation. It is shown that, using a fixed-impedance noise source and suitable ENR correction, this approach permits noise figure characterization for NMR and MRI purposes. The method is demonstrated for two preamplifiers, a generic BF998 MOSFET module and an MRI-dedicated, integrated preamplifier, which were both studied at 128MHz, i.e., at the Larmor frequency of protons at 3 Tesla. Variations in noise figure of 0.01dB or less over repeated measurements reflect high precision even for small noise figures in the order of 0.4dB. For validation, large sets of measured noise figure values are shown to be consistent with the general noise-parameter model of linear two-ports. Finally, the measured noise characteristics of the superior preamplifier are illustrated by SNR measurements in MRI data. PMID:21439871

  7. Amino­silanes derived from 1H-benzimidazole-2(3H)-thione

    PubMed Central

    Palomo-Molina, Juliana; García-Báez, Efrén V.; Contreras, Rosalinda; Pineda-Urbina, Kayim; Ramos-Organillo, Angel

    2015-01-01

    Two new mol­ecular structures, namely 1,3-bis­(tri­methyl­silyl)-1H-benzimidazole-2(3H)-thione, C13H22N2SSi2, (2), and 1-tri­methyl­silyl-1H-benzimidazole-2(3H)-thione, C10H14N2SSi, (3), are reported. Both systems were derived from 1H-benzimidazole-2(3H)-thione. Noncovalent C—H⋯π inter­actions between the centroid of the benzmidazole system and the SiMe3 groups form helicoidal arrangements in (2). Dimerization of (3) results in the formation of R 2 2(8) rings via N—H⋯S inter­actions, along with parallel π–π inter­actions between imidazole and benzene rings. PMID:26322611

  8. Contiguously substituted cyclooctane polyols. configurational assignments via (1)H NMR correlations and symmetry considerations.

    PubMed

    Moura-Letts, Gustavo; Paquette, Leo A

    2008-10-01

    More advanced oxidation of the cyclooctadienol shown, readily available in enantiomerically pure form from D-glucose, has given rise to a series of intermediates whose relative (and ultimately absolute) configuration was assigned on the basis of (1)H/(1)H coupling constant analysis. The selectivities that were deduced in this manner were drawn from the sequential application of CrO3 oxidation in tandem with Luche reduction, two-step NMO-promoted osmylations bracketed by acetonide formation, and wholesale deprotection. The stereoselectivities of these reactions were traced by (1)H NMR spectroscopy, and the stereochemical assignments were confirmed by the presence or absence of symmetry in the final cyclooctane polyols (four shown) generated in this investigation.

  9. Congenital Cataracts and Gut Dysmotility in a DYNC1H1 Dyneinopathy Patient

    PubMed Central

    Gelineau-Morel, Rose; Lukacs, Marshall; Weaver, K. Nicole; Hufnagel, Robert B.; Gilbert, Donald L.; Stottmann, Rolf W.

    2016-01-01

    Whole exome sequencing continues to end the diagnostic odyssey for a number of patients and expands our knowledge of phenotypes associated with gene mutations. We describe an 11-year-old female patient with a constellation of symptoms including congenital cataracts, gut dysmotility, sensory neuropathy, and bifrontal polymicrogyria. Whole exome sequencing was performed and identified a de novo heterozygous missense mutation in the ATPase motor domain of cytoplasmic dynein heavy chain 1 (DYNC1H1), which is known to be involved in neuronal migration and retrograde axonal transport. The mutation was found to be highly damaging by multiple prediction programs. The residue is highly conserved, and reported mutations in this gene result in a variety of phenotypes similar to that of our patient. We report only the second case of congenital cataracts and the first of gut dysmotility in a patient with DYNC1H1, thus expanding the spectrum of disease seen in DYNC1H1 dyneinopathies. PMID:27754416

  10. 17O-Decoupled 1H Spectroscopy and Imaging with a Surface Coil: STEAM Decoupling

    NASA Astrophysics Data System (ADS)

    Charagundla, Sridhar R.; Duvvuri, Umamaheswar; Noyszewski, Elizabeth A.; Dandora, Rahul; Stolpen, Alan H.; Leigh, J. S.; Reddy, Ravinder

    2000-03-01

    17O-decoupled 1H spin-echo imaging has been reported as a means of indirect 17O detection, with potential application to measurement of blood flow and metabolism. In its current form, 17O decoupling requires large RF amplitudes and a 180° refocusing pulse, complicating its application in volume and surface coils, respectively. To overcome this problem, we have developed an 17O-decoupled proton stimulated echo sequence ("STEAM decoupling") to allow 17O detection with a surface coil. A high B1 amplitude is easily generated, allowing complete decoupling of 17O and 1H. Slice-selective, 17O-decoupled 1H imaging is readily performed and the sequence is easily adapted for localized spectroscopy. Intrinsic correction for variations in B1 and further compensation for B1 inhomogeneity are discussed.

  11. Aminosilanes derived from 1H-benzimidazole-2(3H)-thione.

    PubMed

    Palomo-Molina, Juliana; García-Báez, Efrén V; Contreras, Rosalinda; Pineda-Urbina, Kayim; Ramos-Organillo, Angel

    2015-09-01

    Two new molecular structures, namely 1,3-bis(trimethylsilyl)-1H-benzimidazole-2(3H)-thione, C13H22N2SSi2, (2), and 1-trimethylsilyl-1H-benzimidazole-2(3H)-thione, C10H14N2SSi, (3), are reported. Both systems were derived from 1H-benzimidazole-2(3H)-thione. Noncovalent C-H···π interactions between the centroid of the benzmidazole system and the SiMe3 groups form helicoidal arrangements in (2). Dimerization of (3) results in the formation of R2(2)(8) rings via N-H···S interactions, along with parallel π-π interactions between imidazole and benzene rings.

  12. Multislice 1H magnetic resonance spectroscopic imaging: assessment of epilepsy, Alzheimer's disease, and amyotrophic lateral sclerosis

    NASA Astrophysics Data System (ADS)

    Weiner, Michael W.; Maudsley, Andrew A.; Schuff, Norbert; Soher, Brian J.; Vermathen, Peter P.; Fein, George; Laxer, Kenneth D.

    1998-07-01

    Proton magnetic resonance spectroscopic imaging (1H MRSI) with volume pre-selection (i.e. by PRESS) or multislice 1H MRSI was used to investigate changes in brain metabolites in Alzheimer's disease, epilepsy, and amyotrophic lateral sclerosis. Examples of results from several ongoing clinical studies are provided. Multislice 1H MRSI of the human brain, without volume pre-selection offers considerable advantages over previously available techniques. Furthermore, MRI tissue segmentation and completely automated spectra curve fitting greatly facilitate quantitative data analysis. Future efforts will be devoted to obtaining full brain coverage and data acquisition at short spin echo times (TE less than 30 ms) for the detection of metabolites with short T2 relaxation times.

  13. 40 CFR 721.1750 - 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium salts. 721.1750 Section 721.1750... 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium...-tyl-oxy)-, sodium salt (PMN P-92-35), and 1H-benzotriazole, 5-(pentyloxy)- , potassium salt (PMN...

  14. 40 CFR 721.1750 - 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium salts. 721.1750 Section 721.1750... 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium...-tyl-oxy)-, sodium salt (PMN P-92-35), and 1H-benzotriazole, 5-(pentyloxy)- , potassium salt (PMN...

  15. 40 CFR 721.1750 - 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium salts. 721.1750 Section 721.1750... 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium...-tyl-oxy)-, sodium salt (PMN P-92-35), and 1H-benzotriazole, 5-(pentyloxy)- , potassium salt (PMN...

  16. 40 CFR 721.1750 - 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium salts. 721.1750 Section 721.1750... 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium...-tyl-oxy)-, sodium salt (PMN P-92-35), and 1H-benzotriazole, 5-(pentyloxy)- , potassium salt (PMN...

  17. 40 CFR 721.1750 - 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium salts. 721.1750 Section 721.1750... 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium...-tyl-oxy)-, sodium salt (PMN P-92-35), and 1H-benzotriazole, 5-(pentyloxy)- , potassium salt (PMN...

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

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-11-01

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

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

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-11-01

    Previously, we reported a reliable DU8 method for natural bond orbital (NBO)-aided parametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. As sophisticated NMR experiments for precise measurements of carbon-proton SSCCs are becoming more user-friendly and broadly utilized by the organic chemistry community to guide and inform the process of structure determination of complex organic compounds, we have now developed a fast and accurate method for computing (13)C-(1)H SSCCs. Fermi contacts computed with the DU8 basis set are scaled using selected NBO parameters in conjunction with empirical scaling coefficients. The method is optimized for inexpensive B3LYP/6-31G(d) geometries. The parametric scaling is based on a carefully selected training set of 274 ((3)J), 193 ((2)J), and 143 ((1)J) experimental (13)C-(1)H spin-spin coupling constants reported in the literature. The DU8 basis set, optimized for computing Fermi contacts, which by design had evolved from optimization of a collection of inexpensive 3-21G*, 4-21G, and 6-31G(d) bases, offers very short computational (wall) times even for relatively large organic molecules containing 15-20 carbon atoms. The most informative SSCCs for structure determination, i.e., (3)J, were computed with an accuracy of 0.41 Hz (rmsd). The new unified approach for computing (1)H-(1)H and (13)C-(1)H SSCCs is termed "DU8c". PMID:26414291

  20. Synthesis of 1H-indole-2,3-dione-3-thiosemicarbazone ribonucleosides as antibacterial agents.

    PubMed

    Kassab, Shaymaa E; Hegazy, Gehan H; Eid, Nahed M; Amin, Kamelia M; El-Gendy, Adel A

    2010-01-01

    A new isatin ribonucleoside (3) was synthesized in a good yield by trimethylsilyl trifluoromethanesulfonate (TMSOTf) catalyzed coupling reaction between the silylated nitrogenated base of 1H-Indole-2,3-dione (1) and 1,2,3,5-tetra-O-acetyl-beta-D-ribfuranose (2). Thiosemicarbazides 4a-e were utilized by the prepared ribonucleoside (3) to give new series of 1H-indole-2,3-dione-3-thiosemicarbazone ribonucleosides 5a-e. All compounds tested as antibacterial agents showed slight inhibitory activity against the selected bacterial strains.

  1. Fruit juice authentication by 1H NMR spectroscopy in combination with different chemometrics tools.

    PubMed

    Cuny, M; Vigneau, E; Le Gall, G; Colquhoun, I; Lees, M; Rutledge, D N

    2008-01-01

    To discriminate orange juice from grapefruit juice in a context of fraud prevention, (1)H NMR data were submitted to different treatments to extract informative variables which were then analysed using multivariate techniques. Averaging contiguous data points of the spectrum followed by logarithmic transformation improved the results of the data analysis. Moreover, supervised variable selection methods gave better rates of classification of the juices into the correct groups. Last, independent-component analysis gave better classification results than principal-component analysis. Hence, ICA may be an efficient chemometric tool to detect differences in the (1)H NMR spectra of similar samples, and so may be useful for authentication of foods.

  2. 1H and 13C NMR assignments for the cyanine dyes SYBR Safe and thiazole orange.

    PubMed

    Evenson, William E; Boden, Lauren M; Muzikar, Katy A; O'Leary, Daniel J

    2012-12-01

    Analysis of (1)H and (13)C NMR and mass spectral data for the fluorescent nucleic acid stain SYBR Safe indicates that it contains a cyanine-based cationic core structure identical to thiazole orange. The difference between these two compounds is the type of N-substitution on the quinolinium ring system (SYBR Safe, n-Pr; thiazole orange, Me). The (1)H and (13)C NMR resonances for both compounds were assigned on the basis of one- and two-dimensional (COSY, ROESY, HSQC, and HMBC) experiments. The preferred conformation of these compounds was computed by ab initio methods and found to be consistent with the NMR data.

  3. The (1) H NMR spectrum of pyrazole in a nematic phase.

    PubMed

    Provasi, Patricio; Jimeno, María Luisa; Alkorta, Ibon; Reviriego, Felipe; Elguero, José; Jokisaari, Jukka

    2016-08-01

    The experimental (1) H nuclear magnetic resonance (NMR) spectrum of 1H-pyrazole was recorded in thermotropic nematic liquid crystal N-(p-ethoxybenzylidene)-p-butylaniline (EBBA) within the temperature range of 299-308 K. Two of three observable dipolar DHH -couplings appeared to be equal at each temperature because of fast prototropic tautomerism. Analysis of the Saupe orientational order parameters using fixed geometry determined by computations and experimental dipolar couplings results in a situation in which the molecular orientation relative to the magnetic field (and the liquid crystal director) can be described exceptionally by a single parameter. Copyright © 2016 John Wiley & Sons, Ltd.

  4. Detection of hydrogen dissolved in acrylonitrile butadiene rubber by 1H nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Nishimura, Shin; Fujiwara, Hirotada

    2012-01-01

    Rubber materials, which are used for hydrogen gas seal, can dissolve hydrogen during exposure in high-pressure hydrogen gas. Dissolved hydrogen molecules were detected by solid state 1H NMR of the unfilled vulcanized acrylonitrile butadiene rubber. Two signals were observed at 4.5 ppm and 4.8 ppm, which were assignable to dissolved hydrogen, in the 1H NMR spectrum of NBR after being exposed 100 MPa hydrogen gas for 24 h at room temperature. These signals were shifted from that of gaseous hydrogen molecules. Assignment of the signals was confirmed by quantitative estimation of dissolved hydrogen and peak area of the signals.

  5. Elevated Glutamatergic Compounds in Pregenual Anterior Cingulate in Pediatric Autism Spectrum Disorder Demonstrated by 1H MRS and 1H MRSI

    PubMed Central

    Bejjani, Anthony; O'Neill, Joseph; Kim, John A.; Frew, Andrew J.; Yee, Victor W.; Ly, Ronald; Kitchen, Christina; Salamon, Noriko; McCracken, James T.; Toga, Arthur W.; Alger, Jeffry R.; Levitt, Jennifer G.

    2012-01-01

    Recent research in autism spectrum disorder (ASD) has aroused interest in anterior cingulate cortex and in the neurometabolite glutamate. We report two studies of pregenual anterior cingulate cortex (pACC) in pediatric ASD. First, we acquired in vivo single-voxel proton magnetic resonance spectroscopy (1H MRS) in 8 children with ASD and 10 typically developing controls who were well matched for age, but with fewer males and higher IQ. In the ASD group in midline pACC, we found mean 17.7% elevation of glutamate + glutamine (Glx) (p<0.05) and 21.2% (p<0.001) decrement in creatine + phosphocreatine (Cr). We then performed a larger (26 subjects with ASD, 16 controls) follow-up study in samples now matched for age, gender, and IQ using proton magnetic resonance spectroscopic imaging (1H MRSI). Higher spatial resolution enabled bilateral pACC acquisition. Significant effects were restricted to right pACC where Glx (9.5%, p<0.05), Cr (6.7%, p<0.05), and N-acetyl-aspartate + N-acetyl-aspartyl-glutamate (10.2%, p<0.01) in the ASD sample were elevated above control. These two independent studies suggest hyperglutamatergia and other neurometabolic abnormalities in pACC in ASD, with possible right-lateralization. The hyperglutamatergic state may reflect an imbalance of excitation over inhibition in the brain as proposed in recent neurodevelopmental models of ASD. PMID:22848344

  6. Dichloridobis{2-[(1H-1,2,4-triazol-1-yl)meth­yl]-1H-benzimidazole-κN 3}­zinc(II)

    PubMed Central

    Zhang, Wei-Peng; Zhang, Jiao-Lin; Hao, Bao-Lian; Yang, Huai-Xia

    2013-01-01

    In the title complex, [ZnCl2(C10H9N5)2], the ZnII ion is coordinated by two N atoms from two 2-[(1H-1,2,4-triazol-1-yl)meth­yl]-1H-benzimidazole (tmb) ligands and by two chloride ligands in a slightly distorted tetra­hedral geometry. In the tmb ligands, the benzimidazole rings systems are essentially planar, with maximum deviations from the mean plane of 0.021 (3) and 0.030 (3) Å, and form dihedral angles of 73.2 (2) and 83.5 (2)° with the triazole rings. In the crystal, N—H⋯N hydrogen bonds link complex mol­ecules into chains along [010]. In addition, weak C—H⋯Cl and C—H⋯N hydrogen bonds complete a three-dimensional network. Two weak intra­molecular C—H⋯Cl hydrogen bonds are also observed. PMID:23723759

  7. Spectroscopic characterization and density functional studies of (Z)-1-[(2-methoxy-5-(trifluoromethyl)phenylamino)methylene]naphthalene-2(1H)-one

    NASA Astrophysics Data System (ADS)

    Alpaslan, Yelda Bingöl; Gökce, Halil; Alpaslan, Gökhan; Macit, Mustafa

    2015-10-01

    In the current work, the Schiff base compound (Z)-1-[(2-Methoxy-5-(trifluoromethyl)phenylamino)methylene]naphthalene-2(1H)-one (I) has been characterized by using 13C NMR, 1H NMR, FT-IR and UV-vis spectroscopic techniques. Molecular geometry of the compound I in the ground state, vibrational frequencies, electronic absorption spectra and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values have been calculated by using the density functional method (DFT) with 6-311++G(d,p) basis set and compared with the experimental data. The optimized geometric parameters obtained by using DFT (B3LYP/6-311++G(d,p)) show good agreement with the experimental data. The vibrational frequencies were determined based on the recorded FT-IR spectra in the range of 4000-400 cm-1 for solid state. Using the TD-DFT method, electronic absorption spectra of the compound I have been predicted and good agreement is determined with the experimental ones. In addition, molecular electrostatic potential (MEP), frontier molecular orbital analysis (HOMO-LUMO), non-linear optical (NLO) properties, NBO analysis and NBO atomic charges of the compound I were investigated using same theoretical calculations.

  8. 1H, 13C, 195Pt and 15N NMR structural correlations in Pd(II) and Pt(II) chloride complexes with various alkyl and aryl derivatives of 2,2'-bipyridine and 1,10-phenanthroline.

    PubMed

    Pawlak, Tomasz; Pazderski, Leszek; Sitkowski, Jerzy; Kozerski, Lech; Szłyk, Edward

    2011-02-01

    (1)H, (13)C, (195)Pt and (15)N NMR studies of platinide(II) (M = Pd, Pt) chloride complexes with such alkyl and aryl derivatives of 2,2'-bipyridine and 1,10-phenanthroline as LL = 6,6'-dimethyl-bpy, 5,5'-dimethyl-bpy, 4,4'-di-tert-butyl-bpy, 2,9-dimethyl-phen, 2,9-dimethyl-4,7-diphenyl-phen, 3,4,7,8-tetramethyl-phen, having the general [M(LL)Cl(2)] formula were performed and the respective chemical shifts (δ(1H), δ(13C), δ(195Pt), δ(15N)) reported. (1)H high-frequency coordination shifts (Δ(coord)(1H) = δ(complex)(1H)-δ(ligand)(1H)) mostly pronounced for nitrogen-adjacent protons and methyl groups in the nearest adjacency of nitrogen, as well as (15)N low-frequency coordination shifts (Δ(coord)(15H) = δ(complex)(15H)-δ(ligand)(15H)) were discussed in relation to the molecular structures.

  9. Low-frequency wave activity related to dipolarization fronts detected by MMS in the magnetotail

    NASA Astrophysics Data System (ADS)

    Le Contel, O.; Retino, A.; Breuillard, H.; Mirioni, L.; Roux, A.; Chust, T.; Chasapis, A.; Lavraud, B.; Lindqvist, P. A.; Khotyaintsev, Y. V.; Vaivads, A.; Fu, H.; Marklund, G. T.; Nakamura, R.; Burch, J. L.; Torbert, R. B.; Moore, T. E.; Ergun, R.; Goodrich, K.; Needell, J.; Chutter, M.; Rau, D.; Dors, I.; Russell, C. T.; Magnes, W.; Strangeway, R. J.; Le, G.; Bromund, K. R.; Plaschke, F.; Fischer, D.; Leinweber, H. K.; Anderson, B. J.; Argall, M. R.; Slavin, J. A.; Kepko, L.; Baumjohann, W.; Pollock, C. J.; Mauk, B.; Fuselier, S. A.

    2015-12-01

    Dipolarization fronts are often associated to reconnection jets in the magnetotail current sheet and are sites of important energy dissipation and particle energization. Since the launch on March 12th and until the 9th of July 2015, the MMS constellation has been moving from dawn to dusk in a string of pearls formation. Although particle instruments were rarely operating and only FIELDS instrument suite was often gathering data, the MMS spacecraft have detected numerous dipolarization fronts, in particular on May 15th. Since 9th of July, the MMS evolved into a tetrahedral configuration with an average inter-satellite distance of 160 km and was still able to detect dipolarization fronts in the dusk magnetotail. As the Larmor radius of thermal protons is about 500 km in this region and dipolarization fronts have a typical thickness of the order of the Larmor radius, such a separation allows us to investigate in detail the microphysics of dipolarization fronts. In this study, we focus in particular on low-frequency electromagnetic wave activity related to the fronts and discuss possible mechanisms of particle heating and acceleration both at large scales (string of pearls configuration) and at kinetic scales (tetrahedral configuration).

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

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

    PubMed

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

    2014-10-01

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

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

    ERIC Educational Resources Information Center

    Debska, Barbara; Guzowska-Swider, Barbara

    2007-01-01

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

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

    PubMed

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

    1997-01-01

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

  14. (1) H NMR analysis of O-methyl-inositol isomers: a joint experimental and theoretical study.

    PubMed

    De Almeida, Mauro V; Couri, Mara Rubia C; De Assis, João Vitor; Anconi, Cleber P A; Dos Santos, Hélio F; De Almeida, Wagner B

    2012-09-01

    Density functional theory (DFT) calculations of (1) H NMR chemical shifts for l-quebrachitol isomers were performed using the B3LYP functional employing the 6-31G(d,p) and 6-311 + G(2d,p) basis sets. The effect of the solvent on the B3LYP-calculated NMR spectrum was accounted for using the polarizable continuum model. Comparison is made with experimental (1) H NMR spectroscopic data, which shed light on the average uncertainty present in DFT calculations of chemical shifts and showed that the best match between experimental and theoretical B3LYP (1) H NMR profiles is a good strategy to assign the molecular structure present in the sample handled in the experimental measurements. Among four plausible O-methyl-inositol isomers, the l-quebrachitol 2a structure was unambiguously assigned based only on the comparative analysis of experimental and theoretical (1) H NMR chemical shift data. The B3LYP infrared (IR) spectrum was also calculated for the four isomers and compared with the experimental data, with analysis of the theoretical IR profiles corroborating assignment of the 2a structure. Therefore, it is confirmed in this study that a combined experimental/DFT spectroscopic investigation is a powerful tool in structural/conformational analysis studies. PMID:22865668

  15. Aminosilanes derived from 1H-benzimidazole-2(3H)-thione

    SciTech Connect

    Palomo-Molina, Juliana; García-Báez, Efrén V.; Pineda-Urbina, Kayim; Ramos-Organillo, Angel

    2015-08-12

    In two trimethylsilyl-substituted 1H-benzimidazole-2(3H)-thiones, noncovalent C—H⋯π interactions between the centroid of the benzmidazole system and the SiMe{sub 3} groups form helicoidal arrangements in one, and dimerization results in the formation of R{sub s} {sup 2}(8) rings via N—H⋯S interactions, along with parallel π–π interactions between imidazole and benzene rings, in the second compound. Two new molecular structures, namely 1,3-bis(trimethylsilyl)-1H-benzimidazole-2(3H)-thione, C{sub 13}H{sub 22}N{sub 2}SSi{sub 2}, (2), and 1-trimethylsilyl-1H-benzimidazole-2(3H)-thione, C{sub 10}H{sub 14}N{sub 2}SSi, (3), are reported. Both systems were derived from 1H-benzimidazole-2(3H)-thione. Noncovalent C—H⋯π interactions between the centroid of the benzmidazole system and the SiMe{sub 3} groups form helicoidal arrangements in (2). Dimerization of (3) results in the formation of R{sub 2}{sup 2}(8) rings via N—H⋯S interactions, along with parallel π–π interactions between imidazole and benzene rings.

  16. 32 CFR 1630.15 - Class 1-H: Registrant not subject to processing for induction.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... for induction. 1630.15 Section 1630.15 National Defense Other Regulations Relating to National Defense... induction. In Class 1-H shall be placed any registrant who is not eligible for Class 1-A and is not currently subject to processing for induction....

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

    PubMed

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

    2014-10-01

    Urea at ∼12 M in concentrated gelatin gel, that was stretched, gave (1)H and (2)H NMR spectral splitting patterns that varied in a predictable way with changes in the relative proportions of (1)H2O and (2)H2O in the medium. This required consideration of the combinatorics of the two amide groups in urea that have a total of four protonation/deuteration sites giving rise to 16 different isotopologues, if all the atoms were separately identifiable. The rate constant that characterized the exchange of the protons with water was estimated by back-transformation analysis of 2D-EXSY spectra. There was no (1)H NMR spectral evidence that the chiral gelatin medium had caused in-equivalence in the protons bonded to each amide nitrogen atom. The spectral splitting patterns in (1)H and (2)H NMR spectra were accounted for by intra-molecular scalar and dipolar interactions, and quadrupolar interactions with the electric field gradients of the gelatin matrix, respectively. PMID:25241007

  18. In vivo hyperpolarized 13C MR spectroscopic imaging with 1H decoupling

    NASA Astrophysics Data System (ADS)

    Chen, Albert P.; Tropp, James; Hurd, Ralph E.; Van Criekinge, Mark; Carvajal, Lucas G.; Xu, Duan; Kurhanewicz, John; Vigneron, Daniel B.

    2009-03-01

    Application of 13C MRS in vivo on whole body MR system has been limited due to the low static field (and consequent low signal to noise ratio—SNR) of these scanners; thus there have been few reports of 1H decoupled 13C MRS in vivo using a clinical MR platform. The recent development of techniques to retain highly polarized spins in solution following DNP in a solid matrix has provided a mechanism to use endogenous pre-polarized 13C labeled substrates to study real time cellular metabolism in vivo with high SNR. In a recent in vivo hyperpolarized metabolic imaging study using 13C pyruvate, it has been demonstrated that the line shape (signal decay) of the resonances observed are greatly affected by JCH coupling in addition to inhomogeneous broadening. This study demonstrates the feasibility of improving hyperpolarized 13C metabolic imaging in vivo by incorporating 1H decoupling on a clinical whole body 3 T MR scanner. No reduction of T1 of a pre-polarized 13C substrate ([1- 13C] lactate) in solution was observed when 1H decoupling was applied with WALTZ16 sequence. Narrower linewidth for the [1- 13C] lactate resonance was observed in hyperpolarized 13C MRSI data in vivo with 1H decoupling.

  19. (1) H NMR analysis of O-methyl-inositol isomers: a joint experimental and theoretical study.

    PubMed

    De Almeida, Mauro V; Couri, Mara Rubia C; De Assis, João Vitor; Anconi, Cleber P A; Dos Santos, Hélio F; De Almeida, Wagner B

    2012-09-01

    Density functional theory (DFT) calculations of (1) H NMR chemical shifts for l-quebrachitol isomers were performed using the B3LYP functional employing the 6-31G(d,p) and 6-311 + G(2d,p) basis sets. The effect of the solvent on the B3LYP-calculated NMR spectrum was accounted for using the polarizable continuum model. Comparison is made with experimental (1) H NMR spectroscopic data, which shed light on the average uncertainty present in DFT calculations of chemical shifts and showed that the best match between experimental and theoretical B3LYP (1) H NMR profiles is a good strategy to assign the molecular structure present in the sample handled in the experimental measurements. Among four plausible O-methyl-inositol isomers, the l-quebrachitol 2a structure was unambiguously assigned based only on the comparative analysis of experimental and theoretical (1) H NMR chemical shift data. The B3LYP infrared (IR) spectrum was also calculated for the four isomers and compared with the experimental data, with analysis of the theoretical IR profiles corroborating assignment of the 2a structure. Therefore, it is confirmed in this study that a combined experimental/DFT spectroscopic investigation is a powerful tool in structural/conformational analysis studies.

  20. Mutation screen reveals novel variants and expands the phenotypes associated with DYNC1H1

    PubMed Central

    Strickland, Alleene V.; Schabhüttl, Maria; Offenbacher, Hans; Synofzik, Matthis; Hauser, Natalie S.; Brunner-Krainz, Michaela; Gruber-Sedlmayr, Ursula; Moore, Steven A.; Windhager, Reinhard; Bender, Benjamin; Harms, Matthew; Klebe, Stephan; Young, Peter; Kennerson, Marina; Garcia, Avencia Sanchez Mejias; Gonzalez, Michael A.; Züchner, Stephan; Schule, Rebecca; Shy, Michael E.; Auer-Grumbach, Michaela

    2015-01-01

    Dynein, cytoplasmic 1, heavy chain 1 (DYNC1H1) encodes a necessary subunit of the cytoplasmic dynein complex, which traffics cargo along microtubules. Dominant DYNC1H1 mutations are implicated in neural diseases, including spinal muscular atrophy with lower extremity dominance (SMA-LED), intellectual disability with neuronal migration defects, malformations of cortical development (MCD), and Charcot-Marie-Tooth disease, type 2O (CMT2O). We hypothesized that additional variants could be found in these and novel motoneuron and related diseases. Therefore we analysed our database of 1,024 whole exome sequencing samples of motoneuron and related diseases for novel single nucleotide variations. We filtered these results for significant variants, which were further screened using segregation analysis in available family members. Analysis revealed six novel, rare, and highly conserved variants. Three of these are likely pathogenic and encompass a broad phenotypic spectrum with distinct disease clusters. Our findings suggest that DYNC1H1 variants can cause not only lower, but also upper motor neuron disease. It thus adds DYNC1H1 to the growing list of spastic paraplegia related genes in microtubule-dependent motor protein pathways. PMID:26100331

  1. Microwave frequency modulation for improving polarization transfer in DNP experiments

    NASA Astrophysics Data System (ADS)

    Guy, Mallory; Ramanathan, Chandrasekhar

    Dynamic nuclear polarization (DNP) is a driven process that transfers the inherently high electron polarization to surrounding nuclear spins via microwave irradiation at or near the electron Larmor frequency. In a typical DNP experiment, the amplitude and frequency of the applied microwaves are constant. However, by adding time dependence in the form of frequency modulation, the electron excitation bandwidth is increased, thereby increasing the number of electron spins active in the polarization transfer process and improving overall efficiency. Both triangular and sinusoidal modulation show a 3 fold improvement over monochromatic irradiation. In the present study, we compare the nuclear spin polarization after DNP experiments with no modulation of the applied microwaves, triangular and sinusoidal modulation, and modulation schemes derived from the sample's ESR spectrum. We characterize the polarization as a function of the modulation amplitude and frequency and compare the optimal results from each modulation scheme. Working at a field of 3.34 T and at a temperature of 4 K, we show that by using a modulation scheme tailored to the electronic environment of the sample, polarization transfer is improved over other modulation schemes. Small-scale simulations of the spin system are developed to gain further insight into the dynamics of this driven open system. This understanding could enable the design of modulation schemes to achieve even higher polarization transfer efficiencies. With support from NSF (CHE-1410504) and by NIH (U19-A1091173).

  2. The Suppression of Dominant Acoustic Frequencies in MRI

    NASA Astrophysics Data System (ADS)

    Shou, Xingxian; Brown, Robert

    2011-03-01

    Patient discomfort and brain imaging distortion are serious MRI acoustic noise problems arising from the rapid switching on and off of gradient coils in the presence of the strong Larmor magnetic field. A study is made of dominant frequencies in the acoustic noise spectrum and, motivated by both spring and string ideas, we propose the cancellation of selected frequencies by appropriate gradient pulse sequence design. From both simulations and experiments, vibrations resulting from an impulsive force associated with a ramping up of a gradient pulse are shown to be cancelled upon the application of another impulsive force coming from the appropriately timed ramping down of that pulse. A method for the suppression of multiple-frequency contributions involving a series of gradient pulses with variable timings is developed and confirmed by experiment. Whether we refer to reduction in terms of dB (about 30-40 dB per peak), or to the verdict of a listener, the conclusion is that a marked reduction in sound can be achieved when at least three of the dominant frequency peaks are suppressed. A variety of pulse profiles and timing combinations can be used to attenuate important contributions to the acoustic spectrum. Supported by the Ohio Third Frontier Program.

  3. MTR and In-vivo 1H-MRS studies on mouse brain with parkinson's disease

    NASA Astrophysics Data System (ADS)

    Yoon, Moon-Hyun; Kim, Hyeon-Jin; Chung, Jin-Yeung; Doo, Ah-Reum; Park, Hi-Joon; Kim, Seung-Nam; Choe, Bo-Young

    2012-12-01

    The aim of this study was to investigate whether the changes in the magnetization transfer ratio (MTR) histogram are related to specific characteristics of Parkinson's disease (PD) and to investigate whether the MTR histogram parameters are associated with neurochemical dysfunction by performing in vivo proton magnetic resonance spectroscopy (1H-MRS). MTR and in vivo 1H-MRS studies were performed on control mice (n = 10) and 1-methyl-1,2,3,6-tetrahydropyridine intoxicated mice (n = 10). All the MTR and in vivo 1H-MRS experiments were performed on a 9.4 T MRI/MRS system (Bruker Biospin, Germany) using a standard head coil. The protondensity fast spin echo (FSE) images and the T2-weighted spin echo (SE) images were acquired with no gap. Outer volume suppression (OVS), combined with the ultra-short echo-time stimulated echo acquisition mode (STEAM), was used for the localized in-vivo 1H-MRS. The quantitative analysis of metabolites was performed from the 1H spectra obtained in vivo on the striatum (ST) by using jMRUI (Lyon, France). The peak height of the MTR histograms in the PD model group was significantly lower than that in the control group (p < 0.05). The midbrain MTR values for volume were lower in the PD group than the control group(p < 0.05). The complex peak (Glx: glutamine+glutamate+ GABA)/creatine (Cr) ratio of the right ST in the PD group was significantly increased as compared to that of the control group. The present study revealed that the peak height of the MTR histogram was significantly decreased in the ST and substantia nigra, and a significant increase in the Gl x /Cr ratio was found in the ST of the PD group, as compared with that of the control group. These findings could reflect the early phase of neuronal dysfunction of neurotransmitters.

  4. Natural attenuation of oil spills in Patagonian soils. Characterization by 1H NMR spectroscopy.

    PubMed

    Ríos, S M; Nudelman, N S

    2008-01-01

    The natural attenuation of oil spill contaminated soils, with different exposure times, in Patagonian environment was evaluated by the use of several parameters to quantify the degree of changes in the composition. Column (CC) and gas chromatography (GC); UV-visible and 1H NMR techniques were used to determine compositional and structural indexes. The results show that the nC18/Phytane GC index, that was 1.5 for crude oil, decreased with exposure time to values between 0.97-0.17 in the residues. The percentages for the four aliphatic (H1-H4) and the aromatic (H(A)), proton types, determined by 1H NMR, were: 12.9-34.4 (H1), 43.3-60.2 (H2), 4.24-24.2 (H), 1.33-17.9 (H4), and 0.44-4.81 (HA), in crude oil and residues, respectively. Furthermore, the characterization of significant 1H NMR signals indicated the presence of carboxylic acid hydrogens in the polar fraction of the crude oil and of residues of two years age. The Principal Components Analysis (PCA) of the parameters determined by CC, GC and NMR showed that the first three principal components (1st, 2nd, and 3 rd PC), accounted for more than 84% of variance. The 1st PC is largely influenced by H, H,, H, H, and the nC,,/Phytane GC parameter, in the order given. The evaluation of the different parameters by PCA suggests that 1H NMR is more useful than GC to evaluate the degree of the chemical transformations of oil spills in soils

  5. Gas phase synthesis and reactivity of Agn+ and Ag(n-1)H+ cluster cations.

    PubMed

    Khairallah, George N; O'Hair, Richard A J

    2005-08-21

    Multi-stage mass spectrometry (MSn) on [(M + Ag - H)x + Ag]+ precursor ions (where M = an amino acid such as glycine or N,N-dimethylglycine) results in the formation of stable silver (Ag3+, Ag5+ and Ag7+) and silver hydride (Ag2H+, Ag4H+ and Ag6H+) cluster cations in the gas phase. Deuterium labelling studies reveal that the source of the hydride can be either from the alpha carbon or from one of the heteroatoms. When M = glycine, the silver cyanide clusters Ag4CN+ and Ag5(H,C,N)+ are also observed. Collision induced dissociation (CID) and DFT calculations were carried out on each of these clusters to shed some light on their possible structures. CID of the Agn+ and Ag(n-1)H+ clusters generally results in the formation of the same Ag(n-2)+ product ions via the loss of Ag2 and AgH respectively. DFT calculations also reveal that the Agn+ and Ag(n-1)H+ clusters have similar structural features and that the Ag(n-1)H+ clusters are only slightly less stable than their all silver counterparts. In addition, Agn+ and Ag(n-1)H+ clusters react with 2-propanol and 2-butylamine via similar pathways, with multiple ligand addition occurring and a coupled deamination-dehydration reaction occurring upon condensation of a third (for Ag2H+) or a fourth (for all other silver clusters) 2-butylamine molecule onto the clusters. Taken together, these results suggest that the Agn+ and Ag(n-1)H+ clusters are structurally related via the replacement of a silver atom with a hydrogen atom. This replacement does not dramatically alter the cluster stability or its unimolecular or bimolecular chemistry with the 2-propanol and 2-butylamine reagents.

  6. Mutations in the tail domain of DYNC1H1 cause dominant spinal muscular atrophy

    PubMed Central

    Harms, M.B.; Ori-McKenney, K.M.; Scoto, M.; Tuck, E.P.; Bell, S.; Ma, D.; Masi, S.; Allred, P.; Al-Lozi, M.; Reilly, M.M.; Miller, L.J.; Jani-Acsadi, A.; Pestronk, A.; Shy, M.E.; Muntoni, F.; Vallee, R.B.

    2012-01-01

    Objective: To identify the gene responsible for 14q32-linked dominant spinal muscular atrophy with lower extremity predominance (SMA-LED, OMIM 158600). Methods: Target exon capture and next generation sequencing was used to analyze the 73 genes in the 14q32 linkage interval in 3 SMA-LED family members. Candidate gene sequencing in additional dominant SMA families used PCR and pooled target capture methods. Patient fibroblasts were biochemically analyzed. Results: Regional exome sequencing of all candidate genes in the 14q32 interval in the original SMA-LED family identified only one missense mutation that segregated with disease state—a mutation in the tail domain of DYNC1H1 (I584L). Sequencing of DYNC1H1 in 32 additional probands with lower extremity predominant SMA found 2 additional heterozygous tail domain mutations (K671E and Y970C), confirming that multiple different mutations in the same domain can cause a similar phenotype. Biochemical analysis of dynein purified from patient-derived fibroblasts demonstrated that the I584L mutation dominantly disrupted dynein complex stability and function. Conclusions: We demonstrate that mutations in the tail domain of the heavy chain of cytoplasmic dynein (DYNC1H1) cause spinal muscular atrophy and provide experimental evidence that a human DYNC1H1 mutation disrupts dynein complex assembly and function. DYNC1H1 mutations were recently found in a family with Charcot-Marie-Tooth disease (type 2O) and in a child with mental retardation. Both of these phenotypes show partial overlap with the spinal muscular atrophy patients described here, indicating that dynein dysfunction is associated with a range of phenotypes in humans involving neuronal development and maintenance. PMID:22459677

  7. Crystal structures of the two salts 2-methyl-1H-imidazol-3-ium nitrate–2-methyl-1H-imidazole (1/1) and 2-methyl-1H-imidazol-3-ium nitrate

    PubMed Central

    Diop, Mouhamadou Birame; Diop, Libasse; Maris, Thierry

    2016-01-01

    The title salts, C4H7N2 +·NO3 −·C4H6N2, (I), and C4H7N2 +·NO3 −, (II), were obtained from solutions containing 2-methyl­imidazole and nitric acid in different concentrations. In the crystal structure of salt (I), one of the –NH H atoms of the imidazole ring shows half-occupancy, hence only every second mol­ecule is in its cationic form. The nitrate anion in this structure lies on a twofold rotation axis. The neutral 2-methyl­imidazole mol­ecule and the 2-methyl-1H-imidazol-3-ium cation inter­act through N—H⋯N hydrogen bonds to form [(C4H6N2)⋯(C4H7N2)+] pairs. These pairs are linked with two nitrate anions on both sides through bifurcated N—H⋯(O,O) hydrogen bonds into chains running parallel to [001]. In the crystal structure of salt (II), the C4H7N2 + cation and the NO3 − anion are both located on a mirror plane, leading to a statistical disorder of the methyl H atoms. The cations and anions again inter­act through bifurcated N—H⋯(O,O) hydrogen bonds, giving rise to the formation of chains consisting of alternating anions and cations parallel to [100]. PMID:27375869

  8. Crystal structures of the two salts 2-methyl-1H-imidazol-3-ium nitrate-2-methyl-1H-imidazole (1/1) and 2-methyl-1H-imidazol-3-ium nitrate.

    PubMed

    Diop, Mouhamadou Birame; Diop, Libasse; Maris, Thierry

    2016-04-01

    The title salts, C4H7N2 (+)·NO3 (-)·C4H6N2, (I), and C4H7N2 (+)·NO3 (-), (II), were obtained from solutions containing 2-methyl-imidazole and nitric acid in different concentrations. In the crystal structure of salt (I), one of the -NH H atoms of the imidazole ring shows half-occupancy, hence only every second mol-ecule is in its cationic form. The nitrate anion in this structure lies on a twofold rotation axis. The neutral 2-methyl-imidazole mol-ecule and the 2-methyl-1H-imidazol-3-ium cation inter-act through N-H⋯N hydrogen bonds to form [(C4H6N2)⋯(C4H7N2)(+)] pairs. These pairs are linked with two nitrate anions on both sides through bifurcated N-H⋯(O,O) hydrogen bonds into chains running parallel to [001]. In the crystal structure of salt (II), the C4H7N2 (+) cation and the NO3 (-) anion are both located on a mirror plane, leading to a statistical disorder of the methyl H atoms. The cations and anions again inter-act through bifurcated N-H⋯(O,O) hydrogen bonds, giving rise to the formation of chains consisting of alternating anions and cations parallel to [100]. PMID:27375869

  9. Achievement of 1 H-19 F heteronuclear experiments using the conventional spectrometer with a shared single high band amplifier.

    PubMed

    Sakuma, Chiseko; Kurita, Jun-ichi; Furihata, Kazuo; Tashiro, Mitsuru

    2015-05-01

    The (1)H-(19) F heteronuclear NMR experiments were achieved using the conventional spectrometer equipped with a single high band amplifier and a (1)H/(19)F/(13) C double-tuned probe. Although double high band amplifiers are generally required to perform such experiments, a simple modification of pathway in the conventional spectrometer was capable of acquiring various (1)H-(19)F heteronuclear spectra. The efficiency of the present technique was demonstrated in an application for (19)F{(1)H} and (1)H{(19)F} saturation transfer difference experiments. PMID:25808615

  10. Achievement of 1 H-19 F heteronuclear experiments using the conventional spectrometer with a shared single high band amplifier.

    PubMed

    Sakuma, Chiseko; Kurita, Jun-ichi; Furihata, Kazuo; Tashiro, Mitsuru

    2015-05-01

    The (1)H-(19) F heteronuclear NMR experiments were achieved using the conventional spectrometer equipped with a single high band amplifier and a (1)H/(19)F/(13) C double-tuned probe. Although double high band amplifiers are generally required to perform such experiments, a simple modification of pathway in the conventional spectrometer was capable of acquiring various (1)H-(19)F heteronuclear spectra. The efficiency of the present technique was demonstrated in an application for (19)F{(1)H} and (1)H{(19)F} saturation transfer difference experiments.

  11. Optimization of 1H spin density for dynamic nuclear polarization using photo-excited triplet electron spins.

    PubMed

    Kagawa, Akinori; Murokawa, Yu; Takeda, Kazuyuki; Kitagawa, Masahiro

    2009-03-01

    In dynamic nuclear polarization (DNP) using photo-excited triplet electron spins, known as Microwave-Induced Optical Nuclear Polarization (MIONP), the attainable (1)H polarization is determined by the ratio of the buildup rate and the spin-lattice relaxation rate, in turn depend on the (1)H spin density. It is shown that the final (1)H polarization can be enhanced by diluting the (1)H spins with partial deuteration. The DNP experiments are demonstrated in 0.05 mol% pentacene-doped p-terphenyl for various (1)H abundances. It is also shown that the (1)H spin diffusion coefficient can be determined by examining the initial buildup rate of (1)H polarization for various repetition rates of the DNP sequence.

  12. Excitation of high-frequency azimuthal surface waves by an annular electron beam in a waveguide with a noncircular interface of the plasma column

    SciTech Connect

    Girka, V. O. Girka, I. O. Pavlenko, I. V.

    2013-05-15

    An initial stage of the interaction of an electron beam ring rotating along Larmor orbits in a gap between the plasma column and a circular metal chamber of a cylindrical waveguide with extraordinarily polarized electromagnetic waves of the surface type is studied. These waves propagate along the azimuthal angle across an axial magnetic field in the range above the upper hybrid frequency. Using numerical analysis of the dispersion relation, it is shown that by the aid of an appropriate choice of the shape of the plasma-vacuum interface one can achieve a significant increasing of growth rates of the resonant beam instability of these waves.

  13. The effect of chemical stability on the NIPAM gel dosimeter using 1H-NMR

    NASA Astrophysics Data System (ADS)

    Huang, You-Ruei; Hsieh, Ling-Ling; Chang, Yuan-Jen; Hsieh, Bor-Tsung

    2013-06-01

    Radiation-induced chemical changes in the N-isopropylacrylamide (NIPAM) gels used in three-dimensional dosimeters were investigated using 1H-NMR in this study. The experimental results show that the signal from C=C bonds of NIPAM and N,N'-Methylenediacrylamide (BIS) are 5.5 and 6.3 ppm, respectively. The double bonds from the NIPAM and BIS disappeared with half-dose (D50) were about 10.90 Gy ± 0.76 Gy and 10.09 Gy ± 0.29 Gy, respectively. This observation demonstrates that the polymerization rate of BIS is faster than that of the NIPAM monomer. The 1H-NMR can indicate the chemical structure changes of the polymer gel dosimeter after irradiation and successfully determine the D50 in the NIPAM gel dosimeter.

  14. Exploring the 3-piperidin-4-yl-1H-indole scaffold as a novel antimalarial chemotype.

    PubMed

    Santos, Sofia A; Lukens, Amanda K; Coelho, Lis; Nogueira, Fátima; Wirth, Dyann F; Mazitschek, Ralph; Moreira, Rui; Paulo, Alexandra

    2015-09-18

    A series of 3-piperidin-4-yl-1H-indoles with building block diversity was synthesized based on a hit derived from an HTS whole-cell screen against Plasmodium falciparum. Thirty-eight compounds were obtained following a three-step synthetic approach and evaluated for anti-parasitic activity. The SAR shows that 3-piperidin-4-yl-1H-indole is intolerant to most N-piperidinyl modifications. Nevertheless, we were able to identify a new compound (10d) with lead-like properties (MW = 305; cLogP = 2.42), showing antimalarial activity against drug-resistant and sensitive strains (EC50 values ∼ 3 μM), selectivity for malaria parasite and no cross-resistance with chloroquine, thus representing a potential new chemotype for further optimization towards novel and affordable antimalarial drugs.

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

    PubMed Central

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

    2015-01-01

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

  16. 1H nuclear spin relaxation of liquid water from molecular dynamics simulations.

    PubMed

    Calero, C; Martí, J; Guàrdia, E

    2015-02-01

    We have investigated the nuclear spin relaxation properties of (1)H in liquid water with the help of molecular dynamics simulations. We have computed the (1)H nuclear spin relaxation times T1 and T2 and determined the contribution of the different interactions to the relaxation at different temperatures and for different classical water models (SPC/E, TIP3P, TIP4P, and TIP4P/2005). Among the water models considered, the TIP4P/2005 model exhibits the best agreement with the experiment. The same analysis was performed with Car-Parrinello ab initio molecular dynamics simulations of bulk water at T = 330 K, which provided results close to the experimental values at room temperature. To complete the study, we have successfully accounted for the temperature-dependence of T1 and T2 in terms of a simplified model, which considers the reorientation in finite angle jumps and the diffusive translation of water molecules.

  17. Improved Carbohydrate Structure Generalization Scheme for (1)H and (13)C NMR Simulations.

    PubMed

    Kapaev, Roman R; Toukach, Philip V

    2015-07-21

    The improved Carbohydrate Structure Generalization Scheme has been developed for the simulation of (13)C and (1)H NMR spectra of oligo- and polysaccharides and their derivatives, including those containing noncarbohydrate constituents found in natural glycans. Besides adding the (1)H NMR calculations, we improved the accuracy and performance of prediction and optimized the mathematical model of the precision estimation. This new approach outperformed other methods of chemical shift simulation, including database-driven, neural net-based, and purely empirical methods and quantum-mechanical calculations at high theory levels. It can process structures with rarely occurring and noncarbohydrate constituents unsupported by the other methods. The algorithm is transparent to users and allows tracking used reference NMR data to original publications. It was implemented in the Glycan-Optimized Dual Empirical Spectrum Simulation (GODESS) web service, which is freely available at the platform of the Carbohydrate Structure Database (CSDB) project ( http://csdb.glycoscience.ru). PMID:26087011

  18. Amplitude-integrated electroencephalogram 1 h after birth in a preterm infant with cystic periventricular leukomalacia.

    PubMed

    Kato, Toru; Okumura, Akihisa; Hayakawa, Fumio; Tsuji, Takeshi; Hayashi, Seiji; Natsume, Jun

    2013-01-01

    We report a preterm infant, who showed abnormal amplitude-integrated electroencephalogram (aEEG) findings 1 h after birth and later developed cystic periventricular leukomalacia (PVL). The patient was a girl with a gestational age of 29 weeks. She was delivered by emergency cesarean section because of placental abruption and intrauterine co-twin demise. Artificial ventilation and administration of surfactant were needed to treat respiratory distress syndrome. Her cardiovascular condition was stable with artificial ventilation. Cranial ultrasonography showed extended cystic PVL after 11 days of age. aEEG 1 h after birth showed a consistently inactive pattern that resolved completely 28 h after birth. The neurophysiological findings of this patient suggest that aEEG findings during the very early period after birth provide significant information for predicting PVL.

  19. (1)H and DOSY NMR spectroscopy analysis of Ligusticum porteri rhizome extracts.

    PubMed

    León, Alejandra; Chávez, María Isabel; Delgado, Guillermo

    2011-08-01

    The presence of dimeric phthalides and other constituents in extracts of the vegetal species Ligusticum porteri was established by NMR spectroscopy. In comparative qualitative (1)H NMR analyses of acetone extracts of rhizomes from fresh and dried L. porteri samples, we found that the dimeric phthalides tokinolide B (3), diligustilide (4) and riligustilide (5) were naturally produced by the plant and not post-harvest products. We also obtained DOSY (1)H NMR data that provided both virtual separation and structural information for the phthalides present in a dry acetone extract of L. porteri. In addition, we developed a protocol for the quantification of dimeric phthalides, which is performed by calculating the relative ratio of the peak area of selected proton signals for some compounds with respect to the known signal of the internal standard, 4-dimethylaminopyridine. The protocol allows the rapid and direct quantification of dimeric phthalides and others constituents in fresh L. porteri rhizomes. PMID:21761449

  20. Lipid profiling of cancerous and benign gallbladder tissues by 1H NMR spectroscopy.

    PubMed

    Jayalakshmi, Kamaiah; Sonkar, Kanchan; Behari, Anu; Kapoor, Vinay K; Sinha, Neeraj

    2011-05-01

    Qualitative and quantitative (1) H NMR analysis of lipid extracts of gallbladder tissue in chronic cholecystitis (CC, benign) (n = 14), xanthogranulomatous cholecystitis (XGC, intermediate) (n = 9) and gallbladder cancer (GBC, malignant) (n = 8) was carried out to understand the mechanisms involved in the transformation of benign gallbladder tissue to intermediate and malignant tissue. The results revealed alterations in various tissue lipid components in gallbladder in CC, XGC and GBC. The difference in the nature of lipid components in benign and malignant disease may aid in the identification of the biological pathways involved in the etiopathogenesis of GBC. This is the first study on lipid profiling of gallbladder tissue by (1) H NMR spectroscopy, and has possible implications for the development of future diagnostic approaches. PMID:22945290

  1. Nonvortical Rashba Spin Structure on a Surface with C1 h Symmetry

    NASA Astrophysics Data System (ADS)

    Annese, Emilia; Kuzumaki, Takuya; Müller, Beate; Yamamoto, Yuta; Nakano, Hiroto; Kato, Haruki; Araki, Atsushi; Ohtaka, Minoru; Aoki, Takashi; Ishikawa, Hirotaka; Hayashida, Takashi; Osiecki, Jacek R.; Miyamoto, Koji; Takeichi, Yasuo; Harasawa, Ayumi; Yaji, Koichiro; Shirasawa, Tetsuroh; Nittoh, Koh-ichi; Yang, Wooil; Miki, Kazushi; Oda, Tatsuki; Yeom, Han Woong; Sakamoto, Kazuyuki

    2016-07-01

    A totally anisotropic peculiar Rashba-Bychkov (RB) splitting of electronic bands was found on the Tl /Si (110 )-(1 ×1 ) surface with C1 h symmetry by angle- and spin-resolved photoelectron spectroscopy and first-principles theoretical calculation. The constant energy contour of the upper branch of the RB split band has a warped elliptical shape centered at a k point located between Γ ¯ and the edge of the surface Brillouin zone, i.e., at a point without time-reversal symmetry. The spin-polarization vector of this state is in-plane and points almost the same direction along the whole elliptic contour. This novel nonvortical RB spin structure is confirmed as a general phenomenon originating from the C1 h symmetry of the surface.

  2. Shaft Sinking at the Nevada Test Site, U1h Shaft Project

    SciTech Connect

    B. Briggs; R. Musick

    2001-03-01

    The U1h Shaft Project is a design/build subcontract to construct one 6.1 meter (m) (20 feet (ft)) finished diameter shaft to a depth of 321.6 m (1,055 ft.) at the Nevada Test Site. Atkinson Construction was subcontracted by Bechtel Nevada to construct the U1h Shaft for the U.S. Department of Energy. The project consists of furnishing and installing the sinking plant, construction of the 321.6 m (1,055 ft.) of concrete lined shaft, development of a shaft station at a depth of 297.5 m (976 ft.), and construction of a loading pocket at the station. The outfitting of the shaft and installation of a new hoist may be incorporated into the project at a later date. This paper will describe the design phase, the excavation and lining operation, shaft station construction and the contractual challenges encountered on this project.

  3. The morphology of C–S–H: Lessons from {sup 1}H nuclear magnetic resonance relaxometry

    SciTech Connect

    Valori, A.; McDonald, P.J.; Scrivener, K.L.

    2013-07-15

    {sup 1}H nuclear magnetic resonance has been applied to cement pastes, and in particular calcium silicate hydrate (C–S–H), for the characterisation of porosity and pore water interactions for over three decades. However, there is now renewed interest in the method, given that it has been shown to be non-invasive, non-destructive and fully quantitative. It is possible to make measurements of pore size distribution, specific surface area, C–S–H density and water fraction and water dynamics over 6 orders of magnitude from nano- to milli-seconds. This information comes in easily applied experiments that are increasingly well understood, on widely available equipment. This contribution describes the basic experiments for a cement audience new to the field and reviews three decades of work. It concludes with a summary of the current state of understanding of cement pore morphology from the perspective of {sup 1}H NMR.

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

    PubMed

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

    2015-04-15

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

  5. Parameter maps of 1H residual dipolar couplings in tendon under mechanical load

    NASA Astrophysics Data System (ADS)

    Fechete, R.; Demco, D. E.; Blümich, B.

    2003-11-01

    Proton multipolar spin states associated with dipolar encoded longitudinal magnetization (DELM) and double-quantum (DQ) coherences of bound water are investigated for bovine and sheep Achilles tendon under mechanical load. DELM decay curves and DQ buildup and decay curves reveal changes of the 1H residual dipolar couplings for tendon at rest and under local compression forces. The multipolar spin states are used to design dipolar contrast filters for NMR 1H images of heterogeneous tendon. Heterogeneities in tendon samples were artificially generated by local compression parallel and perpendicular to the tendon plug axis. Quotient images obtained from DQ-filtered images by matched and mismatched excitation/reconversion periods are encoded only by the residual dipolar couplings. Semi-quantitative parameter maps of the residual dipolar couplings of bound water were obtained from these quotient images using a reference elastomer sample. This method can be used to quantify NMR imaging of injured ordered tissues.

  6. Nonvortical Rashba Spin Structure on a Surface with C_{1h} Symmetry.

    PubMed

    Annese, Emilia; Kuzumaki, Takuya; Müller, Beate; Yamamoto, Yuta; Nakano, Hiroto; Kato, Haruki; Araki, Atsushi; Ohtaka, Minoru; Aoki, Takashi; Ishikawa, Hirotaka; Hayashida, Takashi; Osiecki, Jacek R; Miyamoto, Koji; Takeichi, Yasuo; Harasawa, Ayumi; Yaji, Koichiro; Shirasawa, Tetsuroh; Nittoh, Koh-Ichi; Yang, Wooil; Miki, Kazushi; Oda, Tatsuki; Yeom, Han Woong; Sakamoto, Kazuyuki

    2016-07-01

    A totally anisotropic peculiar Rashba-Bychkov (RB) splitting of electronic bands was found on the Tl/Si(110)-(1×1) surface with C_{1h} symmetry by angle- and spin-resolved photoelectron spectroscopy and first-principles theoretical calculation. The constant energy contour of the upper branch of the RB split band has a warped elliptical shape centered at a k point located between Γ[over ¯] and the edge of the surface Brillouin zone, i.e., at a point without time-reversal symmetry. The spin-polarization vector of this state is in-plane and points almost the same direction along the whole elliptic contour. This novel nonvortical RB spin structure is confirmed as a general phenomenon originating from the C_{1h} symmetry of the surface. PMID:27419582

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

    PubMed

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

    2015-12-01

    This work describes the total and unambiguous assignment of the 750 MHz (1)H NMR spectrum of 3β-acetoxypregna-5,16-dien-20-one or 16-DPA (1), the well-known intermediate utilized in the synthesis of biological important commercial steroids. The task was accomplished by extracting the coupling constant values in the overlapped spectrum region by HSQC, and using these values in the (1)H iterative full spin analysis integrated in the PERCH NMR software. Comparison of the experimental vicinal coupling constants of 1 with the values calculated using Altona provides an excellent correlation. The same procedure, when applied to the published data of progesterone (2) and testosterone (3), afforded an acceptable correlation for 2 and a poor correlation for 3. In the last case, this suggested the reassignment of all four vicinal coupling constants for the methylene signals at the C-15 and C-16 positions, demonstrating the utility of this methodology. PMID:26476187

  8. Human phase response curve to a 1 h pulse of bright white light

    PubMed Central

    St Hilaire, Melissa A; Gooley, Joshua J; Khalsa, Sat Bir S; Kronauer, Richard E; Czeisler, Charles A; Lockley, Steven W

    2012-01-01

    The phase resetting response of the human circadian pacemaker to light depends on the timing of exposure and is described by a phase response curve (PRC). The current study aimed to construct a PRC for a 1 h exposure to bright white light (∼8000 lux) and to compare this PRC to a <3 lux dim background light PRC. These data were also compared to a previously completed 6.7 h bright white light PRC and a <15 lux dim background light PRC constructed under similar conditions. Participants were randomized for exposure to 1 h of either bright white light (n= 18) or <3 lux dim background light (n= 18) scheduled at 1 of 18 circadian phases. Participants completed constant routine (CR) procedures in dim light (<3 lux) before and after the light exposure to assess circadian phase. Phase shifts were calculated as the difference in timing of dim light melatonin onset (DLMO) during pre- and post-stimulus CRs. Exposure to 1 h of bright white light induced a Type 1 PRC with a fitted peak-to-trough amplitude of 2.20 h. No discernible PRC was observed in the <3 lux dim background light PRC. The fitted peak-to-trough amplitude of the 1 h bright light PRC was ∼40% of that for the 6.7 h PRC despite representing only 15% of the light exposure duration, consistent with previous studies showing a non-linear duration–response function for the effects of light on circadian resetting. PMID:22547633

  9. (1)H-MRS metabolites in adults with Down syndrome: Effects of dementia.

    PubMed

    Lin, A-L; Powell, D; Caban-Holt, A; Jicha, G; Robertson, W; Gold, B T; Davis, R; Abner, E; Wilcock, D M; Schmitt, F A; Head, E

    2016-01-01

    To determine if proton magnetic resonance spectroscopy ((1)H-MRS) detect differences in dementia status in adults with Down syndrome (DS), we used (1)H-MRS to measure neuronal and glial metabolites in the posterior cingulate cortex in 22 adults with DS and in 15 age- and gender-matched healthy controls. We evaluated associations between (1)H-MRS results and cognition among DS participants. Neuronal biomarkers, including N-acetylaspartate (NAA) and glutamate-glutamine complex (Glx), were significantly lower in DS patients with Alzheimer's should probably be changed to Alzheimer (without ' or s) through ms as per the new naming standard disease (DSAD) when compared to non-demented DS (DS) and healthy controls (CTL). Neuronal biomarkers therefore appear to reflect dementia status in DS. In contrast, all DS participants had significantly higher myo-inositol (MI), a putative glial biomarker, compared to CTL. Our data indicate that there may be an overall higher glial inflammatory component in DS compared to CTL prior to and possibly independent of developing dementia. When computing the NAA to MI ratio, we found that presence or absence of dementia could be distinguished in DS. NAA, Glx, and NAA/MI in all DS participants were correlated with scores from the Brief Praxis Test and the Severe Impairment Battery. (1)H-MRS may be a useful diagnostic tool in future longitudinal studies to measure AD progression in persons with DS. In particular, NAA and the NAA/MI ratio is sensitive to the functional status of adults with DS, including prior to dementia. PMID:27330972

  10. Multicomponent assembly of diverse pyrazin-2(1H)-one chemotypes.

    PubMed

    Azuaje, Jhonny; El Maatougui, Abdelaziz; Pérez-Rubio, José M; Coelho, Alberto; Fernández, Franco; Sotelo, Eddy

    2013-05-01

    An expedient and concise Ugi-based approach for the rapid assembly of pyrazin-2(1H)-one-based frameworks has been developed. This convergent approach encompasses skeletal, functional and stereochemical diversity, exhibiting an unusually high bond-forming efficiency as well as high structure and step economies. The method involves the use of readily available commercial reagents and is an example of the reconciliation of structural complexity with operational simplicity in a time- and cost-effective manner.

  11. Quantitative 1H MRI and MRS Microscopy of Individual V79 Lung Tumor Spheroids

    NASA Astrophysics Data System (ADS)

    Minard, Kevin R.; Guo, Xiuling; Wind, Robert A.

    1998-08-01

    In this Communication1H MRI and MRS microscopy experiments of individual V79 lung tumor spheroids with diameters between 550 and 650 μm are reported. The results have been used to determine theT1,T2, andDvalues as well as the concentrations of water, total choline, creatine/phosphocreatine, and mobile lipids in the viable rims and in the necrotic centers.

  12. Characterisation of Human Embryonic Stem Cells Conditioning Media by 1H-Nuclear Magnetic Resonance Spectroscopy

    PubMed Central

    MacIntyre, David A.; Melguizo Sanchís, Darío; Jiménez, Beatriz; Moreno, Rubén; Stojkovic, Miodrag; Pineda-Lucena, Antonio

    2011-01-01

    Background Cell culture media conditioned by human foreskin fibroblasts (HFFs) provide a complex supplement of protein and metabolic factors that support in vitro proliferation of human embryonic stem cells (hESCs). However, the conditioning process is variable with different media batches often exhibiting differing capacities to maintain hESCs in culture. While recent studies have examined the protein complement of conditioned culture media, detailed information regarding the metabolic component of this media is lacking. Methodology/Principal Findings Using a 1H-Nuclear Magnetic Resonance (1H-NMR) metabonomics approach, 32 metabolites and small compounds were identified and quantified in media conditioned by passage 11 HFFs (CMp11). A number of metabolites were secreted by HFFs with significantly higher concentration of lactate, alanine, and formate detected in CMp11 compared to non-conditioned media. In contrast, levels of tryptophan, folate and niacinamide were depleted in CMp11 indicating the utilisation of these metabolites by HFFs. Multivariate statistical analysis of the 1H-NMR data revealed marked age-related differences in the metabolic profile of CMp11 collected from HFFs every 24 h over 72 h. Additionally, the metabolic profile of CMp11 was altered following freezing at −20°C for 2 weeks. CM derived from passage 18 HFFs (CMp18) was found to be ineffective at supporting hESCs in an undifferentiated state beyond 5 days culture. Multivariate statistical comparison of CMp11 and CMp18 metabolic profiles enabled rapid and clear discrimination between the two media with CMp18 containing lower concentrations of lactate and alanine as well as higher concentrations of glucose and glutamine. Conclusions/Significance 1H-NMR-based metabonomics offers a rapid and accurate method of characterising hESC conditioning media and is a valuable tool for monitoring, controlling and optimising hESC culture media preparation. PMID:21347425

  13. Application of 1H-NMR metabolomic profiling for reef-building corals.

    PubMed

    Sogin, Emilia M; Anderson, Paul; Williams, Philip; Chen, Chii-Shiarng; Gates, Ruth D

    2014-01-01

    In light of global reef decline new methods to accurately, cheaply, and quickly evaluate coral metabolic states are needed to assess reef health. Metabolomic profiling can describe the response of individuals to disturbance (i.e., shifts in environmental conditions) across biological models and is a powerful approach for characterizing and comparing coral metabolism. For the first time, we assess the utility of a proton-nuclear magnetic resonance spectroscopy (1H-NMR)-based metabolomics approach in characterizing coral metabolite profiles by 1) investigating technical, intra-, and inter-sample variation, 2) evaluating the ability to recover targeted metabolite spikes, and 3) assessing the potential for this method to differentiate among coral species. Our results indicate 1H-NMR profiling of Porites compressa corals is highly reproducible and exhibits low levels of variability within and among colonies. The spiking experiments validate the sensitivity of our methods and showcase the capacity of orthogonal partial least squares discriminate analysis (OPLS-DA) to distinguish between profiles spiked with varying metabolite concentrations (0 mM, 0.1 mM, and 10 mM). Finally, 1H-NMR metabolomics coupled with OPLS-DA, revealed species-specific patterns in metabolite profiles among four reef-building corals (Pocillopora damicornis, Porites lobata, Montipora aequituberculata, and Seriatopora hystrix). Collectively, these data indicate that 1H-NMR metabolomic techniques can profile reef-building coral metabolomes and have the potential to provide an integrated picture of the coral phenotype in response to environmental change. PMID:25354140

  14. Application of 1H-NMR Metabolomic Profiling for Reef-Building Corals

    PubMed Central

    Sogin, Emilia M.; Anderson, Paul; Williams, Philip; Chen, Chii-Shiarng; Gates, Ruth D.

    2014-01-01

    In light of global reef decline new methods to accurately, cheaply, and quickly evaluate coral metabolic states are needed to assess reef health. Metabolomic profiling can describe the response of individuals to disturbance (i.e., shifts in environmental conditions) across biological models and is a powerful approach for characterizing and comparing coral metabolism. For the first time, we assess the utility of a proton-nuclear magnetic resonance spectroscopy (1H-NMR)-based metabolomics approach in characterizing coral metabolite profiles by 1) investigating technical, intra-, and inter-sample variation, 2) evaluating the ability to recover targeted metabolite spikes, and 3) assessing the potential for this method to differentiate among coral species. Our results indicate 1H-NMR profiling of Porites compressa corals is highly reproducible and exhibits low levels of variability within and among colonies. The spiking experiments validate the sensitivity of our methods and showcase the capacity of orthogonal partial least squares discriminate analysis (OPLS-DA) to distinguish between profiles spiked with varying metabolite concentrations (0 mM, 0.1 mM, and 10 mM). Finally, 1H-NMR metabolomics coupled with OPLS-DA, revealed species-specific patterns in metabolite profiles among four reef-building corals (Pocillopora damicornis, Porites lobata, Montipora aequituberculata, and Seriatopora hystrix). Collectively, these data indicate that 1H-NMR metabolomic techniques can profile reef-building coral metabolomes and have the potential to provide an integrated picture of the coral phenotype in response to environmental change. PMID:25354140

  15. Microwave-enhanced transition metal-catalyzed decoration of 2(1H)-pyrazinone scaffolds.

    PubMed

    Kaval, Nadya; Bisztray, Katalin; Dehaen, Wim; Kappe, C Oliver; Van der Eycken, Erik

    2003-01-01

    The 2(1H)-pyrazinones have been demonstrated to be versatile building blocks for the synthesis of biologically active compounds. Here, an efficient method is described for the decoration of these interesting scaffolds. Microwave-assisted palladium catalyzed reactions allow the easy introduction of different substituents at the C3- and even at the rather unreactive C5-position of the pyrazinones. Stille, Suzuki, Heck, Sonogashira reactions, in addition to reductive dechlorinations, and cyanation reactions are investigated.

  16. Aromatic derivatives of 2,3-dihydro-1H-1,5-benzodiazepine

    SciTech Connect

    Orlov, V.D.; Desenko, S.M.; Kiroga, Kh.

    1987-09-01

    The formation of 2,2,4-trisubstituted 2,3-dihydro-1H-1,5-benzodiazepines in the reactions of acetylarenes with 4-ethoxy- and 3,5-dimethyl-1,2-phenylenediamine was studied. The effect of the substituents on the individual stages of the reactions is discussed. A quantum-chemical calculation of the relative nucleophilicity of 1,2-phenylenediamine, 2,3-diaminopyridine, and 3,4-diaminofurazan was undertaken.

  17. Stereoelectronic effects on 1H nuclear magnetic resonance chemical shifts in methoxybenzenes.

    PubMed

    Lambert, Maja; Olsen, Lars; Jaroszewski, Jerzy W

    2006-12-01

    Investigation of all O-methyl ethers of 1,2,3-benzenetriol and 4-methyl-1,2,3-benzenetriol (3-16) by 1H NMR spectroscopy and density-functional calculations disclosed practically useful conformational effects on 1H NMR chemical shifts in the aromatic ring. While the conversion of phenol (2) to anisole (1) causes only small positive changes of 1H NMR chemical shifts (Delta delta < 0.08 ppm) that decrease in the order Hortho > Hmeta > Hpara, the experimental O-methylation induced shifts in ortho-disubstituted phenols are largest for Hpara, Delta delta equals; 0.19 +/- 0.02 ppm (n = 11). The differences are due to different conformational behavior of the OH and OCH3 groups; while the ortho-disubstituted OH group remains planar in polyphenols due to hydrogen bonding and conjugative stabilization, the steric congestion in ortho-disubstituted anisoles outweighs the conjugative effects and forces the Ar-OCH3 torsion out of the ring plane, resulting in large stereoelectronic effects on the chemical shift of Hpara. Conformational searches and geometry optimizations for 3-16 at the B3LYP/6-31G** level, followed by B3LYP/6-311++G(2d,2p) calculations for all low-energy conformers, gave excellent correlation between computed and observed 1H NMR chemical shifts, including agreement between computed and observed chemical shift changes caused by O-methylation. The observed regularities can aid structure elucidation of partly O-methylated polyphenols, including many natural products and drugs, and are useful in connection with chemical shift predictions by desktop computer programs. PMID:17137372

  18. Complete 1H and 13C NMR assignments of two phytosterols from roots of Piper nigrum.

    PubMed

    Wei, Kun; Li, Wei; Koike, Kazuo; Pei, Yuping; Chen, Yingjie; Nikaido, Tamotsu

    2004-03-01

    Using modern NMR techniques, including DQF-COSY, NOESY, HETCOR and HMBC, the full assignments of all 1H and 13C chemical shifts were made for stigmastane-3,6-dione and stigmast-4-ene-3,6-dione, isolated from the roots of Piper nigrum (Piperaceae). Their stereochemistry was resolved by a combination of 2D NOESY data and analysis of coupling constants. The two compounds were isolated from the genus Piper for the first time.

  19. An efficient spectra processing method for metabolite identification from 1H-NMR metabolomics data.

    PubMed

    Jacob, Daniel; Deborde, Catherine; Moing, Annick

    2013-06-01

    The spectra processing step is crucial in metabolomics approaches, especially for proton NMR metabolomics profiling. During this step, noise reduction, baseline correction, peak alignment and reduction of the 1D (1)H-NMR spectral data are required in order to allow biological information to be highlighted through further statistical analyses. Above all, data reduction (binning or bucketing) strongly impacts subsequent statistical data analysis and potential biomarker discovery. Here, we propose an efficient spectra processing method which also provides helpful support for compound identification using a new data reduction algorithm that produces relevant variables, called buckets. These buckets are the result of the extraction of all relevant peaks contained in the complex mixture spectra, rid of any non-significant signal. Taking advantage of the concentration variability of each compound in a series of samples and based on significant correlations that link these buckets together into clusters, the method further proposes automatic assignment of metabolites by matching these clusters with the spectra of reference compounds from the Human Metabolome Database or a home-made database. This new method is applied to a set of simulated (1)H-NMR spectra to determine the effect of some processing parameters and, as a proof of concept, to a tomato (1)H-NMR dataset to test its ability to recover the fruit extract compositions. The implementation code for both clustering and matching steps is available upon request to the corresponding author. PMID:23525538

  20. 2-Substituted-1H-perimidines: Synthesis, crystal structure and DFT calculations

    NASA Astrophysics Data System (ADS)

    Sović, Irena; Pavlović, Gordana; Papadopoulos, Anastasios G.; Šišak, Dubravka; Karminski-Zamola, Grace

    2013-06-01

    Perimidines or 1H-perimidines represent an important class of heterocyclic compounds built up of a dihydropyrimidine ring peri-fused to a naphthalene moiety. They exhibit 1,3-annular tautomerism due to two possible hydrogen positions at one or the other endocyclic nitrogen atoms or both resulting in the imine or enamine forms, respectively. The imine forms of 2-substituted-1H-perimidines can exhibit cis or trans orientation of 2-substituent in respect of the double Cdbnd N bond. Here we report synthesis of four 2-substituted perimidine derivatives: 2-hydroxymethyl-perimidine 2, ethyl-1H-perimidine-2-carboxylate 3, perimidine-2-carboxylic acid 4 and 2-cyanomethyl-perimidine 5. The compounds are characterized by MS, IR spectroscopy, single-crystal X-ray diffraction (SCXRD) (2), and powder X-ray diffraction (PXRD) (5), as well as DFT calculations (3, 4 and 5) and by the NMR spectroscopy in the solution (2-5). Single-crystal X-ray diffraction proved that the compound 2 exists in the solid state as imine tautomer. The molecular structure that compound 5 adopt in its crystalline state could not be determined reliably. The results from the PXRD structural analysis cannot univocally indicate which of the forms is more likely to be present in the solid state. On the contrary, DFT calculation shows that the enamine form of 5 is more stable than imine form.

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

    PubMed

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

    2011-04-01

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

  2. Clinical Relevance of Single-Voxel 1H MRS Metabolites in Discriminating Suprasellar Tumors

    PubMed Central

    Virani, Rahul A

    2016-01-01

    Introdution Spatially resolved metabolic data obtained from Proton Magnetic Resonance Spectroscopy (1H MRS) provides information which increases the diagnostic accuracy of imaging sequences in predicting the histology of suprasellar tumors. Aim To evaluate the role of 1H MRS in the diagnosis of various suprasellar tumors. Materials and Methods Sixty cases of various suprasellar, hypothalamic and third ventricular neoplasms were investigated with long-echo single voxel 1H -MRS using 1.5 Tesla clinical imager. Single-voxel spectroscopic examinations were guided by T1-weighted or T2-weighted images. Statistical analysis was carried out using IBM SPSS software version 19. Results We observed that whenever brain tissue was damaged or replaced by any process, NAA was markedly reduced. Extra-axial lesions which do not infiltrate brain or contain neuroglial tissue, didn’t demonstrate any NAA resonances. Cr was used as an internal standard for semi-quantitative evaluation of metabolic changes of other brain metabolites. Increased Cho was seen in processes with elevated cell-membrane turnover. Conclusion Spectra obtained from different tumors exhibit reproducible differences while histologically similar tumors yield characteristic spectra with only minor differences. Pituitary tumors were typically characterized by significant reduction of NAA, Cr peak and moderate elevation of Cho peak. Gliomas were typically characterized by decrease of NAA and Cr peaks and increase of Cho peak. Craniopharyngiomas were typically characterized by significant decrease of all metabolites. PMID:27630921

  3. Effect of biological factors on successful measurements with skeletal-muscle 1H-MRS

    PubMed Central

    Isobe, Tomonori; Okamoto, Yoshikazu; Hirano, Yuji; Ando, Hiroki; Takada, Kenta; Sato, Eisuke; Shinoda, Kazuya; Tadano, Kiichi; Takei, Hideyuki; Kamizawa, Satoshi; Mori, Yutaro; Suzuki, Hiroaki

    2016-01-01

    Background Our purpose in this study was to clarify whether differences in subject group attributes could affect data acquisition in proton magnetic resonance spectroscopy (1H-MRS). Methods Subjects without diabetes mellitus (DM) were divided into two groups (group A, in their 20s; group B, 30–60 years old). Subjects with DM formed group C (30–60 years old). The numbers of subjects were 19, 27, and 22 for group A, B, and C respectively. For all subjects, 1H-MRS measurements were taken of the soleus muscle (SOL) and the anterior tibial muscle (AT). We defined the success of the measurements by the detection of intramyocellular lipids. Moreover, we also measured the full width at half maximum of the water peaks for all subjects. Results The success rate was significantly higher for the AT (100%) than for the SOL (81.6%) (P<0.01). For the SOL, the success rate was 100% in group A, 85.2% in group B, and 77.3% in group C. There was a significant difference (P<0.05) between groups A and B, as well as between groups A and C. In all subjects, there was a significant difference (P<0.01) in the full width at half maximum (Hz) of the water peak between the AT and SOL measurements. Conclusion We conclude that differences in the age and DM history of subjects could affect the probability of successful 1H-MRS data acquisition. PMID:27499626

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

    SciTech Connect

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

    2014-01-03

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

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

    PubMed

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

    2017-02-15

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

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

    PubMed

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

    2017-02-15

    Saffron, the dried red stigmas of Crocus sativus L., is considered as one of the most expensive spices worldwide, and as such, it is prone to adulteration. This study introduces an NMR-based approach to identify and determine the adulteration of saffron with Sudan I-IV dyes. A complete (1)H and (13)C resonance assignment for Sudan I-IV, achieved by two-dimensional homonuclear and heteronuclear NMR experiments, is reported for the first time. Specific different proton signals for the identification of each Sudan dye in adulterated saffron can be utilised for quantitative (1)H NMR (qHNMR), a well-established method for quantitative analysis. The quantification of Sudan III, as a paradigm, was performed in varying levels (0.14-7.1g/kg) by considering the NMR signal occurring at 8.064ppm. The high linearity, accuracy and rapidity of investigation enable high resolution (1)H NMR spectroscopy to be used for evaluation of saffron adulteration with Sudan dyes. PMID:27664653

  7. Anti-Toxoplasma Activity of 2-(Naphthalene-2-γlthiol)-1H Indole

    PubMed Central

    ASGARI, Qasem; KESHAVARZ, Hossein; REZAEIAN, Mostafa; SADEGHPOUR, Hossein; MIRI, Ramin; MOTAZEDIAN, Mohammad Hossein

    2015-01-01

    Background: This study was undertaken to evaluate the viability, infectivity and immunity of Toxoplasma gondii tachyzoites exposed to 2-(naphthalene-2-ylthio)-1H-indole. Methods: Tachyzoites of RH strain were incubated in various concentrations of 2-(naphthalene-2-ylthio)-1H-indole (25–800 μM) for 1.5 hours. Then, they were stained by PI and analyzed by Fluorescence-activated cell sorting (FACS). To evaluate the infectivity, the tachyzoites exposed to the different concentrations of the compound were inoculated to 10 BALB/c mice groups. For Control, parasites exposed to DMSO (0.2% v/v) were also intraperitoneally inoculated into two groups of mice. The immunity of the exposed tachyzoites was evaluated by inoculation of the naïve parasite to the survived mice. Results: The LD50 of 2-(naphthalene-2-ylthio)-1H-indole was 57 μmol. The longevity of mice was dose dependent. Five mice out of group 400μmol and 3 out of group 800μmol showed immunization to the parasite. Conclusion: Our findings demonstrated the toxoplasmocidal activity of the compound. The presence of a well-organized transporter mechanism for indole compounds within the parasite in conjunction with several effective mechanisms of these compounds on Toxoplasma viability would open a window for production of new drugs and vaccines. PMID:26246814

  8. A Comprehensive Review of the 1H-MRS Metabolite Spectrum in Autism Spectrum Disorder

    PubMed Central

    Ford, Talitha C.; Crewther, David P.

    2016-01-01

    Neuroimaging studies of neuropsychiatric behavior biomarkers across spectrum disorders are typically based on diagnosis, thus failing to account for the heterogeneity of multi-dimensional spectrum disorders such as autism (ASD). Control group trait phenotypes are also seldom reported. Proton magnetic resonance spectroscopy (1H-MRS) measures the abundance of neurochemicals such as neurotransmitters and metabolites and hence can probe disorder phenotypes at clinical and sub-clinical levels. This detailed review summarizes and critiques the current 1H-MRS research in ASD. The literature reports reduced N-acetylaspartate (NAA), glutamate and glutamine (Glx), γ-aminobutyric acid (GABA), creatine and choline, and increased glutamate for children with ASD. Adult studies are few and results are inconclusive. Overall, the literature has several limitations arising from differences in 1H-MRS methodology and sample demographics. We argue that more consistent methods and greater emphasis on phenotype studies will advance understanding of underlying cortical metabolite disturbance in ASD, and the detection, diagnosis, and treatment of ASD and other multi-dimensional psychiatric disorders. PMID:27013964

  9. Molecular structure, spectroscopic characterization and DFT calculations of a novel (Z)-1-[(2-Ethylphenylamino)methylene]naphthalene-2(1H)-one

    NASA Astrophysics Data System (ADS)

    Alpaslan, Yelda Bingöl; Gökce, Halil; Macit, Mustafa; Alpaslan, Gökhan; Özdemir, Namık

    2015-09-01

    A novel Schiff base compound (Z)-1-[(2-Ethylphenylamino)methylene]naphthalene-2(1H)-one was synthesized from the reaction of 2-hydroxy-1-naphthaldehyde with 2-ethylaniline. The structural properties of the compound have been characterized by using FT-IR, 1H and 13C NMR, UV-vis and X-ray single-crystal methods. According to X-ray diffraction result, the title compound exists in the keto-amine tautomeric form. The molecular geometry, vibrational frequencies, electronic absorption spectra and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the title compound in the ground state have been calculated by using density functional theory (DFT/B3LYP) method with 6-311G++(d,p) basis set, and compared with the experimental data. The obtained results indicate that optimized geometry can well reflect the crystal structural parameters. The theoretical values are in good agreement with the experimental ones. The energetic behavior of the compound in solvent media has been examined using B3LYP method with the 6-311G++(d,p) basis set by applying the polarizable continuum model (PCM). The total energy of the compound decreases with increasing polarity of the solvent. The molecular electrostatic potential (MEP), HOMO-LUMO energy gap and non-linear optical (NLO) properties of the compound were investigated using theoretical calculations.

  10. Mechanistic Assessment of PD-1H Coinhibitory Receptor-Induced T-Cell Tolerance to Allogeneic Antigens1

    PubMed Central

    Flies, Dallas B.; Higuchi, Tomoe; Chen, Lieping

    2015-01-01

    PD-1H is a recently identified cell surface co-inhibitory molecule of the B7/CD28 immune modulatory gene family. We showed previously that single injection of a PD-1H agonistic monoclonal antibody (mAb) protected mice from graft versus host disease (GVHD). We report here two distinct mechanisms operate in PD-1H-induced T cell tolerance. First, signaling via PD-1H co-inhibitory receptor potently arrests allo-reactive donor T cells from activation and expansion in the initiation phase. Second, donor regulatory T cells are subsequently expanded to maintain long-term tolerance and GVHD suppression. Our study reveals the crucial function of PD-1H as a co-inhibitory receptor on allo-reactive T cells and its function in the regulation of T cell tolerance. Therefore, PD-1H may be a target for the modulation of allo-reactive T cells in GVHD and transplantation. PMID:25917101

  11. Change of translational-rotational coupling in liquids revealed by field-cycling {sup 1}H NMR

    SciTech Connect

    Meier, R.; Schneider, E.; Rössler, E. A.

    2015-01-21

    Applying the field-cycling nuclear magnetic resonance technique, the frequency dependence of the {sup 1}H spin-lattice relaxation rate, R{sub 1}(ω)=T{sub 1}{sup −1}(ω), is measured for propylene glycol (PG) which is increasingly diluted with deuterated chloroform. A frequency range of 10 kHz–20 MHz and a broad temperature interval from 220 to about 100 K are covered. The results are compared to those of experiments, where glycerol and o-terphenyl are diluted with their deuterated counter-part. Reflecting intra- as well as intermolecular relaxation, the dispersion curves R{sub 1}(ω,x) (x denotes mole fraction PG) allow to extract the rotational time constant τ{sub rot}(T, x) and the self-diffusion coefficient D(T, x) in a single experiment. The Stokes-Einstein-Debye (SED) relation is tested in terms of the quantity D(T, x) τ{sub rot}(T, x) which provides a measure of an effective hydrodynamic radius or equivalently of the spectral separation of the translational and the rotational relaxation contribution. In contrast to o-terphenyl, glycerol and PG show a spectral separation much larger than suggested by the SED relation. In the case of PG/chloroform mixtures, not only an acceleration of the PG dynamics is observed with increasing dilution but also the spectral separation of rotational and translational relaxation contributions continuously decreases. Finally, following a behavior similar to that of o-terphenyl already at about x = 0.6; i.e., while D(T, x) τ{sub rot}(T, x) in the mixture is essentially temperature independent, it strongly increases with x signaling thus a change of translational-rotational coupling. This directly reflects the dissolution of the hydrogen-bond network and thus a change of solution structure.

  12. Complete 1H and 13C NMR assignments of four new steroidal glycosides from a gorgonian coral Junceella juncea.

    PubMed

    Qi, Shuhua; Zhang, Si; Huang, Jianshe; Xiao, Zhihui; Wu, Jun; Li, Qingxin

    2005-03-01

    Four new cholest-type steroidal glycosides, junceellosides A-D, isolated from the EtOH/CH(2)Cl(2) extracts of the South China Sea gorgonian coral Junceella juncea, were identified. Complete assignments of the (1)H and (13)C NMR chemical shifts for these compounds were achieved by means of one- and two-dimensional NMR techniques, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectra.

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

    USGS Publications Warehouse

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

    1987-01-01

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

  14. Daily and peak 1 h indoor air pollution and driving factors in a rural Chinese village.

    PubMed

    Fischer, Susan L; Koshland, Catherine P

    2007-05-01

    We investigate wintertime indoor air quality and personal exposures to carbon monoxide (CO) in a rural village in Jilin province, where relatively homogeneous climatic and sociocultural factors facilitate investigation of household structural, fuel-related, and behavioral determinants of air pollution as well as relationships between different measures of air quality. Our time-resolved wintertime measurements of carbon monoxide and respirable particles (RSP) enable exploration of peak pollution periods in a village in Jilin Province, China, characterized by household use of both coal and biomass, as well as several "improved" (gas or electric) fuels. Our data indicate a 6-fold increase in peak 1 h PM (1.9 mg/m3) concentrations relative to 24 h mean PM (0.31 mg/m3). Peak 1 h CO concentrations (20.5 ppm) routinely approached and often (27%) exceeded the World Health Organization's 1 h guideline of 26 ppm, although the vast majority (95%) of kitchens were within China's residential indoor air quality guideline for CO on a 24 h basis. Choice of heating fuel and household smoking status were significant predictors of indoor air quality. Whether solid or "improved" (gas or electric) fuel was used for cooking had an even stronger effect, but in the opposite direction from expected, on both peak and daily average measures of air pollution. Peak pollution period concentrations of CO and PM were strongly correlated to daily concentrations of CO and RSP, respectively. Our results suggestthat due to the primary role of heating as a determinant of wintertime indoor air quality in northern Chinese villages, health-oriented interventions limited to provision of improved cooking fuel are insufficient. Our results illustrate that peak pollution periods may routinely exceed exposure regulations and evacuation limits, although this and previous studies document typical 24 h CO concentrations in rural Chinese kitchens to be within guidelines. Within a given village and for a given

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  16. Co(III)-Carbene Radical Approach to Substituted 1H-Indenes.

    PubMed

    Das, Braja Gopal; Chirila, Andrei; Tromp, Moniek; Reek, Joost N H; Bruin, Bas de

    2016-07-20

    A new strategy for the catalytic synthesis of substituted 1H-indenes via metalloradical activation of o-cinnamyl N-tosyl hydrazones is presented, taking advantage of the intrinsic reactivity of a Co(III) carbene radical intermediate. The reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of functionalized 1H-indene derivatives. The cheap and easy to prepare low spin cobalt(II) complex [Co(II)(MeTAA)] (MeTAA = tetramethyltetraaza[14]annulene) proved to be the most active catalyst among those investigated, which demonstrates catalytic carbene radical reactivity for a nonporphyrin cobalt(II) complex, and for the first time catalytic activity of [Co(II)(MeTAA)] in general. The methodology has been successfully applied to a broad range of substrates, producing 1H-indenes in good to excellent yields. The metallo-radical catalyzed indene synthesis in this paper represents a unique example of a net (formal) intramolecular carbene insertion reaction into a vinylic C(sp(2))-H bond, made possible by a controlled radical ring-closure process of the carbene radical intermediate involved. The mechanism was investigated computationally, and the results were confirmed by a series of supporting experimental reactions. Density functional theory calculations reveal a stepwise process involving activation of the diazo compound leading to formation of a Co(III)-carbene radical, followed by radical ring-closure to produce an indanyl/benzyl radical intermediate. Subsequent indene product elimination involving a 1,2-hydrogen transfer step regenerates the catalyst. Trapping experiments using 2,2,6,6-tetra-methylpiperidine-1-oxyl (TEMPO) radical or dibenzoylperoxide (DBPO) confirm the involvement of cobalt(III) carbene radical intermediates. Electron paramagnetic resonance spectroscopic spin-trapping experiments using phenyl N-tert-butylnitrone (PBN) reveal the radical nature of the reaction. PMID

  17. (1)H NMR spectroscopy for the in vitro understanding of the glycaemic index.

    PubMed

    Dona, Anthony C; Landrey, Karola; Atkinson, Fiona S; Brand Miller, Jennie C; Kuchel, Philip W

    2013-06-01

    The glycaemic index (GI) characterises foods by using the incremental area under the glycaemic response curve relative to the same amount of oral glucose. Its ability to differentiate between curves of different shapes, the peak response and other aspects of the glycaemic response is contentious. The present pilot study aimed to explore the possibility of using 1H NMR spectroscopy to better understand in vivo digestion characteristics as reflected in the glycaemic response of carbohydrate-rich foods; such an approach might be an adjunct to the in vivo GI test. The glycaemic response of two types of raw wheat flour (2005 from Griffith NSW, Chara, Row 10, Plot 6:181 and store-bought Colese Plain Flour) and a cooked store-bought flour was tested and compared with results recorded during the in vitro enzymatic digestion of the wheat flour samples by glucoamylase from Aspergillus niger (EC 3.2.1.3) as monitored by 1H NMR spectroscopy. Comparing the digestion time courses of raw and cooked wheat starch recorded in vitro strongly suggests that the initial rate of glucose release in vitro correlates with the glycaemic spike in vivo. During the in vitro time courses, approximately four times as much glucose was released from cooked starch samples than from raw starch samples in 90 min. Monitoring enzymatic digestion of heterogeneous mixtures (food) by 1H NMR spectroscopy showcases the effectiveness of the technique in measuring glucose release and its potential use as the basis of an in vitro method for a better understanding of the GI.

  18. Rate and regulation of copper transport by human copper transporter 1 (hCTR1).

    PubMed

    Maryon, Edward B; Molloy, Shannon A; Ivy, Kristin; Yu, Huijun; Kaplan, Jack H

    2013-06-21

    Human copper transporter 1 (hCTR1) is a homotrimer of a 190-amino acid monomer having three transmembrane domains believed to form a pore for copper permeation through the plasma membrane. The hCTR1-mediated copper transport mechanism is not well understood, nor has any measurement been made of the rate at which copper ions are transported by hCTR1. In this study, we estimated the rate of copper transport by the hCTR1 trimer in cultured cells using (64)Cu uptake assays and quantification of plasma membrane hCTR1. For endogenous hCTR1, we estimated a turnover number of about 10 ions/trimer/s. When overexpressed in HEK293 cells, a second transmembrane domain mutant of hCTR1 (H139R) had a 3-fold higher Km value and a 4-fold higher turnover number than WT. Truncations of the intracellular C-terminal tail and an AAA substitution of the putative metal-binding HCH C-terminal tripeptide (thought to be required for transport) also exhibited elevated transport rates and Km values when compared with WT hCTR1. Unlike WT hCTR1, H139R and the C-terminal mutants did not undergo regulatory endocytosis in elevated copper. hCTR1 mutants combining methionine substitutions that block transport (M150L,M154L) on the extracellular side of the pore and the high transport H139R or AAA intracellular side mutations exhibited the blocked transport of M150L,M154L, confirming that Cu(+) first interacts with the methionines during permeation. Our results show that hCTR1 elements on the intracellular side of the hCTR1 pore, including the carboxyl tail, are not essential for permeation, but serve to regulate the rate of copper entry.

  19. Experimental design and environmental parameters affect Rhodospirillum rubrum S1H response to space flight.

    PubMed

    Mastroleo, Felice; Van Houdt, Rob; Leroy, Baptiste; Benotmane, M Abderrafi; Janssen, Ann; Mergeay, Max; Vanhavere, Filip; Hendrickx, Larissa; Wattiez, Ruddy; Leys, Natalie

    2009-12-01

    In view of long-haul space exploration missions, the European Space Agency initiated the Micro-Ecological Life Support System Alternative (MELiSSA) project targeting the total recycling of organic waste produced by the astronauts into oxygen, water and food using a loop of bacterial and higher plant bioreactors. In that purpose, the alpha-proteobacterium, Rhodospirillum rubrum S1H, was sent twice to the International Space Station and was analyzed post-flight using a newly developed R. rubrum whole genome oligonucleotide microarray and high throughput gel-free proteomics with Isotope-Coded Protein Label technology. Moreover, in an effort to identify a specific response of R. rubrum S1H to space flight, simulation of microgravity and space-ionizing radiation were performed on Earth under identical culture set-up and growth conditions as encountered during the actual space journeys. Transcriptomic and proteomic data were integrated and permitted to put forward the importance of medium composition and culture set-up on the response of the bacterium to space flight-related environmental conditions. In addition, we showed for the first time that a low dose of ionizing radiation (2 mGy) can induce a significant response at the transcriptomic level, although no change in cell viability and only a few significant differentially expressed proteins were observed. From the MELiSSA perspective, we could argue the effect of microgravity to be minimized, whereas R. rubrum S1H could be more sensitive to ionizing radiation during long-term space exploration mission.

  20. Experimental design and environmental parameters affect Rhodospirillum rubrum S1H response to space flight.

    PubMed

    Mastroleo, Felice; Van Houdt, Rob; Leroy, Baptiste; Benotmane, M Abderrafi; Janssen, Ann; Mergeay, Max; Vanhavere, Filip; Hendrickx, Larissa; Wattiez, Ruddy; Leys, Natalie

    2009-12-01

    In view of long-haul space exploration missions, the European Space Agency initiated the Micro-Ecological Life Support System Alternative (MELiSSA) project targeting the total recycling of organic waste produced by the astronauts into oxygen, water and food using a loop of bacterial and higher plant bioreactors. In that purpose, the alpha-proteobacterium, Rhodospirillum rubrum S1H, was sent twice to the International Space Station and was analyzed post-flight using a newly developed R. rubrum whole genome oligonucleotide microarray and high throughput gel-free proteomics with Isotope-Coded Protein Label technology. Moreover, in an effort to identify a specific response of R. rubrum S1H to space flight, simulation of microgravity and space-ionizing radiation were performed on Earth under identical culture set-up and growth conditions as encountered during the actual space journeys. Transcriptomic and proteomic data were integrated and permitted to put forward the importance of medium composition and culture set-up on the response of the bacterium to space flight-related environmental conditions. In addition, we showed for the first time that a low dose of ionizing radiation (2 mGy) can induce a significant response at the transcriptomic level, although no change in cell viability and only a few significant differentially expressed proteins were observed. From the MELiSSA perspective, we could argue the effect of microgravity to be minimized, whereas R. rubrum S1H could be more sensitive to ionizing radiation during long-term space exploration mission. PMID:19571896

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  2. Water ingestion does not improve 1-h cycling performance in moderate ambient temperatures.

    PubMed

    Robinson, T A; Hawley, J A; Palmer, G S; Wilson, G R; Gray, D A; Noakes, T D; Dennis, S C

    1995-01-01

    Eight endurance-trained cyclists rode as far as possible in 1 h on a stationary cycle simulator in a moderate environment (20 degrees C, 60% relative humidity, 3 m.s-1 wind speed) while randomly receiving either no fluid (NF) or attempting to replace their approximate 1.71 sweat loss measured in a previous 1-h familiarisation performance ride at approximately 85% of peak oxygen uptake with artificially sweetened, coloured water (F). During F, the cyclists drank mean 1.49 (SEM 0.14) 1 of which mean 0.27 (SEM 0.08) 1 remained in the stomach at the end of exercise and mean 0.20 (SEM 0.05) 1 was urinated after the trial. Thus, only mean 1.02 (SEM 0.12) 1 of the ingested fluid was available to replace sweat losses during the 1-h performance ride. That fluid decreased the mean average heart rate from 166 (SEM 3) to 157 (SEM 5) beats.min-1 (P < 0.0001) and reduced the final mean serum [Na+] and osmolalities from 143 (SEM 0.6) to 139 (SEM 0.6) matom.l-1 (P < 0.005) and from 294 (SEM 1.7) to 290 (SEM 1.9) mosmol.l-1 (P = 0.05), respectively. Fluid ingestion did not significantly attenuate rises in plasma anti-diuretic hormone and angiotensin concentrations, or decrease the approximate-15% falls in estimated plasma volume in the F and NF trials. Nor did fluid ingestion significantly affect the approximate 1.71.h-1 sweat rates, the rises in rectal temperature (from 36.6 degrees to 38.3 degrees C) or the ratings of perceived exertion in the two trials.(ABSTRACT TRUNCATED AT 250 WORDS)

  3. Detection of epithelial ovarian cancer using 1H-NMR-based metabonomics.

    PubMed

    Odunsi, Kunle; Wollman, Robert M; Ambrosone, Christine B; Hutson, Alan; McCann, Susan E; Tammela, Jonathan; Geisler, John P; Miller, Gregory; Sellers, Thomas; Cliby, William; Qian, Feng; Keitz, Bernadette; Intengan, Marilyn; Lele, Shashikant; Alderfer, James L

    2005-02-20

    Currently available serum biomarkers are insufficiently reliable to distinguish patients with epithelial ovarian cancer (EOC) from healthy individuals. Metabonomics, the study of metabolic processes in biologic systems, is based on the use of (1)H-NMR spectroscopy and multivariate statistics for biochemical data generation and interpretation and may provide a characteristic fingerprint in disease. In an effort to examine the utility of the metabonomic approach for discriminating sera from women with EOC from healthy controls, we performed (1)H-NMR spectroscopic analysis on preoperative serum specimens obtained from 38 patients with EOC, 12 patients with benign ovarian cysts and 53 healthy women. After data reduction, we applied both unsupervised Principal Component Analysis (PCA) and supervised Soft Independent Modeling of Class Analogy (SIMCA) for pattern recognition. The sensitivity and specificity tradeoffs were summarized for each variable using the area under the receiver-operating characteristic (ROC) curve. In addition, we analyzed the regions of NMR spectra that most strongly influence separation of sera of EOC patients from healthy controls. PCA analysis allowed correct separation of all serum specimens from 38 patients with EOC (100%) from all of the 21 premenopausal normal samples (100%) and from all the sera from patients with benign ovarian disease (100%). In addition, it was possible to correctly separate 37 of 38 (97.4%) cancer specimens from 31 of 32 (97%) postmenopausal control sera. SIMCA analysis using the Cooman's plot demonstrated that sera classes from patients with EOC, benign ovarian cysts and the postmenopausal healthy controls did not share multivariate space, providing validation for the class separation. ROC analysis indicated that the sera from patients with and without disease could be identified with 100% sensitivity and specificity at the (1)H-NMR regions 2.77 parts per million (ppm) and 2.04 ppm from the origin (AUC of ROC curve = 1

  4. Determination of metabolite profiles in tropical wines by 1H NMR spectroscopy and chemometrics.

    PubMed

    da Silva Neto, Humberto G; da Silva, João B P; Pereira, Giuliano E; Hallwass, Fernando

    2009-12-01

    Traditionally, wines are produced in temperate climate zones, with one harvest per year. Tropical wines are a new concept of vitiviniculture that is being developed, principally in Brazil. The new Brazilian frontier is located in the northeast region (São Francisco River Valley) in Pernambuco State, close to the equator, between 8 and 9 degrees S. Compared with other Brazilian and worldwide vineyards, the grapes of this region possess peculiar characteristics. The aim of this work is a preliminary study of commercial São Francisco River Valley wines, analyzing their metabolite profiles by (1)H NMR and chemometric methods. PMID:19810052

  5. 1H and 13C NMR study on some substituted azolidine derivatives

    NASA Astrophysics Data System (ADS)

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

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

  6. Identification of Gastric Cancer Biomarkers Using 1H Nuclear Magnetic Resonance Spectrometry

    PubMed Central

    Yong, Wei Peng; Yeow, Chen Hua

    2016-01-01

    Existing gastric cancer diagnosing methods were invasive, hence, a reliable non-invasive gastric cancer diagnosing method is needed. As a starting point, we used 1H NMR for identifying gastric cancer biomarkers using a panel of gastric cancer spheroids and normal gastric spheroids. We were able to identify 8 chemical shift biomarkers for gastric cancer spheroids. Our data suggests that the cancerous and non-cancerous spheroids significantly differ in the lipid composition and energy metabolism. These results encourage the translation of these biomarkers into in-vivo gastric cancer detection methodology using MRI-MS. PMID:27611679

  7. In vivo localized 1H NMR spectroscopy at 11.7 Tesla

    NASA Astrophysics Data System (ADS)

    Crozier, Stuart; Field, James; Brereton, Ian M.; Moxon, Leith N.; Shannon, Gerald F.; Doddrell, David M.

    The SPACE volume-selection technique has been used to acquire high-resolution 1H spectra from the brain of neonate mice at 11.7 T (500 MHz). Spectra were acquired from voxels smaller than 20 μl. The spectra display elevated intensities of resonances arising from taurine and reduced intensities of those arising from N-acetylaspartate, when compared to those of mature animals, correlating well with in vitro studies. An integrated probe design consisting of separate transmission and reception RF coils and linear gradient coils is described. Comments are made concerning the advantages and disadvantages of performing gradient-encoded localized spectroscopy at this field strength.

  8. 1-Benzyl-4-(naphthalen-1-yl)-1H-1,2,3-triazole

    PubMed Central

    Sarmiento-Sánchez, Juan I.; Aguirre, Gerardo; Rivero, Ignacio A.

    2011-01-01

    In the title compound, C19H15N3, the benzyl group is almost perpendicular to the triazole ring [dihedral angle = 80.64 (8)°], while the napthyl group makes an angle of 30.27 (12)° with the plane of the triazole ring. This conformation is different from the 1-benzyl-4-phenyl-1H-1,2,3-triazole analogue, which has the benzyl ring system at an angle of 87.94° and the phenyl group at an angle of 3.35° to the plane of the triazole ring. PMID:21837221

  9. Identification of Gastric Cancer Biomarkers Using 1H Nuclear Magnetic Resonance Spectrometry.

    PubMed

    Ramachandran, Gokula Krishnan; Yong, Wei Peng; Yeow, Chen Hua

    2016-01-01

    Existing gastric cancer diagnosing methods were invasive, hence, a reliable non-invasive gastric cancer diagnosing method is needed. As a starting point, we used 1H NMR for identifying gastric cancer biomarkers using a panel of gastric cancer spheroids and normal gastric spheroids. We were able to identify 8 chemical shift biomarkers for gastric cancer spheroids. Our data suggests that the cancerous and non-cancerous spheroids significantly differ in the lipid composition and energy metabolism. These results encourage the translation of these biomarkers into in-vivo gastric cancer detection methodology using MRI-MS. PMID:27611679

  10. V/STOL AND digital avionics system for UH-1H

    NASA Technical Reports Server (NTRS)

    Liden, S.

    1978-01-01

    A hardware and software system for the Bell UH-1H helicopter was developed that provides sophisticated navigation, guidance, control, display, and data acquisition capabilities for performing terminal area navigation, guidance and control research. Two Sperry 1819B general purpose digital computers were used. One contains the development software that performs all the specified system flight computations. The second computer is available to NASA for experimental programs that run simultaneously with the other computer programs and which may, at the push of a button, replace selected computer computations. Other features that provide research flexibility include keyboard selectable gains and parameters and software generated alphanumeric and CRT displays.

  11. 1H NMR investigation of self-association of vanillin in aqueous solution

    NASA Astrophysics Data System (ADS)

    Bogdan, Mircea; Floare, Calin G.; Pîrnau, Adrian

    2009-08-01

    A self-association of vanillin have been studied by 1H NMR spectroscopy using the analysis of proton chemical shifts changes in aqueous solution as a function of concentration. The experimental results have been analysed using indefinite non-cooperative and cooperative models of molecular self-association, enabling the determination of equilibrium constants, parameters of cooperativity and the limiting values of vanillin proton chemical shifts in the complex. It was found that the dimer formation creates energetically favourable conditions for subsequent molecular association.

  12. Crystal structure of 2-methyl-1H-imidazol-3-ium hydrogen oxalate dihydrate.

    PubMed

    Diop, Mouhamadou Birame; Diop, Libasse; Plasseraud, Laurent; Cattey, Hélène

    2016-08-01

    Single crystals of the title mol-ecular salt, C4H7N2 (+)·HC2O4 (-)·2H2O, were isolated from the reaction of 2-methyl-1H-imidazole and oxalic acid in a 1:1 molar ratio in water. In the crystal, the cations and anions are positioned alternately along an infinite [010] ribbon and linked together through bifurcated N-H⋯(O,O) hydrogen bonds. The water mol-ecules of crystallization link the chains into (10-1) bilayers, with the methyl groups of the cations organized in an isotactic manner. PMID:27536393

  13. Investigation of the exclusive 3He(e,e' pn)1H reaction.

    PubMed

    Middleton, D G; Annand, J R M; Antelo, M Ases; Ayerbe, C; Barneo, P; Baumann, D; Bermuth, J; Bernauer, J; Blok, H P; Böhm, R; Bosnar, D; Ding, M; Distler, M O; Friedrich, J; Llongo, J García; Glazier, D I; Golak, J; Glöckle, W; Grabmayr, P; Hehl, T; Heim, J; Hesselink, W H A; Jans, E; Kamada, H; Mañas, G Jover; Kohl, M; Lapikás, L; MacGregor, I J D; Martin, I; McGeorge, J C; Merkel, H; Merle, P; Monstad, K; Moschini, F; Müller, U; Nogga, A; Pérez-Benito, R; Pospischil, Th; Potokar, M; Rosner, G; Seimetz, M; Skibiński, R; de Vries, H; Walcher, Th; Watts, D P; Weinriefer, M; Weiss, M; Witała, H; Zihlmann, B

    2009-10-01

    Cross sections for the 3He(e,e' pn)1H reaction were measured for the first time at energy transfers of 220 and 270 MeV for several momentum transfers ranging from 300 to 450 MeV/c. Cross sections are presented as a function of the momentum of the recoil proton and the momentum transfer. Continuum Faddeev calculations using the Argonne V18 and Bonn-B nucleon-nucleon potentials overestimate the measured cross sections by a factor 5 at low recoil proton momentum with the discrepancy becoming smaller at higher recoil proton momentum. PMID:19905628

  14. Determination of the delta(2H/1H)of Water: RSIL Lab Code 1574

    USGS Publications Warehouse

    Revesz, Kinga; Coplen, Tyler B.

    2008-01-01

    Reston Stable Isotope Laboratory (RSIL) lab code 1574 describes a method used to determine the relative hydrogen isotope-ratio delta(2H,1H), abbreviated hereafter as d2H of water. The d2H measurement of water also is a component of the National Water Quality Laboratory (NWQL) schedules 1142 and 1172. The water is collected unfiltered in a 60-mL glass bottle and capped with a Polyseal cap. In the laboratory, the water sample is equilibrated with gaseous hydrogen using a platinum catalyst (Horita, 1988; Horita and others, 1989; Coplen and others, 1991). The reaction for the exchange of one hydrogen atom is shown in equation 1.

  15. Determination of metabolite profiles in tropical wines by 1H NMR spectroscopy and chemometrics.

    PubMed

    da Silva Neto, Humberto G; da Silva, João B P; Pereira, Giuliano E; Hallwass, Fernando

    2009-12-01

    Traditionally, wines are produced in temperate climate zones, with one harvest per year. Tropical wines are a new concept of vitiviniculture that is being developed, principally in Brazil. The new Brazilian frontier is located in the northeast region (São Francisco River Valley) in Pernambuco State, close to the equator, between 8 and 9 degrees S. Compared with other Brazilian and worldwide vineyards, the grapes of this region possess peculiar characteristics. The aim of this work is a preliminary study of commercial São Francisco River Valley wines, analyzing their metabolite profiles by (1)H NMR and chemometric methods.

  16. Complete (1)H and (13)C signal assignment of prenol-10 with 3D NMR spectroscopy.

    PubMed

    Misiak, Maria; Koźmiński, Wiktor; Kwasiborska, Maria; Wójcik, Jacek; Ciepichal, Ewa; Swiezewska, Ewa

    2009-10-01

    The complete assignment of (1)H and (13)C chemical shifts of natural abundance prenol-10 is reported for the first time. It was achieved using 3D NMR experiments, which were based on random sampling of the evolution time space followed by multidimensional Fourier transform. This approach makes it possible to acquire 3D NMR spectra in a reasonable time and preserves high resolution in indirectly detected dimensions. It is shown that the interpretation of 3D COSY-HMBC and 3D TOCSY-HSQC spectra is crucial in the structural analysis of prenol-10.

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

    NASA Astrophysics Data System (ADS)

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

    1997-12-01

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

  18. Using Magnetic Coupling to Improve the (1)H/(2)H Double Tuned Circuit.

    PubMed

    Taber, Bob; Zens, Albert

    2015-10-01

    We report in this paper an analysis of double-tuned (1)H/(2)H circuits that are capacitively or inductively matched to 50 Ω ports. In this analysis we use a novel new parameter called the circuit fill factor (CFF). It provides a means of characterizing the performance degradation associated with additional inductors in the circuit in addition to circuit losses. This parameter allows for quick and insightful analysis of multiple tuned circuits for efficiency. It is also shown that magnetically coupled double-tuned circuits are less prone to unwanted spurious resonances due to their general symmetry which eliminates multiple ground paths in the circuit.

  19. Lactate rise detected by sup 1 H NMR in human visual cortex during physiologic stimulation

    SciTech Connect

    Prichard, J.; Rothman, D.; Novotny, E.; Petroff, O.; Kuwabara, Takeo; Avison, M.; Howseman, A.; Shulman, R. ); Hanstock, C. )

    1991-07-01

    Brain lactate concentration is usually assumed to be stable except when pathologic conditions cause a mismatch between glycolysis and respiration. Using newly developed {sup 1}H NMR spectroscopic techniques that allow measurement of lactate in vivo, the authors detected lactate elevations of 0.3-0.9 mM in human visual cortex during physiologic photic stimulation. The maximum rise appeared in the first few minutes; thereafter lactate concentration declined while stimulation continued. The results are consistent with a transient excess of glycolysis over respiration in the visual cortex, occurring as a normal response to stimulation in the physiologic range.

  20. Crystal structure of 2-methyl-1H-imidazol-3-ium hydrogen oxalate dihydrate

    PubMed Central

    Diop, Mouhamadou Birame; Diop, Libasse; Plasseraud, Laurent; Cattey, Hélène

    2016-01-01

    Single crystals of the title mol­ecular salt, C4H7N2 +·HC2O4 −·2H2O, were isolated from the reaction of 2-methyl-1H-imidazole and oxalic acid in a 1:1 molar ratio in water. In the crystal, the cations and anions are positioned alternately along an infinite [010] ribbon and linked together through bifurcated N—H⋯(O,O) hydrogen bonds. The water mol­ecules of crystallization link the chains into (10-1) bilayers, with the methyl groups of the cations organized in an isotactic manner. PMID:27536393

  1. Study of stereospecificity of 1H, 13C, 15N and 77Se shielding constants in the configurational isomers of the selenophene-2-carbaldehyde azine by NMR spectroscopy and MP2-GIAO calculations.

    PubMed

    Afonin, Andrei V; Pavlov, Dmitry V; Albanov, Alexander I; Levanova, Ekaterina P; Levkovskaya, Galina G

    2011-11-01

    In the (1)H and (13)C NMR spectra of selenophene-2-carbaldehyde azine, the (1)H-5, (13)C-3 and (13)C-5 signals of the selenophene ring are shifted to higher frequencies, whereas those of the (1)H-1, (13)C-1, (13)C-2 and (13)C-4 are shifted to lower frequencies on going from the EE to ZZ isomer or from the E moiety to the Z moiety of EZ isomer. The (15)N chemical shift is significantly larger in the EE isomer relative to the ZZ isomer and in the E moiety relative to the Z moiety of EZ isomer. A very pronounced difference (60-65 mg/g) between the (77)Se resonance positions is revealed in the studied azine isomers, the (77)Se peak being shifted to higher frequencies in the ZZ isomer and in the Z moiety of EZ isomer. The trends in the changes of the measured chemical shifts are reasonably reproduced by the GIAO calculations at the MP2 level of the (1)H, (13)C, (15)N and (77)Se shielding constants in the energy-favorable conformation with the syn orientation of both selenophene rings relative to the C = N groups. The NBO analysis suggests that such an arrangement of the selenophene rings may take place because of a higher energy of some intramolecular interactions. PMID:22002712

  2. Validating a robust double‐quantum‐filtered 1H MRS lactate measurement method in high‐grade brain tumours

    PubMed Central

    Harris, L.M.; Cairns, G.S.; Messiou, C.; deSouza, N.M.; Macdonald, A.; Saran, F.; Leach, M.O.

    2016-01-01

    1H MRS measurements of lactate are often confounded by overlapping lipid signals. Double‐quantum (DQ) filtering eliminates lipid signals and permits single‐shot measurements, which avoid subtraction artefacts in moving tissues. This study evaluated a single‐voxel‐localized DQ filtering method qualitatively and quantitatively for measuring lactate concentrations in the presence of lipid, using high‐grade brain tumours in which the results could be compared with standard acquisition as a reference. Paired standard acquisition and DQ‐filtered 1H MR spectra were acquired at 3T from patients receiving treatment for glioblastoma, using fLASER (localization by adiabatic selective refocusing using frequency offset corrected inversion pulses) single‐voxel localization. Data were acquired from 2 × 2 × 2 cm3 voxels, with a repetition time of 1 s and 128 averages (standard acquisition) or 256 averages (DQ‐filtered acquisition), requiring 2.15 and 4.3 min respectively. Of 37 evaluated data pairs, 20 cases (54%) had measureable lactate (fitted Cramér–Rao lower bounds ≤ 20%) in either the DQ‐filtered or the standard acquisition spectra. The measured DQ‐filtered lactate signal was consistently downfield of lipid (1.33 ± 0.03 ppm vs 1.22 ± 0.08 ppm; p = 0.002), showing that it was not caused by lipid breakthrough, and that it matched the lactate signal seen in standard measurements (1.36 ± 0.02 ppm). In the absence of lipid, similar lactate concentrations were measured by the two methods (mean ratio DQ filtered/standard acquisition = 1.10 ± 0.21). In 7/20 cases with measurable lactate, signal was not measureable in the standard acquisition owing to lipid overlap but was quantified in the DQ‐filtered acquisition. Conversely, lactate was undetected in seven DQ‐filtered acquisitions but visible using the standard acquisition. In conclusion, the DQ filtering method has proven robust in eliminating lipid and permits uncontaminated measurement of

  3. Radio-frequency excitation of harmonic microwave radiation from a Penning reflex discharge

    SciTech Connect

    Tate, J.P.; Wharton, C.B. )

    1993-04-01

    Experimental results on multiple-harmonic emission at 8.8 GHz from a Penning reflex discharge (PRD) are reported. Observations of the frequency spectra of microwave emission showed copius harmonic generation of frequencies having two completely different origins: (1) spontaneously excited high harmonics of the electron cyclotron frequency and (2) high harmonics of the frequency of an injected signal independent of the magnetic field strength, a phenomenon reported here for the first time. For spontaneous harmonic emission there was a current threshold, whose magnitude depended on gas pressure and magnetic field strength. When a signal was injected, however, high harmonics (up to the 18th) could be seen at discharge currents well below this threshold value. Comparisons between the two types of radiation are made and discussion of possible mechanisms is provided. It is concluded that the coupling efficiency of the radio-frequency (rf)-excited emission is dependent on the relationship between the rf drive frequency and the electron cyclotron frequency. Finite Larmor radius effects may also influence this coupling. The plasma sheath size will also be a factor in the transfer of energy from the probe to the bulk plasma. Results which seek to elucidate these effects are presented.

  4. Conformational stability and thermal pathways of relaxation in triclosan (antibacterial/excipient/contaminant) in solid-state: combined spectroscopic ((1)H NMR) and computational (periodic DFT) study.

    PubMed

    Latosińska, Jolanta Natalia; Latosińska, Magdalena; Tomczak, Marzena Agnieszka; Medycki, Wojciech

    2015-05-21

    The mechanism of molecular dynamics in the antibacterial/antifungal agent, triclosan (5-chloro-2-(2',4'-dichlorophenoxy)-phenol), in solid state was studied by (1)H NMR spectroscopy and periodic density functional theory (DFT) calculations. Temperature dependencies of the proton spin-lattice relaxation time (T1) in the ranges 86-293 and 90-250 K (at 15 and 24.667 MHz, respectively) and the second moment (M2) of the (1)H NMR resonant line in the range 103-300 K were measured. Two minima in the temperature dependence of T1 revealed a classical Arrhenius governed activation processes. The low temperature shallow minimum T1(T) of 71 s at 115 K, 15 MHz, which shifts with frequency, was assigned to classical hindered jumps of hydroxyl group around OC axis and with respect to a 5-chloro-2-phenol ring. The activation energy of this motion estimated on the basis of the fit of the theoretical model to the experimental points is 9.68 kJ/mol. The pointed high temperature minimum T1(T) of 59 s at 190 K, 15 MHz, which also shifts with frequency, was assigned to the small angle librations by Θlib= ± 9° between two positions of equilibrium differing in energy by 7.42 kJ/mol. The activation energy of this motion estimated on the basis of the fit of the theoretical model to the experimental points is 31.1 kJ/mol. Both motions result in a negligible reduction in the (1)H NMR line second moment, thus the second moment delivers an irrelevant description of the molecular motions in triclosan.

  5. Metabolic characterization of natural and cultured Ophicordyceps sinensis from different origins by 1H NMR spectroscopy.

    PubMed

    Zhang, Jianshuang; Zhong, Xin; Li, Shaosong; Zhang, Guren; Liu, Xin

    2015-11-10

    Ophicordyceps sinensis is a well-known traditional Chinese medicine and cultured mycelium is a substitute for wild O. sinensis. Metabolic profiles of wild O. sinensis from three geographical locations and cultivated mycelia derived from three origins were investigated using (1)H nuclear magnetic resonance (NMR) analysis combined with multivariate statistical analysis. A total of 56 primary metabolites were identified and quantified from O. sinensis samples. The principle component analysis (PCA) showed significant differences between natural O. sinensis and fermentation mycelia. Seven metabolites responsible for differentiation were screened out by orthogonal partial least squares discriminant analysis (OPLS-DA). The concentrations of mannitol, trehalose, arginine, trans-4-hydroxyproline, alanine and glucitol were significantly different between wild and cultured groups. The variation in metabolic profiling among artificial mycelia was greater than that among wild O. sinensis. Furthermore, wild samples from different origins were clearly distinguished by the levels of mannitol, trehalose and some amino acids. This study indicates that (1)H NMR-based metabolomics is useful for fingerprinting and discriminating O. sinensis of different geographical regions and cultivated mycelia of different strains. The present study provided an efficient approach for investigating chemical compositions and evaluating the quality of medicine and health food derived from O. sinensis. PMID:26279370

  6. Effect of Exercise on the Creatine Resonances in 1H MR Spectra of Human Skeletal Muscle

    NASA Astrophysics Data System (ADS)

    Kreis, R.; Jung, B.; Slotboom, J.; Felblinger, J.; Boesch, C.

    1999-04-01

    1H MR spectra of human muscles were recorded before, during, and after fatiguing exercise. In contrast to expectations, it was found that the spectral contributions of creatine/phosphocreatine (Cr/PCr) were subject to change as a function of exercise. In particular, the dipolar-coupled methylene protons of Cr/PCr were found to be reduced in intensity in proportion to the co-registered PCr levels. Recovery after exercise and behavior under ischemic conditions provide further evidence to suggest that the contributions of the CH2protons of Cr/PCr to1H MR spectra of human musclein vivoreflect PCr rather than Cr levels. Variation of experimental parameters showed that this effect is not due to a trivial change in relaxation times. At present it can only be speculated about why the Cr resonances have reduced NMR visibility. If temporary binding to macromolecules should be involved, the free Cr concentration-important for equilibrium calculations of the creatine kinase reaction-might be different from what was previously assumed.

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

    SciTech Connect

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

    1988-03-01

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

  8. An improved technique for the 2H/1H analysis of urines from diabetic volunteers

    USGS Publications Warehouse

    Coplen, T.B.; Harper, I.T.

    1994-01-01

    The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, ~ 1-2???, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, approximately 1-2%, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.

  9. Reliability of a 1-h endurance performance test in trained female cyclists.

    PubMed

    Bishop, D

    1997-04-01

    Endurance performance is a common criterion used to evaluate training or dietary interventions. However, to accurately appraise the effects of an intervention, the endurance performance measure must be reliable. The purpose of the investigation was to establish the reliability of a 1-h endurance performance test. Twenty trained female subjects (peak VO2 = 47.4 +/- 7.2 ml.kg-1.min-1) completed two trials in which they had to generate the highest power output possible throughout 60 min of cycling. Heart rates (HR) and ratings of perceived exertion (RPE) were also recorded during these two trials. All tests were conducted on a wind-braked cycle ergometer set up to closely resemble the subject's own cycle. The trials were separated by 1 wk, conducted on the same day of the week, and completed at a similar time of the day. The average power outputs (+/-SD) for the two trials were 180.0 (+/-18.1) W and 180.0 (+/-20.6) W. The results revealed that average absolute power output, HR, and RPE were not significantly different between trials. The intraclass correlation coefficient (one way ANOVA) for average absolute power output was 0.97, the coefficient of variation was 2.7%, and the SEM was 3.4 W. These results suggest that under controlled conditions average absolute power output during a 1-h endurance test is a reliable measure for trained female cyclists.

  10. (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.

  11. Antifungal properties of wheat histones (H1-H4) and purified wheat histone H1.

    PubMed

    De Lucca, Anthony J; Heden, Lars-Olof; Ingber, Bruce; Bhatnagar, Deepak

    2011-07-13

    Wheat ( Triticum spp.) histones H1, H2, H3, and H4 were extracted, and H1 was further purified. The effect of these histones on specific fungi that may or may not be pathogenic to wheat was determined. These fungi included Aspergillus flavus , Aspergillus fumigatus , Aspergillus niger , Fusarium oxysporum , Fusarium verticillioides , Fusarium solani , Fusarium graminearum , Penicillium digitatum , Penicillium italicum , and Greeneria uvicola . Non-germinated and germinating conidia of these fungi were bioassayed separately. The non-germinated and germinating conidia of all Fusarium species were highly susceptible to the mixture (H1-H4) as well as pure H1, with viability losses of 99-100% found to be significant (p < 0.001) at ≤10 μM or less for the histone mixture and pure H1. F. graminearum was the most sensitive to histone activity. The histones were inactive against all of the non-germinated Penicillium spp. conidia. However, they significantly reduced the viability of the germinating conidia of the Penicillium spp. conidia, with 95% loss at 2.5 μM. Non-germinated and germinating conidia viability of the Aspergillus spp. and G. uvicola were unaffected when exposed to histones up to 10 μM. Results indicate that Fusarium spp. pathogenic to wheat are susceptible to wheat histones, indicating that these proteins may be a resistance mechanism in wheat against fungal infection.

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

    PubMed

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

    2015-05-15

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

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

    PubMed

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

    2013-08-15

    Based on a model system approach, five different proton populations were distinguished in pound cake crumb using one dimensional low resolution (1)H NMR spectroscopy. In free induction decay (FID) measurements, proton populations were assigned to (i) non-exchanging CH protons of crystalline starch, proteins and crystalline fat and (ii) non-exchanging CH protons of amorphous starch and gluten, which are in little contact with water. In Carr-Purcell-Meiboom-Gill (CPMG) measurements, three proton populations were distinguished. The CPMG population with the lowest mobility and the FID population with the highest mobility represent the same proton population. The two CPMG proton populations with the highest mobility were assigned to exchanging protons (i.e., protons of water, starch, gluten, egg proteins and sugar) and protons of lipids (i.e., protons of egg yolk lipids and amorphous lipid fraction of margarine) respectively. Based on their spin-lattice relaxation times (T1), two dimensional (1)H NMR spectroscopy further resolved the two proton populations with the highest mobility into three and two proton populations, respectively. PMID:23561087

  14. Wastewater Colloidal Organic Carbon: Characterization of Filtration Fractions Using 1H NMR.

    PubMed

    McPhedran, Kerry N; Seth, Rajesh

    2016-04-01

    The current study separates colloidal organic carbon (COC) of municipal wastewater using membrane and ultrafiltration filters followed by characterization using 1H nuclear magnetic resonance (NMR) and UV absorbance with the goal of determination of size-specific characteristics, which may be used to correlate contaminant partitioning to natural COC. Passing fractions included 49.7, 44.8, 39.3, and 33.1 mg/L COC for filter sizes 1.5 μm, 0.45 μm, 100 kDa, and 1 kDa, respectively. The methodology used for processing COC prior to 1H NMR characterization was novel and successful in concentrating COC without modification of structures, which is the general drawback of other separation techniques such as resin extractions. This concentration technique is quite simple (i.e., not dependent on specialized instrumentation) and allows much shorter NMR experimental durations saving time and cost of analysis. Further work using NMR techniques will allow for greater understanding of COC molecular characteristics and be valuable for use in predictive modeling improvements. PMID:27131054

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

    PubMed

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

    2013-08-15

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

  16. Nuclear localization of human DNA mismatch repair protein exonuclease 1 (hEXO1)

    PubMed Central

    Knudsen, Nina Østergaard; Nielsen, Finn Cilius; Vinther, Lena; Bertelsen, Ronni; Holten-Andersen, Steen; Liberti, Sascha Emilie; Hofstra, Robert; Kooi, Krista; Rasmussen, Lene Juel

    2007-01-01

    Human exonuclease 1 (hEXO1) is implicated in DNA mismatch repair (MMR) and mutations in hEXO1 may be associated with hereditary nonpolyposis colorectal cancer (HNPCC). Since the subcellular localization of MMR proteins is essential for proper MMR function, we characterized possible nuclear localization signals (NLSs) in hEXO1. Using fluorescent fusion proteins, we show that the sequence 418KRPR421, which exhibit strong homology to other monopartite NLS sequences, is responsible for correct nuclear localization of hEXO1. This NLS sequence is located in a region that is also required for hEXO1 interaction with hMLH1 and we show that defective nuclear localization of hEXO1 mutant proteins could be rescued by hMLH1 or hMSH2. Both hEXO1 and hMLH1 form complexes with the nuclear import factors importin β/α1,3,7 whereas hMSH2 specifically recognizes importin β/α3. Taken together, we infer that hEXO1, hMLH1 and hMSH2 form complexes and are imported to the nucleus together, and that redundant NLS import signals in the proteins may safeguard nuclear import and thereby MMR activity. PMID:17426132

  17. 1H NMR metabonomics approach to the disease continuum of diabetic complications and premature death.

    PubMed

    Mäkinen, Ville-Petteri; Soininen, Pasi; Forsblom, Carol; Parkkonen, Maija; Ingman, Petri; Kaski, Kimmo; Groop, Per-Henrik; Ala-Korpela, Mika

    2008-01-01

    Subtle metabolic changes precede and accompany chronic vascular complications, which are the primary causes of premature death in diabetes. To obtain a multimetabolite characterization of these high-risk individuals, we measured proton nuclear magnetic resonance (1H NMR) data from the serum of 613 patients with type I diabetes and a diverse spread of complications. We developed a new metabonomics framework to visualize and interpret the data and to link the metabolic profiles to the underlying diagnostic and biochemical variables. Our results indicate complex interactions between diabetic kidney disease, insulin resistance and the metabolic syndrome. We illustrate how a single 1H NMR protocol is able to identify the polydiagnostic metabolite manifold of type I diabetes and how its alterations translate to clinical phenotypes, clustering of micro- and macrovascular complications, and mortality during several years of follow-up. This work demonstrates the diffuse nature of complex vascular diseases and the limitations of single diagnostic biomarkers. However, it also promises cost-effective solutions through high-throughput analytics and advanced computational methods, as applied here in a case that is representative of the real clinical situation.

  18. (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

  19. Characterization of dandelion species using 1H NMR- and GC-MS-based metabolite profiling.

    PubMed

    Jung, Youngae; Ahn, Yun Gyong; Kim, Ho Kyoung; Moon, Byeong Cheol; Lee, A Yeong; Ryu, Do Hyun; Hwang, Geum-Sook

    2011-10-21

    Taraxacum, known as dandelion, is a large genus of plants in the family Asteraceae. Pharmacological studies have shown that these plants display a wide variety of medicinal properties because Taraxacum extracts contain many pharmacologically active metabolites that display anti-inflammatory, antinociceptive, antioxidant, and anticancer activity. Each plant species displays several different natural constituents, the majority of which have not been studied as no global metabolite screen of the diverse Taraxacum species has been performed. In this study, we investigated the metabolite difference in three species of Taraxacum (T. coreanum, T. officinale, and T. platycarpum) by (1)H NMR spectroscopy and gas chromatography-mass spectrometry (GC-MS) coupled with multivariate statistical analyses. The aim of this study was to identify the different chemical compositions of the polar and nonpolar extracts in these species. A partial least-squares discriminant analysis showed a significantly higher separation among nonpolar extracts (mainly fatty acids and sterols) compared to polar extracts (mainly amino acids, organic acids, and sugars) between these species. A one-way ANOVA was performed to statistically certify the metabolite differences of these nonpolar extracts. Taken together, these data suggest that a metabolomic approach using combined (1)H NMR and GC-MS analysis is an effective analytical method to differentiate biochemical compositions among different species in plants.

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

    PubMed

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

    2015-02-14

    Four model thiosemicarbazide anion chemosensors containing three N-H bonds, substituted with phenyl and/or 4-nitrophenyl units, were synthesised and studied for their anion binding abilities with hydroxide, fluoride, acetate, dihydrogen phosphate and chloride. The anion binding properties were studied in DMSO and 9 : 1 DMSO-H2O by UV-visible absorption and (1)H/(13)C/(15)N NMR spectroscopic techniques and corroborated with DFT studies. Significant changes were observed in the UV-visible absorption spectra with all anions, except for chloride, accompanied by dramatic colour changes visible to the naked eye. These changes were determined to be due to the deprotonation of the central N-H proton and not due to hydrogen bonding based on (1)H/(15)N NMR titration studies with acetate in DMSO-d6-0.5% water. Direct evidence for deprotonation was confirmed by the disappearance of the central thiourea proton and the formation of acetic acid. DFT and charge distribution calculations suggest that for all four compounds the central N-H proton is the most acidic. Hence, the anion chemosensors operate by a deprotonation mechanism of the central N-H proton rather than by hydrogen bonding as is often reported. PMID:25451865

  1. Antimalarial 4(1H)-pyridones bind to the Qi site of cytochrome bc1

    PubMed Central

    Capper, Michael J.; O’Neill, Paul M.; Fisher, Nicholas; Strange, Richard W.; Moss, Darren; Ward, Stephen A.; Berry, Neil G.; Lawrenson, Alexandre S.; Hasnain, S. Samar; Biagini, Giancarlo A.; Antonyuk, Svetlana V.

    2015-01-01

    Cytochrome bc1 is a proven drug target in the prevention and treatment of malaria. The rise in drug-resistant strains of Plasmodium falciparum, the organism responsible for malaria, has generated a global effort in designing new classes of drugs. Much of the design/redesign work on overcoming this resistance has been focused on compounds that are presumed to bind the Qo site (one of two potential binding sites within cytochrome bc1) using the known crystal structure of this large membrane-bound macromolecular complex via in silico modeling. Cocrystallization of the cytochrome bc1 complex with the 4(1H)-pyridone class of inhibitors, GSK932121 and GW844520, that have been shown to be potent antimalarial agents in vivo, revealed that these inhibitors do not bind at the Qo site but bind at the Qi site. The discovery that these compounds bind at the Qi site may provide a molecular explanation for the cardiotoxicity and eventual failure of GSK932121 in phase-1 clinical trial and highlight the need for direct experimental observation of a compound bound to a target site before chemical optimization and development for clinical trials. The binding of the 4(1H)-pyridone class of inhibitors to Qi also explains the ability of this class to overcome parasite Qo-based atovaquone resistance and provides critical structural information for future design of new selective compounds with improved safety profiles. PMID:25564664

  2. Distinguishing sources of groundwater nitrate by 1H NMR of dissolved organic matter.

    PubMed

    Lu, Jianhang; Chang, Andrew C; Wu, Laosheng

    2004-11-01

    Dissolved organic matter (DOM) originating from a certain source usually carries characteristic marks in its molecular structures that can be recognized by spectroscopic analysis. Sources of water-borne contaminants, such as nitrate, can be identified by recognition of the characteristics of DOM entrained in the water. In this study, DOM in groundwaters sampled from a dairy/crop production area (Chino Basin, CA) was analyzed by 1H nuclear magnetic resonance (1H NMR). Results showed that DOM derived from natural soil organic matter has a characteristic resonance at a chemical shift region of 4.0-4.3 ppm, while DOM derived from dairy wastes has a characteristic resonance at a lower chemical shift region of 3.2-3.6 ppm. These signature resonances were then used to distinguish the origins of nitrate in the groundwater. It was found that disposal of dairy wastes on croplands is the primary source of nitrate contamination in groundwater underlying the Chino Basin dairy area.

  3. Novel 1H low field nuclear magnetic resonance applications for the field of biodiesel

    PubMed Central

    2013-01-01

    Background Biodiesel production has increased dramatically over the last decade, raising the need for new rapid and non-destructive analytical tools and technologies. 1H Low Field Nuclear Magnetic Resonance (LF-NMR) applications, which offer great potential to the field of biodiesel, have been developed by the Phyto Lipid Biotechnology Lab research team in the last few years. Results Supervised and un-supervised chemometric tools are suggested for screening new alternative biodiesel feedstocks according to oil content and viscosity. The tools allowed assignment into viscosity groups of biodiesel-petrodiesel samples whose viscosity is unknown, and uncovered biodiesel samples that have residues of unreacted acylglycerol and/or methanol, and poorly separated and cleaned glycerol and water. In the case of composite materials, relaxation time distribution, and cross-correlation methods were successfully applied to differentiate components. Continuous distributed methods were also applied to calculate the yield of the transesterification reaction, and thus monitor the progress of the common and in-situ transesterification reactions, offering a tool for optimization of reaction parameters. Conclusions Comprehensive applied tools are detailed for the characterization of new alternative biodiesel resources in their whole conformation, monitoring of the biodiesel transesterification reaction, and quality evaluation of the final product, using a non-invasive and non-destructive technology that is new to the biodiesel research area. A new integrated computational-experimental approach for analysis of 1H LF-NMR relaxometry data is also presented, suggesting improved solution stability and peak resolution. PMID:23590829

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

    NASA Astrophysics Data System (ADS)

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

    1999-10-01

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

  5. 1H NMR metabolite fingerprinting as a new tool for body fluid identification in forensic science.

    PubMed

    Scano, Paola; Locci, Emanuela; Noto, Antonio; Navarra, Gabriele; Murgia, Federica; Lussu, Milena; Barberini, Luigi; Atzori, Luigi; De Giorgio, Fabio; Rosa, Maria Francesca; d'Aloja, Ernesto

    2013-08-01

    In this feasibility study, we propose, for the first time, (1)H NMR spectroscopy coupled with mathematical strategies as a valid tool for body fluid (BF) trace identification in forensic science. In order to assess the ability of this approach to identify traces composed either by a single or by two different BFs, samples of blood, urine, saliva, and semen were collected from different donors, and binary mixtures were prepared. (1)H NMR analyses were carried out for all samples. Spectral data of the whole set were firstly submitted to unsupervised principal component analysis (PCA); it showed that samples of the same BF cluster well on the basis of their characterizing molecular components and that mixtures exhibit intermediate characteristics among BF typologies. Furthermore, samples were divided into a training set and a test set. An average NMR spectral profile for each typology of BF was obtained from the training set and validated as representative of each BF class. Finally, a fitting procedure, based on a system of linear equations with the four obtained average spectral profiles, was applied to the test set and the mixture samples; it showed that BFs can be unambiguously identified, even as components of a mixture. The successful use of this mathematical procedure has the advantage, in forensics, of overcoming bias due to the analyst's personal judgment. We therefore propose this combined approach as a valid, fast, and non-destructive tool for addressing the challenges in the identification of composite traces in forensics.

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

    PubMed Central

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

    2015-01-01

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

  7. Metabolic characterization of natural and cultured Ophicordyceps sinensis from different origins by 1H NMR spectroscopy.

    PubMed

    Zhang, Jianshuang; Zhong, Xin; Li, Shaosong; Zhang, Guren; Liu, Xin

    2015-11-10

    Ophicordyceps sinensis is a well-known traditional Chinese medicine and cultured mycelium is a substitute for wild O. sinensis. Metabolic profiles of wild O. sinensis from three geographical locations and cultivated mycelia derived from three origins were investigated using (1)H nuclear magnetic resonance (NMR) analysis combined with multivariate statistical analysis. A total of 56 primary metabolites were identified and quantified from O. sinensis samples. The principle component analysis (PCA) showed significant differences between natural O. sinensis and fermentation mycelia. Seven metabolites responsible for differentiation were screened out by orthogonal partial least squares discriminant analysis (OPLS-DA). The concentrations of mannitol, trehalose, arginine, trans-4-hydroxyproline, alanine and glucitol were significantly different between wild and cultured groups. The variation in metabolic profiling among artificial mycelia was greater than that among wild O. sinensis. Furthermore, wild samples from different origins were clearly distinguished by the levels of mannitol, trehalose and some amino acids. This study indicates that (1)H NMR-based metabolomics is useful for fingerprinting and discriminating O. sinensis of different geographical regions and cultivated mycelia of different strains. The present study provided an efficient approach for investigating chemical compositions and evaluating the quality of medicine and health food derived from O. sinensis.

  8. (1)H NMR Spectroscopy of Fecal Extracts Enables Detection of Advanced Colorectal Neoplasia.

    PubMed

    Amiot, Aurelien; Dona, Anthony C; Wijeyesekera, Anisha; Tournigand, Christophe; Baumgaertner, Isabelle; Lebaleur, Yann; Sobhani, Iradj; Holmes, Elaine

    2015-09-01

    Colorectal cancer (CRC) is a growing cause of mortality in developing countries, warranting investigation into its etiopathogenesis and earlier diagnosis. Here, we investigated the fecal metabolic phenotype of patients with advanced colorectal neoplasia and controls using (1)H-nuclear magnetic resonance (NMR) spectroscopy and multivariate modeling. The fecal microbiota composition was assessed by quantitative real-time PCR as well as Wif-1 methylation levels in stools, serum, and urine and correlated to the metabolic profile of each patient. The predictivity of the model was 0.507 (Q(2)Y), and the explained variance was 0.755 (R(2)Y). Patients with advanced colorectal neoplasia demonstrated increased fecal concentrations of four short-chain fatty acids (valerate, acetate, propionate, and butyrate) and decreased signals relating to β-glucose, glutamine, and glutamate. The predictive accuracy of the multivariate (1)H NMR model was higher than that of the guaiac-fecal occult blood test and the Wif-1 methylation test for predicting advanced colorectal neoplasia. Correlation analysis between fecal metabolites and bacterial profiles revealed strong associations between Faecalibacterium prausnitzii and Clostridium leptum species with short-chain fatty acids concentration and inverse correlation between Faecalibacterium prausnitzii and glucose. These preliminary results suggest that fecal metabonomics may potentially have a future role in a noninvasive colorectal screening program and may contribute to our understanding of the role of these dysregulated molecules in the cross-talk between the host and its bacterial microbiota.

  9. 1H-NMR METABONOMICS ANALYSIS OF SERA DIFFERENTIATES BETWEEN MAMMARY TUMOR-BEARING MICE AND HEALTHY CONTROLS

    EPA Science Inventory

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

  10. In vivo and ex vivo measurements: noninvasive assessment of alcoholic fatty liver using 1H-MR spectroscopy

    PubMed Central

    Keese, Daniel; Korkusuz, Hüdayi; Huebner, Frank; Namgaladze, Dmitry; Raschidi, Bahram; Vogl, Thomas J.

    2016-01-01

    PURPOSE We aimed to evaluate the ability of 1H-magnetic resonance spectroscopy (1H-MRS) to detect and quantify hepatic fat content in vivo and ex vivo in an experimental rat model of alcoholic fatty liver using histopathology, biochemistry, and laboratory analyses as reference. METHODS Alcoholic fatty liver was induced within 48 hours in 20 Lewis rats; 10 rats served as control. Intrahepatic fat content determined by 1H-MRS was expressed as the percent ratio of the lipid and water peaks and was correlated with intrahepatic fat content determined histologically and biochemically. Liver enzymes were measured in serum. RESULTS Fatty liver could be detected in vivo as well as ex vivo using 1H-MRS, in all 20 animals. Histologic analysis showed a fatty liver in 16 of 20 animals. Histology and 1H-MRS results were highly correlated (in vivo, r=0.93, P = 0.0005; ex vivo, r=0.92, P = 0.0006). Also a strong correlation was noted between in vivo 1H-MRS measurements and the fat content determined biochemically (r=0.96, P = 0.0003). Ex vivo results showed a similarly strong correlation between 1H-MRS and biochemistry (r=0.89, P = 0.0011). CONCLUSION 1H-MRS can be carried out in ex vivo models, as well as in vivo, to detect and quantify intrahepatic fat content in the acute fatty liver. PMID:26627137

  11. 40 CFR 721.4468 - 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 1H-Imidazole, 2-ethyl-4,5-dihydro-4... Specific Chemical Substances § 721.4468 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  12. 40 CFR 721.4468 - 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 1H-Imidazole, 2-ethyl-4,5-dihydro-4... Specific Chemical Substances § 721.4468 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  13. 40 CFR 721.4468 - 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false 1H-Imidazole, 2-ethyl-4,5-dihydro-4... Specific Chemical Substances § 721.4468 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  14. 40 CFR 721.4468 - 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 1H-Imidazole, 2-ethyl-4,5-dihydro-4... Specific Chemical Substances § 721.4468 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  15. 40 CFR 721.4468 - 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 1H-Imidazole, 2-ethyl-4,5-dihydro-4... Specific Chemical Substances § 721.4468 1H-Imidazole, 2-ethyl-4,5-dihydro-4-methyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  16. Frequency spirals

    NASA Astrophysics Data System (ADS)

    Ottino-Löffler, Bertrand; Strogatz, Steven H.

    2016-09-01

    We study the dynamics of coupled phase oscillators on a two-dimensional Kuramoto lattice with periodic boundary conditions. For coupling strengths just below the transition to global phase-locking, we find localized spatiotemporal patterns that we call "frequency spirals." These patterns cannot be seen under time averaging; they become visible only when we examine the spatial variation of the oscillators' instantaneous frequencies, where they manifest themselves as two-armed rotating spirals. In the more familiar phase representation, they appear as wobbly periodic patterns surrounding a phase vortex. Unlike the stationary phase vortices seen in magnetic spin systems, or the rotating spiral waves seen in reaction-diffusion systems, frequency spirals librate: the phases of the oscillators surrounding the central vortex move forward and then backward, executing a periodic motion with zero winding number. We construct the simplest frequency spiral and characterize its properties using analytical and numerical methods. Simulations show that frequency spirals in large lattices behave much like this simple prototype.

  17. Monoclonal antibody against recombinant Fasciola gigantica cathepsin L1H could detect juvenile and adult cathepsin Ls of Fasciola gigantica.

    PubMed

    Wongwairot, Sirima; Kueakhai, Pornanan; Changklungmoa, Narin; Jaikua, Wipaphorn; Sansri, Veerawat; Meemon, Krai; Songkoomkrong, Sineenart; Riengrojpitak, Suda; Sobhon, Prasert

    2015-01-01

    Cathepsin Ls (CatLs), the major cysteine protease secreted by Fasciola spp., are important for parasite digestion and tissue invasion. Fasciola gigantica cathepsin L1H (FgCatL1H) is the isotype expressed in the early stages for migration and invasion. In the present study, a monoclonal antibody (MoAb) against recombinant F. gigantica cathepsin L1H (rFgCatL1H) was produced by hybridoma technique using spleen cells from BALB/c mice immunized with recombinant proFgCatL1H (rproFgCatL1H). This MoAb is an immunoglobulin (Ig)G1 with κ light chain isotype. The MoAb reacted specifically with rproFgCatL1H, the native FgCatL1H at a molecular weight (MW) 38 to 48 kDa in the extract of whole body (WB) of metacercariae and newly excysted juvenile (NEJ) and cross-reacted with rFgCatL1 and native FgCatLs at MW 25 to 28 kDa in WB of 2- and 4-week-old juveniles, adult, and adult excretory-secretory (ES) fractions by immunoblotting and indirect ELISA. It did not cross-react with antigens in WB fractions from other parasites, including Gigantocotyle explanatum, Paramphistomum cervi, Gastrothylax crumenifer, Eurytrema pancreaticum, Setaria labiato-papillosa, and Fischoederius cobboldi. By immunolocalization, MoAb against rFgCatL1H reacted with the native protein in the gut of metacercariae and NEJ and also cross-reacted with CatL1 in 2- and 4-week-old juveniles and adult F. gigantica. Therefore, FgCatL1H and its MoAb may be used for immunodiagnosis of both early and late fasciolosis in ruminants and humans.

  18. Monoclonal antibody against recombinant Fasciola gigantica cathepsin L1H could detect juvenile and adult cathepsin Ls of Fasciola gigantica.

    PubMed

    Wongwairot, Sirima; Kueakhai, Pornanan; Changklungmoa, Narin; Jaikua, Wipaphorn; Sansri, Veerawat; Meemon, Krai; Songkoomkrong, Sineenart; Riengrojpitak, Suda; Sobhon, Prasert

    2015-01-01

    Cathepsin Ls (CatLs), the major cysteine protease secreted by Fasciola spp., are important for parasite digestion and tissue invasion. Fasciola gigantica cathepsin L1H (FgCatL1H) is the isotype expressed in the early stages for migration and invasion. In the present study, a monoclonal antibody (MoAb) against recombinant F. gigantica cathepsin L1H (rFgCatL1H) was produced by hybridoma technique using spleen cells from BALB/c mice immunized with recombinant proFgCatL1H (rproFgCatL1H). This MoAb is an immunoglobulin (Ig)G1 with κ light chain isotype. The MoAb reacted specifically with rproFgCatL1H, the native FgCatL1H at a molecular weight (MW) 38 to 48 kDa in the extract of whole body (WB) of metacercariae and newly excysted juvenile (NEJ) and cross-reacted with rFgCatL1 and native FgCatLs at MW 25 to 28 kDa in WB of 2- and 4-week-old juveniles, adult, and adult excretory-secretory (ES) fractions by immunoblotting and indirect ELISA. It did not cross-react with antigens in WB fractions from other parasites, including Gigantocotyle explanatum, Paramphistomum cervi, Gastrothylax crumenifer, Eurytrema pancreaticum, Setaria labiato-papillosa, and Fischoederius cobboldi. By immunolocalization, MoAb against rFgCatL1H reacted with the native protein in the gut of metacercariae and NEJ and also cross-reacted with CatL1 in 2- and 4-week-old juveniles and adult F. gigantica. Therefore, FgCatL1H and its MoAb may be used for immunodiagnosis of both early and late fasciolosis in ruminants and humans. PMID:25324133

  19. Improving Assessment of Lipoprotein Profile in Type 1 Diabetes by 1H NMR Spectroscopy

    PubMed Central

    Brugnara, Laura; Mallol, Roger; Ribalta, Josep; Vinaixa, Maria; Murillo, Serafín; Casserras, Teresa; Guardiola, Montse; Vallvé, Joan Carles; Kalko, Susana G.; Correig, Xavier; Novials, Anna

    2015-01-01

    Patients with type 1 diabetes (T1D) present increased risk of cardiovascular disease (CVD). The aim of this study is to improve the assessment of lipoprotein profile in patients with T1D by using a robust developed method 1H nuclear magnetic resonance spectroscopy (1H NMR), for further correlation with clinical factors associated to CVD. Thirty patients with T1D and 30 non-diabetes control (CT) subjects, matched for gender, age, body composition (DXA, BMI, waist/hip ratio), regular physical activity levels and cardiorespiratory capacity (VO2peak), were analyzed. Dietary records and routine lipids were assessed. Serum lipoprotein particle subfractions, particle sizes, and cholesterol and triglycerides subfractions were analyzed by 1H NMR. It was evidenced that subjects with T1D presented lower concentrations of small LDL cholesterol, medium VLDL particles, large VLDL triglycerides, and total triglycerides as compared to CT subjects. Women with T1D presented a positive association with HDL size (p<0.005; R = 0.601) and large HDL triglycerides (p<0.005; R = 0.534) and negative (p<0.005; R = -0.586) to small HDL triglycerides. Body fat composition represented an important factor independently of normal BMI, with large LDL particles presenting a positive correlation to total body fat (p<0.005; R = 0.505), and total LDL cholesterol and small LDL cholesterol a positive correlation (p<0.005; R = 0.502 and R = 0.552, respectively) to abdominal fat in T1D subjects; meanwhile, in CT subjects, body fat composition was mainly associated to HDL subclasses. VO2peak was negatively associated (p<0.005; R = -0.520) to large LDL-particles only in the group of patients with T1D. In conclusion, patients with T1D with adequate glycemic control and BMI and without chronic complications presented a more favourable lipoprotein profile as compared to control counterparts. In addition, slight alterations in BMI and/or body fat composition showed to be relevant to provoking alterations in

  20. Discovery, Synthesis, and Optimization of Antimalarial 4(1H)-Quinolone-3-Diarylethers

    PubMed Central

    2014-01-01

    The historical antimalarial compound endochin served as a structural lead for optimization. Endochin-like quinolones (ELQ) were prepared by a novel chemical route and assessed for in vitro activity against multidrug resistant strains of Plasmodium falciparum and against malaria infections in mice. Here we describe the pathway to discovery of a potent class of orally active antimalarial 4(1H)-quinolone-3-diarylethers. The initial prototype, ELQ-233, exhibited low nanomolar IC50 values against all tested strains including clinical isolates harboring resistance to atovaquone. ELQ-271 represented the next critical step in the iterative optimization process, as it was stable to metabolism and highly effective in vivo. Continued analoging revealed that the substitution pattern on the benzenoid ring of the quinolone core significantly influenced reactivity with the host enzyme. This finding led to the rational design of highly selective ELQs with outstanding oral efficacy against murine malaria that is superior to established antimalarials chloroquine and atovaquone. PMID:24720377

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

    PubMed

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

    2016-04-01

    Capsaicinoids are the compounds responsible for the pungency of chili peppers. These substances have attracted the attention of many research groups in recent decades because of their antinociceptive, analgesic, anti-inflammatory, and anti-obesity properties, among others. There are nearly 160 capsaicinoids reported in the literature. Approximately 25 of them are natural products, while the rest are synthetic or semi-synthetic products. A large amount of NMR data for the capsaicinoids is dispersed throughout literature. Therefore, there is a need to organize all this NMR data in a systematic and orderly way. This review summarizes the (1) H and (13) C NMR data on 159 natural and synthetic capsaicinoids, with a brief discussion of some typical and relevant aspects of these NMR data. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26626418

  2. Single-Quantum Coherence Filter for Strongly Coupled Spin Systems for Localized 1H NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Trabesinger, Andreas H.; Mueller, D. Christoph; Boesiger, Peter

    2000-08-01

    A pulse sequence for localized in vivo1H NMR spectroscopy is presented, which selectively filters single-quantum coherence built up by strongly coupled spin systems. Uncoupled and weakly coupled spin systems do not contribute to the signal output. Analytical calculations using a product operator description of the strongly coupled AB spin system as well as in vitro tests demonstrate that the proposed filter produces a signal output for a strongly coupled AB spin system, whereas the resonances of a weakly coupled AX spin system and of uncoupled spins are widely suppressed. As a potential application, the detection of the strongly coupled AA‧BB‧ spin system of taurine at 1.5 T is discussed.

  3. High-pressure low-field 1H NMR relaxometry in nanoporous materials.

    PubMed

    Horch, Carsten; Schlayer, Stefan; Stallmach, Frank

    2014-03-01

    A low-field NMR sensor with NdFeB permanent magnets (B0=118 mT) and a pressure cell made of PEEK (4 cm outer diameter) were designed for (1)H relaxation time studies of adsorbed molecules at pressures of up to 300 bar. The system was used to investigate methane uptake of microporous metal-organic frameworks and nanoporous activated carbon. T2 relaxation time distribution of pure methane and of methane under co-adsorption of carbon dioxide show that the host-guest interaction lead to a relaxation time contrasts, which may be used to distinguish between the gas phase and the different adsorbed phases of methane. Adsorption isotherms, exchange of methane between adsorbent particles and the surrounding gas phase, successive displacement of methane from adsorption sites by co-adsorption of carbon dioxide and CO2/CH4 adsorption separation factors were determined from the observed NMR relaxation time distributions.

  4. Key metabolites in tissue extracts of Elliptio complanata identified using (1)H nuclear magnetic resonance spectroscopy.

    PubMed

    Hurley-Sanders, Jennifer L; Levine, Jay F; Nelson, Stacy A C; Law, J M; Showers, William J; Stoskopf, Michael K

    2015-01-01

    We used (1)H nuclear magnetic resonance spectroscopy to describe key metabolites of the polar metabolome of the freshwater mussel, Elliptio complanata. Principal components analysis documented variability across tissue types and river of origin in mussels collected from two rivers in North Carolina (USA). Muscle, digestive gland, mantle and gill tissues yielded identifiable but overlapping metabolic profiles. Variation in digestive gland metabolic profiles between the two mussel collection sites was characterized by differences in mono- and disaccharides. Variation in mantle tissue metabolomes appeared to be associated with sex. Nuclear magnetic resonance spectroscopy is a sensitive means to detect metabolites in the tissues of E. complanata and holds promise as a tool for the investigation of freshwater mussel health and physiology.

  5. 1H NMR study of the complexation of aromatic drugs with dimethylxanthine derivatives

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    PubMed

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

    2016-04-01

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

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed Central

    2015-01-01

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

  9. Quantitative determination of glyphosate in human serum by 1H NMR spectroscopy.

    PubMed

    Cartigny, Bernard; Azaroual, Nathalie; Imbenotte, Michel; Mathieu, Daniel; Parmentier, Erika; Vermeersch, Gaston; Lhermitte, Michel

    2008-01-15

    The determination and quantification of glyphosate in serum using (1)H NMR spectroscopy is reported. This method permitted serum samples to be analysed without derivatization or any other sample pre-treatment, using 3-trimethylsilyl 2,2',3,3'-tetradeuteropropionic acid (TSP-d(4)) as a qualitative and quantitative standard. Characterization of the herbicide N-(phosphonomethyl)glycine was performed by analysing chemical shifts and coupling constant patterns. Quantification was performed by relative integration of CH(2)-P protons to the TSP-d(4) resonance peak. The method was tested for repeatability (n=5) and yielded coefficients of variation of 1% and 3%, respectively: detection and quantification limits were also determined and were 0.03 and 0.1mmol/L, respectively. The method was applied to the quantification of glyphosate in a case of acute poisoning. PMID:18371753

  10. 1H NMR Relaxation Investigation of Inhibitors Interacting with Torpedo californica Acetylcholinesterase

    NASA Astrophysics Data System (ADS)

    Delfini, Maurizio; Gianferri, Raffaella; Dubbini, Veronica; Manetti, Cesare; Gaggelli, Elena; Valensin, Gianni

    2000-05-01

    Two naphthyridines interacting with Torpedo californica acetylcholinesterase (AChE) were investigated. 1H NMR spectra were recorded and nonselective, selective, and double-selective spin-lattice relaxation rates were measured. The enhancement of selective relaxation rates could be titrated by different ligand concentrations at constant AChE (yielding 0.22 and 1.53 mM for the dissociation constants) and was providing evidence of a diverse mode of interaction. The double-selective relaxation rates were used to evaluate the motional correlation times of bound ligands at 34.9 and 36.5 ns at 300 K. Selective relaxation rates of bound inhibitors could be interpreted also in terms of dipole-dipole interactions with protons in the enzyme active site.

  11. The estimation of local brain temperature by in vivo 1H magnetic resonance spectroscopy.

    PubMed

    Cady, E B; D'Souza, P C; Penrice, J; Lorek, A

    1995-06-01

    Brain temperature may be important for investigating pathology and cerebroprotective effects of pharmaceuticals and hypothermia. Two methods for estimating temperature using 1H magnetic resonance spectroscopy are described: a partially water-suppressed binomial sequence and non-water-suppressed point-resolved spectroscopy. Relative to N-acetylaspartate (Naa), water chemical shift (delta H2O-Naa) in piglet brain depended linearly on temperature from 30 degrees to 40 degrees C: temperature was 286.9-94.0 delta H2O-Naa degrees C. Thalamic temperature in six normal infants was 38.1 degrees +/- 0.4 degree C indicating that local brain temperature could be estimated with adequate sensitivity for studying pathologic and therapeutic changes.

  12. Key metabolites in tissue extracts of Elliptio complanata identified using 1H nuclear magnetic resonance spectroscopy

    PubMed Central

    Hurley-Sanders, Jennifer L.; Levine, Jay F.; Nelson, Stacy A. C.; Law, J. M.; Showers, William J.; Stoskopf, Michael K.

    2015-01-01

    We used 1H nuclear magnetic resonance spectroscopy to describe key metabolites of the polar metabolome of the freshwater mussel, Elliptio complanata. Principal components analysis documented variability across tissue types and river of origin in mussels collected from two rivers in North Carolina (USA). Muscle, digestive gland, mantle and gill tissues yielded identifiable but overlapping metabolic profiles. Variation in digestive gland metabolic profiles between the two mussel collection sites was characterized by differences in mono- and disaccharides. Variation in mantle tissue metabolomes appeared to be associated with sex. Nuclear magnetic resonance spectroscopy is a sensitive means to detect metabolites in the tissues of E. complanata and holds promise as a tool for the investigation of freshwater mussel health and physiology. PMID:27293708

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

    SciTech Connect

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

    2007-09-05

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

  14. Total assignment of 1H and 13C NMR data for the sesquiterpene lactone 15-deoxygoyazensolide.

    PubMed

    Heleno, Vladimir Constantino Gomes; Crotti, Antônio Eduardo Miller; Constantino, Mauricio Gomes; Lopes, Norberto Peporine; Lopes, João Luis Callegari

    2004-03-01

    We describe a complete analysis of the 1H and 13C spectra of the anti-inflamatory, schistossomicidal and trypanosomicidal sesquiterpene lactone 15-deoxygoyazensolide. This lactone, with a structure similar to other important ones, was studied by NMR techniques such as COSY, HMQC, HMBC, Jres and NOE experiments. The comparison of the data with some computational results led to an unequivocal assignment of all hydrogen and carbon chemical shifts, even eliminating some previous ambiguities. We were able to determine all hydrogen coupling constants (J) and signal multiplicities and to confirm the stereochemistry. A new method for the determination of the relative position of the lactonization and the position of the ester group on a medium-sized ring by NMR was developed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  16. Low-field (1)H NMR spectroscopy for distinguishing between arabica and robusta ground roast coffees.

    PubMed

    Defernez, Marianne; Wren, Ella; Watson, Andrew D; Gunning, Yvonne; Colquhoun, Ian J; Le Gall, Gwénaëlle; Williamson, David; Kemsley, E Kate

    2017-02-01

    This work reports a new screening protocol for addressing issues of coffee authenticity using low-field (60MHz) bench-top (1)H NMR spectroscopy. Using a simple chloroform-based extraction, useful spectra were obtained from the lipophilic fraction of ground roast coffees. It was found that 16-O-methylcafestol (16-OMC, a recognized marker compound for robusta beans) gives rise to an isolated peak in the 60MHz spectrum, which can be used as an indicator of the presence of robusta beans in the sample. A total of 81 extracts from authenticated coffees and mixtures were analysed, from which the detection limit of robusta in arabica was estimated to be between 10% and 20% w/w. Using the established protocol, a surveillance exercise was conducted of 27 retail samples of ground roast coffees which were labelled as "100% arabica". None were found to contain undeclared robusta content above the estimated detection limit. PMID:27596398

  17. 2-(1H-Pyrazol-3-yl)pyridinium chloride monohydrate

    PubMed Central

    Amarante, Tatiana R.; Gonçalves, Isabel S.; Almeida Paz, Filipe A.

    2009-01-01

    The title organic salt, C8H8N3 +·Cl−·H2O, exhibits a rich hydrogen-bonding network involving all constituent species. The water mol­ecules are engaged in strong O—H⋯Cl inter­actions with the chloride anions, two neighboring protonated 2-(1H-pyrazol-3-yl)pyridinium species inter­act via N—H⋯N bonds with two pyrazole rings. Further, a short and highly directional C—H⋯O inter­action is observed connecting the pyridinium ring to the water mol­ecule of crystallization. Weak C—H⋯Cl and N—H⋯Cl inter­actions contribute to the stabilization of the crystal structure. PMID:21583640

  18. Quantitative analysis of sesquiterpene lactones in extract of Arnica montana L. by 1H NMR spectroscopy.

    PubMed

    Staneva, Jordanka; Denkova, Pavletta; Todorova, Milka; Evstatieva, Ljuba

    2011-01-01

    (1)H NMR spectroscopy was used as a method for quantitative analysis of sesquiterpene lactones present in a crude lactone fraction isolated from Arnica montana. Eight main components - tigloyl-, methacryloyl-, isobutyryl- and 2-methylbutyryl-esters of helenalin (H) and 11α,13-dihydrohelenalin (DH) were identified in the studied sample. The method allows the determination of the total amount of sesquiterpene lactones and the quantity of both type helenalin and 11α,13-dihydrohelenalin esters separately. Furthermore, 6-O-tigloylhelenalin (HT, 1), 6-O-methacryloylhelenalin (HM, 2), 6-O-tigloyl-11α,13-dihydrohelenalin (DHT, 5), and 6-O-methacryloyl-11α,13-dihydrohelenalin (DHM, 6) were quantified as individual components.

  19. 1H NMR Cryoporometry Study of the Melting Behavior of Water in White Cement

    NASA Astrophysics Data System (ADS)

    Boguszyńska, Joanna; Tritt-Goc, Jadwiga

    2004-09-01

    The pore size of white cement samples is studied by the melting behaviour of water confined in it, using 1H NMR cryopormetry. The influence of the preparing method and antifreeze admixture on the pore size and distribution in cement samples is investigated at 283 K. The addition of an antifreeze admixture [containing 1% Sika Rapid 2 by weight of the dry cement] influences the porosity. In wet prepared samples we observed a significant increase in the quantity of mesopores between 0.8 and 5 nm and a smaller increase of mesopores between 5 and 10 nm, when compared to cement without admixture. The compressive strength is related to the porosity of the cement. Therefore the cement with Sika Rapid 2, wet prepared at 278 K shows a higher strength than all other measured samples.

  20. 1H NMR and UV-visible data fusion for determining Sudan dyes in culinary spices.

    PubMed

    Di Anibal, Carolina V; Callao, M Pilar; Ruisánchez, Itziar

    2011-05-15

    Two data fusion strategies (variable and decision level) combined with a multivariate classification approach (Partial Least Squares-Discriminant Analysis, PLS-DA) have been applied to get benefits from the synergistic effect of the information obtained from two spectroscopic techniques: UV-visible and (1)H NMR. Variable level data fusion consists of merging the spectra obtained from each spectroscopic technique in what is called "meta-spectrum" and then applying the classification technique. Decision level data fusion combines the results of individually applying the classification technique in each spectroscopic technique. Among the possible ways of combinations, we have used the fuzzy aggregation connective operators. This procedure has been applied to determine banned dyes (Sudan III and IV) in culinary spices. The results show that data fusion is an effective strategy since the classification results are better than the individual ones: between 80 and 100% for the individual techniques and between 97 and 100% with the two fusion strategies.

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

    PubMed

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

    2005-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-05-01

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

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

    PubMed Central

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

    2016-01-01

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

  4. Equilibrium 2H/ 1H fractionations in organic molecules: I. Experimental calibration of ab initio calculations

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A., III

    2009-12-01

    Carbon-bound hydrogen in sedimentary organic matter can undergo exchange over geologic timescales, altering its isotopic composition. Studies investigating the natural abundance distribution of 1H and 2H in such molecules must account for this exchange, which in turn requires quantitative knowledge regarding the endpoint of exchange, i.e., the equilibrium isotopic fractionation factor ( α eq). To date, relevant data have been lacking for molecules larger than methane. Here we describe an experimental method to measure α eq for C-bound H positions adjacent to carbonyl group (H α) in ketones. H at these positions equilibrates on a timescale of days as a result of keto-enol tautomerism, allowing equilibrium 2H/ 1H distributions to be indirectly measured. Molecular vibrations for the same ketone molecules are then computed using Density Functional Theory at the B3LYP/6-311G∗∗ level and used to calculate α eq values for H α. Comparison of experimental and computational results for six different straight and branched ketones yields a temperature-dependent linear calibration curve with slope = 1.081-0.00376 T and intercept = 8.404-0.387 T, where T is temperature in degrees Celsius. Since the dominant systematic error in the calculation (omission of anharmonicity) is of the same size for ketones and C-bound H in most other linear compounds, we propose that this calibration can be applied to analogous calculations for a wide variety of organic molecules with linear carbon skeletons for temperatures below 100 °C. In a companion paper ( Wang et al., 2009) we use this new calibration dataset to calculate the temperature-dependent equilibrium isotopic fractionation factors for a range of linear hydrocarbons, alcohols, ethers, ketones, esters and acids.

  5. Multivariate modelling with 1H NMR of pleural effusion in murine cerebral malaria

    PubMed Central

    2011-01-01

    Background Cerebral malaria is a clinical manifestation of Plasmodium falciparum infection. Although brain damage is the predominant pathophysiological complication of cerebral malaria (CM), respiratory distress, acute lung injury, hydrothorax/pleural effusion are also observed in several cases. Immunological parameters have been assessed in pleural fluid in murine models; however there are no reports of characterization of metabolites present in pleural effusion. Methods 1H NMR of the sera and the pleural effusion of cerebral malaria infected mice were analyzed using principal component analysis, orthogonal partial least square analysis, multiway principal component analysis, and multivariate curve resolution. Results It has been observed that there was 100% occurrence of pleural effusion (PE) in the mice affected with CM, as opposed to those are non-cerebral and succumbing to hyperparasitaemia (NCM/HP). An analysis of 1H NMR and SDS-PAGE profile of PE and serum samples of each of the CM mice exhibited a similar profile in terms of constituents. Multivariate analysis on these two classes of biofluids was performed and significant differences were detected in concentrations of metabolites. Glucose, creatine and glutamine contents were high in the PE and lipids being high in the sera. Multivariate curve resolution between sera and pleural effusion showed that changes in PE co-varied with that of serum in CM mice. The increase of glucose in PE is negatively correlated to the glucose in serum in CM as obtained from the result of multiway principal component analysis. Conclusions This study reports for the first time, the characterization of metabolites in pleural effusion formed during murine cerebral malaria. The study indicates that the origin of PE metabolites in murine CM may be the serum. The loss of the components like glucose, glutamine and creatine into the PE may worsen the situation of patients, in conjunction with the enhanced glycolysis, glutaminolysis and

  6. The peculiar radio-loud narrow line Seyfert 1 galaxy 1H 0323+342

    SciTech Connect

    Paliya, Vaidehi S.; Stalin, C. S.; Sahayanathan, S.; Parker, M. L.; Fabian, A. C.; Anjum, Ayesha; Pandey, S. B.

    2014-07-10

    We present a multiwavelength study of the radio-loud narrow-line Seyfert 1 galaxy (NLSy1) 1H 0323+342, detected by the Fermi Gamma-Ray Space Telescope. Multiband light curves show many orphan X-ray and optical flares having no corresponding γ-ray counterparts. Such anomalous variability behavior can be due to different locations of the emission region from the central source. During a large flare, a γ-ray flux doubling timescale as small as ∼3 hr is noticed. We built spectral energy distributions (SEDs) during different activity states and modeled them using a one-zone leptonic model. The shape of the optical/UV component of the SEDs is dominated by accretion disk emission in all the activity states. In the X-ray band, significant thermal emission from the hot corona is inferred during quiescent and first flaring states; however, during subsequent flares, the nonthermal jet component dominates. The γ-ray emission in all the states can be well explained by inverse-Compton scattering of accretion disk photons reprocessed by the broad-line region. The source showed violent intra-night optical variability, coinciding with one of the high γ-ray activity states. An analysis of the overall X-ray spectrum fitted with an absorbed power-law plus relativistic reflection component hints at the presence of an Fe Kα line and returns a high black hole spin value of a = 0.96 ± 0.14. We argue that 1H 0323+342 possesses dual characteristics, akin to both flat-spectrum radio quasars (FSRQs) and radio-quiet NLSy1 galaxies, though at a low jet power regime compared to powerful FSRQs.

  7. Application of ICA to realistically simulated 1H-MRS data

    PubMed Central

    Kalyanam, Ravi; Boutte, David; Hutchison, Kent E; Calhoun, Vince D

    2015-01-01

    Introduction 1H-MRS signals from brain tissues capture information on in vivo brain metabolism and neuronal biomarkers. This study aims to advance the use of independent component analysis (ICA) for spectroscopy data by objectively comparing the performance of ICA and LCModel in analyzing realistic data that mimics many of the known properties of in vivo data. Methods This work identifies key features of in vivo 1H-MRS signals and presents methods to simulate realistic data, using a basis set of 12 metabolites typically found in the human brain. The realistic simulations provide a much needed ground truth to evaluate performances of various MRS analysis methods. ICA is applied to collectively analyze multiple realistic spectra and independent components identified with our generative model to obtain ICA estimates. These same data are also analyzed using LCModel and the comparisons between the ground-truth and the analysis estimates are presented. The study also investigates the potential impact of modeling inaccuracies by incorporating two sets of model resonances in simulations. Results The simulated fid signals incorporating line broadening, noise, and residual water signal closely resemble the in vivo signals. Simulation analyses show that the resolution performances of both LCModel and ICA are not consistent across metabolites and that while ICA resolution can be improved for certain resonances, ICA is as effective as, or better than, LCModel in resolving most model resonances. Conclusion The results show that ICA can be an effective tool in comparing multiple spectra and complements existing approaches for providing quantified estimates. PMID:26221570

  8. Detection of intramyocardial hemorrhage using high-field proton (1H) nuclear magnetic resonance imaging

    SciTech Connect

    Lotan, C.S.; Miller, S.K.; Bouchard, A.; Cranney, G.B.; Reeves, R.C.; Bishop, S.P.; Elgavish, G.A.; Pohost, G.M. )

    1990-07-01

    Proton (1H) nuclear magnetic resonance (NMR) imaging has been used to define zones of myocardial infarction (MI), which appear as areas of relatively increased signal intensity (SI). However, zones of decreased SI have been observed within the areas of infarction and have been postulated to result from intramyocardial hemorrhage. To explore this phenomenon further, ex vivo spin-echo 1H NMR imaging at 1.5 Tesla was performed in 17 dogs after 24 hr (n = 9) and after 72 hr (n = 8) of coronary artery occlusion. In all dogs, a zone of increased SI (118 +/- 9% compared with normal myocardium) was observed in the distribution of the occluded coronary artery. In 12 of the 17 dogs, zones of decreased SI (92 +/- 8% compared with normal) were seen within or around the central zone of increased SI. Gross inspection and histological assessment of sliced myocardium usually disclosed hemorrhage in the regions of decreased SI. In three of the five dogs with no apparent zones of decreased SI on NMR, the infarct was small, and only minor hemorrhage was observed by gross inspection, whereas in the remaining two dogs no hemorrhage was seen. Myocardial flow in the hemorrhagic regions was significantly higher than in the necrotic core (59 +/- 29% vs. 31 +/- 24% compared with control, P less than 0.05). Image-derived calculation of T2 relaxation times in the different infarcted regions revealed a significant shortening of T2 in the infarcted hemorrhagic zones with decreased SI compared with the infarct zones with increased SI (49 +/- 8 msec vs. 66 +/- 8 msec, P less than 0.05).

  9. Scientific approach to the 1-h cycling world record: a case study.

    PubMed

    Padilla, S; Mujika, I; Angulo, F; Goiriena, J J

    2000-10-01

    The purpose of this study was to describe the physiological and aerodynamic characteristics and the preparation for a successful attempt to break the 1-h cycling world record. An elite professional road cyclist (30 yr, 188 cm, 81 kg) performed an incremental laboratory test to assess maximal power output (W(max)) and power output (W(OBLA)), estimated speed (V(OBLA)), and heart rate (HR(OBLA)) at the onset of blood lactate accumulation (OBLA). He also completed an incremental velodrome (cycling track) test (VT1), during which V(OBLAVT1) and HR(OBLAVT1) were measured and W(OBLAVT1) was estimated. W(max) was 572 W, W(OBLA) 505 W, V(OBLA) 52.88 km/h, and HR(OBLA) 183 beats/min. V(OBLAVT1), HR(OBLAVT1), and W(OBLAVT1) were 52.7 km/h, 180 beats/min, and 500.6 W, respectively. Drag coefficient and shape coefficient, measured in a wind tunnel, were 0. 244 and 0.65 m(2), respectively. The cyclist set a world record of 53,040 m, with an estimated average power output of 509.5 W. Based on direct laboratory data of the power vs. oxygen uptake relationship for this cyclist, this is slightly higher than the 497. 25 W corresponding to his oxygen uptake at OBLA (5.65 l/min). In conclusion, 1) the 1-h cycling world record is the result of the interaction between physiological and aerodynamic characteristics; and 2) performance in this event can be predicted using mathematical models that integrate the principal performance-determining variables.

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

    SciTech Connect

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

    2007-06-06

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

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

    PubMed

    Ventrella, Domenico; Laghi, Luca; Barone, Francesca; Elmi, Alberto; Romagnoli, Noemi; Bacci, Maria Laura

    2016-01-01

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

  12. BEBEtr and BUBI: J-compensated concurrent shaped pulses for 1H-13C experiments

    NASA Astrophysics Data System (ADS)

    Ehni, Sebastian; Luy, Burkhard

    2013-07-01

    Shaped pulses designed for broadband excitation, inversion and refocusing are important tools in modern NMR spectroscopy to achieve robust pulse sequences especially in heteronuclear correlation experiments. A large variety of mostly computer-optimized pulse shapes exist for different desired bandwidths, available rf-field strengths, and tolerance to B1-inhomogeneity. They are usually derived for a single spin 1/2, neglecting evolution due to J-couplings. While pulses with constant resulting phase are selfcompensated for heteronuclear coupling evolution as long as they are applied exclusively on a single nucleus, the situation changes for concurrently applied pulse shapes. Using the example of a 1H,13C two spin system, two J-compensated pulse pairs for the application in INEPT-type transfer elements were optimized: a point-to-point pulse sandwich called BEBEtr, consisting of a broadband excitation and time-reversed excitation pulse, and a combined universal rotation and point-to-point pulse pair called BUBI, which acts as a refocusing pulse on 1H and a corresponding inversion pulse on 13C. After a derivation of quality factors and optimization protocols, a theoretical and experimental comparison with conventionally derived BEBOP, BIBOP, and BURBOP-180° pulses is given. While the overall transfer efficiency of a single pulse pair is only reduced by approximately 0.1%, resulting transfer to undesired coherences is reduced by several percent. In experiments this can lead to undesired phase distortions for pairs of uncompensated pulse shapes and even differences in signal intensities of 5-10% in HSQC and up to 68% in more complex COB-HSQC experiments.

  13. 1H NMR metabolomics of earthworm responses to polychlorinated biphenyl (PCB) exposure in soil.

    PubMed

    Whitfield Åslund, Melissa L; Simpson, André J; Simpson, Myrna J

    2011-06-01

    (1)H NMR-based metabolomics was used to examine the metabolic profile of D(2)O-buffer extracted tissues of Eisenia fetida earthworms exposed for 2 days to an artificial soil spiked with sub-lethal concentrations of polychlorinated biphenyls (PCBs) (0, 0.5, 1, 5, 10, or 25 mg/kg Aroclor 1254). Univariate statistical analysis of the identified metabolites revealed a significant increase in ATP concentration in earthworms exposed to the highest soil PCB concentration, but detected no significant changes in other metabolites. However, a multivariate approach which considers alterations in multiple metabolites simultaneously, identified a significant linear relationship between earthworm metabolic profiles and PCB concentration (cross-validated PLS-regression with 7 components, R(2)X = 0.99, R(2)Y = 0.77, Q(2)Y = 0.45, P < 0.001). Significant changes in pair-wise metabolic correlations were also detected as PCB concentration increased. For example, lysine and ATP concentrations showed no apparent correlation in control earthworms (r = 0.22, P = 0.54), but were positively correlated in earthworms from the 25 mg/kg treatment (r = 0.87, P = 0.001). Overall, the observed metabolic responses suggest that PCBs disrupted both carbohydrate (energy) metabolism and membrane (osmolytic) function in E. fetida. The ability of (1)H NMR-based metabolomics to detect these responses suggests that this method offers significant potential for direct assessment of sub-lethal PCB toxicity in soil. PMID:21424327

  14. The Peculiar Radio-loud Narrow Line Seyfert 1 Galaxy 1H 0323+342

    NASA Astrophysics Data System (ADS)

    Paliya, Vaidehi S.; Sahayanathan, S.; Parker, M. L.; Fabian, A. C.; Stalin, C. S.; Anjum, Ayesha; Pandey, S. B.

    2014-07-01

    We present a multiwavelength study of the radio-loud narrow-line Seyfert 1 galaxy (NLSy1) 1H 0323+342, detected by the Fermi Gamma-Ray Space Telescope. Multiband light curves show many orphan X-ray and optical flares having no corresponding γ-ray counterparts. Such anomalous variability behavior can be due to different locations of the emission region from the central source. During a large flare, a γ-ray flux doubling timescale as small as ~3 hr is noticed. We built spectral energy distributions (SEDs) during different activity states and modeled them using a one-zone leptonic model. The shape of the optical/UV component of the SEDs is dominated by accretion disk emission in all the activity states. In the X-ray band, significant thermal emission from the hot corona is inferred during quiescent and first flaring states; however, during subsequent flares, the nonthermal jet component dominates. The γ-ray emission in all the states can be well explained by inverse-Compton scattering of accretion disk photons reprocessed by the broad-line region. The source showed violent intra-night optical variability, coinciding with one of the high γ-ray activity states. An analysis of the overall X-ray spectrum fitted with an absorbed power-law plus relativistic reflection component hints at the presence of an Fe Kα line and returns a high black hole spin value of a = 0.96 ± 0.14. We argue that 1H 0323+342 possesses dual characteristics, akin to both flat-spectrum radio quasars (FSRQs) and radio-quiet NLSy1 galaxies, though at a low jet power regime compared to powerful FSRQs.

  15. Membrane-induced structure of novel human tachykinin hemokinin-1 (hHK1).

    PubMed

    Ganjiwale, Anjali; Cowsik, Sudha M

    2015-12-01

    PPT-C encoded hemokinin-1(hHK-1) of Homo sapiens (TGKASQFFGLM) is a structurally distinct neuropeptide among the tachykinin family that participate in the NK-1 receptor downstream signaling processes. Subsequently, signal transduction leads to execution of various effector functions which includes aging, immunological, and central nervous system (CNS) regulatory actions. However the conformational pattern of ligand receptor binding is unclear. The three-dimensional structure of the hemokinin-1 in aqueous and micellar environment has been studied by one and two-dimensional proton nuclear magnetic resonance (2D 1H-NMR spectroscopy) and distance geometry calculations. Data shows that hemokinin-1 was unstructured in aqueous environment; anionic detergent SDS induces α-helix formation. Proton NMR assignments have been carried out with the aid of correlation spectroscopy (gradient-COSY and TOCSY) and nuclear Overhauser effect spectroscopy (NOESY and ROESY) experiments. The inter proton distances and dihedral angle constraints obtained from the NMR data have been used in torsion angle dynamics algorithm for NMR applications (CYANA) to generate a family of structures, which have been refined using restrained energy minimization and dynamics. Helical conformation is observed from residue K3-M11. The conformational range of the peptide revealed by NMR studies has been analyzed in terms of characteristic secondary features. Observed conformational features have been compared to that of Substance P potent NK1 agonist. Thus the report provides a structural insight to study hHK-1-NK1 interaction that is essential for hHK1 based signaling events. PMID:26297926

  16. Microwave spectra and gas phase structural parameters for N-hydroxypyridine-2(1H)-thione.

    PubMed

    Daly, Adam M; Mitchell, Erik G; Sanchez, Daniel A; Block, Eric; Kukolich, Stephen G

    2011-12-22

    The microwave spectrum for N-hydroxypyridine-2(1H)-thione (pyrithione) was measured in the frequency range 6-18 GHz, providing accurate rotational constants and nitrogen quadrupole coupling strengths for three isotopologues, C(5)H(4)(32)S(14)NOH, C(5)H(4)(32)S(14)NOD, and C(5)H(4)(34)S(14)NOH. Pyrithione was found to be in a higher concentration in the gas phase than the other tautomer, 2-mercaptopyridine-N-oxide (MPO). Microwave spectroscopy is best suited to determine which structure predominates in the gas phase. The measured rotational constants were used to accurately determine the coordinates of the substituted atoms and provided sufficient data to determine some of the important structural parameters for pyrithione, the only tautomer observed in the present work. The spectra were obtained using a pulsed-beam Fourier transform microwave spectrometer, with sufficient resolution to allow accurate measurements of the (14)N nuclear quadrupole hyperfine interactions. Ab initio calculations provided structural parameters and quadrupole coupling strengths that are in very good agreement with measured values. The experimental rotational constants for the parent compound are A = 3212.10(1), B = 1609.328(7), and C = 1072.208(6) MHz, yielding the inertial defect Δ(0) = -0.023 amu·Å(2) for the C(5)H(4)(32)S(14)NOH isotopologue. The observed near zero inertial defect clearly indicates a planar structure. The least-squares fit structural analysis yielded the experimental bond lengths R(O-H) = 0.93(2) Å, R(C-S) = 1.66(2) Å, and angle (N-O-H) = 105(4)° for the ground state structure.

  17. Microwave spectra and gas phase structural parameters for N-hydroxypyridine-2(1H)-thione.

    PubMed

    Daly, Adam M; Mitchell, Erik G; Sanchez, Daniel A; Block, Eric; Kukolich, Stephen G

    2011-12-22

    The microwave spectrum for N-hydroxypyridine-2(1H)-thione (pyrithione) was measured in the frequency range 6-18 GHz, providing accurate rotational constants and nitrogen quadrupole coupling strengths for three isotopologues, C(5)H(4)(32)S(14)NOH, C(5)H(4)(32)S(14)NOD, and C(5)H(4)(34)S(14)NOH. Pyrithione was found to be in a higher concentration in the gas phase than the other tautomer, 2-mercaptopyridine-N-oxide (MPO). Microwave spectroscopy is best suited to determine which structure predominates in the gas phase. The measured rotational constants were used to accurately determine the coordinates of the substituted atoms and provided sufficient data to determine some of the important structural parameters for pyrithione, the only tautomer observed in the present work. The spectra were obtained using a pulsed-beam Fourier transform microwave spectrometer, with sufficient resolution to allow accurate measurements of the (14)N nuclear quadrupole hyperfine interactions. Ab initio calculations provided structural parameters and quadrupole coupling strengths that are in very good agreement with measured values. The experimental rotational constants for the parent compound are A = 3212.10(1), B = 1609.328(7), and C = 1072.208(6) MHz, yielding the inertial defect Δ(0) = -0.023 amu·Å(2) for the C(5)H(4)(32)S(14)NOH isotopologue. The observed near zero inertial defect clearly indicates a planar structure. The least-squares fit structural analysis yielded the experimental bond lengths R(O-H) = 0.93(2) Å, R(C-S) = 1.66(2) Å, and angle (N-O-H) = 105(4)° for the ground state structure. PMID:22070758

  18. Characterization of active phosphorus surface sites at synthetic carbonate-free fluorapatite using single-pulse 1H, 31P, and 31P CP MAS NMR.

    PubMed

    Jarlbring, Mathias; Sandström, Dan E; Antzutkin, Oleg N; Forsling, Willis

    2006-05-01

    The chemically active phosphorus surface sites defined as PO(x), PO(x)H, and PO(x)H2, where x = 1, 2, or 3, and the bulk phosphorus groups of PO4(3-) at synthetic carbonate-free fluorapatite (Ca5(PO4)3F) have been studied by means of single-pulse 1H,31P, and 31P CP MAS NMR. The changes in composition and relative amounts of each surface species are evaluated as a function of pH. By combining spectra from single-pulse 1H and 31P MAS NMR and data from 31P CP MAS NMR experiments at varying contact times in the range 0.2-3.0 ms, it has been possible to distinguish between resonance lines in the NMR spectra originating from active surface sites and bulk phosphorus groups and also to assign the peaks in the NMR spectra to the specific phosphorus species. In the 31P CP MAS NMR experiments, the spinning frequency was set to 4.2 kHz; in the single-pulse 1H MAS NMR experiments, the spinning frequency was 10 kHz. The 31P CP MAS NMR spectrum of fluorapatite at pH 5.9 showed one dominating resonance line at 2.9 ppm assigned to originate from PO4(3-) groups and two weaker shoulder peaks at 5.4 and 0.8 ppm which were assigned to the unprotonated PO(x) (PO, PO2-, and PO3(2-)) and protonated PO(x)H (PO2H and PO3H-) surface sites. At pH 12.7, the intensity of the peak representing unprotonated PO(x) surface sites has increased 1.7% relative to the bulk peak, while the intensity of the peaks of the protonated species PO(x)H have decreased 1.4% relative to the bulk peak. At pH 3.5, a resonance peak at -4.5 ppm has appeared in the 31P CP MAS NMR spectrum assigned to the surface species PO(x)H2 (PO3H2). The results from the 1H MAS and 31P CP MAS NMR measurements indicated that H+, OH-, and physisorbed H2O at the surface were released during the drying process at 200 degrees C.

  19. The alveolin IMC1h is required for normal ookinete and sporozoite motility behaviour and host colonisation in Plasmodium berghei.

    PubMed

    Volkmann, Katrin; Pfander, Claudia; Burstroem, Charlotte; Ahras, Malika; Goulding, David; Rayner, Julian C; Frischknecht, Friedrich; Billker, Oliver; Brochet, Mathieu

    2012-01-01

    Alveolins, or inner membrane complex (IMC) proteins, are components of the subpellicular network that forms a structural part of the pellicle of malaria parasites. In Plasmodium berghei, deletions of three alveolins, IMC1a, b, and h, each resulted in reduced mechanical strength and gliding velocity of ookinetes or sporozoites. Using time lapse imaging, we show here that deletion of IMC1h (PBANKA_143660) also has an impact on the directionality and motility behaviour of both ookinetes and sporozoites. Despite their marked motility defects, sporozoites lacking IMC1h were able to invade mosquito salivary glands, allowing us to investigate the role of IMC1h in colonisation of the mammalian host. We show that IMC1h is essential for sporozoites to progress through the dermis in vivo but does not play a significant role in hepatoma cell transmigration and invasion in vitro. Colocalisation of IMC1h with the residual IMC in liver stages was detected up to 30 hours after infection and parasites lacking IMC1h showed developmental defects in vitro and a delayed onset of blood stage infection in vivo. Together, these results suggest that IMC1h is involved in maintaining the cellular architecture which supports normal motility behaviour, access of the sporozoites to the blood stream, and further colonisation of the mammalian host.

  20. 1-Aryl-5-(1H-pyrrol-1-yl)-1H-pyrazole-3-carboxamide: an effective scaffold for the design of either CB1 or CB2 receptor ligands.

    PubMed

    Piscitelli, Francesco; Ligresti, Alessia; La Regina, Giuseppe; Gatti, Valerio; Brizzi, Antonella; Pasquini, Serena; Allarà, Marco; Carai, Mauro Antonio Maria; Novellino, Ettore; Colombo, Giancarlo; Di Marzo, Vincenzo; Corelli, Federico; Silvestri, Romano

    2011-11-01

    New 1-aryl-5-(1H-pyrrol-1-yl)-1H-pyrazole-3-carboxamides were synthesized as cannabinoid (CB) receptor ligands. Compound 11 (CB(1)K(i) = 2.3 nM, CB(1) SI = 163.6) showed CB(1) receptor affinity and selectivity superior to Rimonabant and AM251. Acute administration of 2mg/kg 11 reduced sucrose, but not regular food, intake in rats. On the other hand, compound 23 (CB(2)K(i) = 0.51 nM, CB(2) SI = 30.0) showed significant affinity and selectivity for the CB(2) receptor. The results presented here show that the 1-aryl-5-(1H-pyrrol-1-yl)-1H-pyrazole-3-carboxamide may serve as an effective scaffold for the design of either CB(1) or CB(2) receptor ligands. PMID:21996466

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

    PubMed

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

    2008-08-14

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

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

    PubMed

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

    2008-08-14

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

  3. Swelling of peat soil samples as determined by 1H NMR relaxometry

    NASA Astrophysics Data System (ADS)

    Jaeger, F.; Schaumann, G. E.

    2009-04-01

    The swelling of soil organic matter (SOM) rich samples like peat soils may affect sorption and desorption of nutrients and contaminants. In the course of swelling the state of water may change and SOM may form a gel phase. Two peat soil samples in different degradation states from one location in Germany were saturated with water. Their swelling kinetics were studied at 5°C, 19°C and 30°C using 1H NMR relaxometry at 7.5 MHz. CPMG pulse sequence and the inversion recovery method were used to determine transverse (T2) and longitudinal (T1) relaxation time distributions, respectively. The gel phase and the state of water were both characterized with 1H NMR relaxometry, Cryo-NMR and differential scanning calorimetry (DSC). Three types of water were found in both peats: Non-freezing bound water and two types of freezable water which showed a splitting of the melting peak in the DSC thermogram. The stepwise water drainage of the peat samples by centrifugation revealed increasing T1/T2 ratios, which were not caused by proton relaxation, due to spin diffusion in internal field gradients. It can be assumed that both the splitting of the melting peak and the increasing T1/T2 ratios were caused by a phase separation of the "free" freezable water as found for conventional biopolymers like starch. Due to the organic surfaces one phase of the freezable water is structured which affects the rotational motion of water molecules, and thus caused different T1 and T2 values. From the swelling kinetics three processes (fast, medium, slow) of water dislocation from larger to smaller T2 values were distinguished. The time constants of the processes were found to be in the range of minutes (fast), hours (medium) and days/weeks (slow). The activation energies ranged between 15 - 50 KJ mol-1 suggesting that physical and physical/chemical processes are governing the swelling of SOM like a sterical re-orientation of SOM macromolecules, the water-structuring and hydration of SOM.

  4. Elevated levels of GABA+ in migraine detected using (1) H-MRS.

    PubMed

    Aguila, Maria-Eliza R; Lagopoulos, Jim; Leaver, Andrew M; Rebbeck, Trudy; Hübscher, Markus; Brennan, Patrick C; Refshauge, Kathryn M

    2015-07-01

    γ-Aminobutyric acid (GABA) has been implicated in several pain conditions, yet no study has systematically evaluated GABA levels in migraine using (1) H-MRS. The accurate detection, separation and quantification of GABA in individuals with migraine could elucidate the role of this neurotransmitter in migraine pathophysiology. Such information may eventually be useful in the diagnosis and development of more effective treatments for migraine. The aims of this study were therefore to compare the concentration of GABA+ in individuals with migraine with that in asymptomatic individuals, and to determine the diagnostic potential of GABA+ in the classification of those with or without migraine. In this case-control study, GABA+ levels in the brain were determined in 19 participants with migraine and 19 matched controls by (1) H-MRS using Mescher-Garwood point-resolved spectroscopy (MEGA-PRESS) sequence. The diagnostic accuracy of GABA+ for the detection of migraine and the optimal cut-off value were determined by receiver operating characteristic analysis. GABA+ levels were significantly higher (p = 0.002) in those with migraine [median, 1.41 institutional units (IU); interquartile range, 1.31-1.50 IU] than in controls (median, 1.18 IU; interquartile range, 1.12-1.35 IU). The GABA+ concentration appears to have good accuracy for the classification of individuals with or without migraine [area under the curve (95% confidence interval), 0.837 (0.71-0.96); p < 0.001]. The optimal GABA+ cut-off value for migraine was 1.30 IU, with a sensitivity of 84.2%, specificity of 68.4% and positive likelihood ratio of +2.67. The outcomes of this study suggest altered GABA metabolism in migraine. These results add to the scarce evidence on the putative role of GABA in migraine and provide a basis to further explore the causal relationship between GABA+ and the pathophysiology of migraine. This study also demonstrates that GABA+ concentration has good diagnostic accuracy for migraine

  5. Hydrochemistry and 18O/16O and 2H/1H Ratios of Ugandan Waters

    NASA Astrophysics Data System (ADS)

    Gebremichael, M. G.; Jasechko, S.

    2013-12-01

    Today, 70% of the 35 million people living in Uganda have access to an improved water source, ranking Uganda 148 out of 179 nations reporting in 2010 (Millennium Development Goals Indicators). 80% of Ugandans rely on groundwater as their primary drinking water source, collecting at springs or from shallow wells. Similarly, 80% of Ugandans rely upon agriculture - usually rain fed - as their primary income source. Despite lack of access to protected water sources faced by 10 million Ugandans, and the importance of the blue economy to Uganda's continued development, a country-wide investigation of the chemistry and the stable oxygen and hydrogen isotope compositions of waters has yet to be completed. Here we present 250 analyses of 18O/16O, 2H/1H and dissolved ion concentrations of Ugandan lakes, rivers, groundwaters and springs collected during July, 2013. We use the new data to characterize regional scale groundwater recharge sources, advection pathways and interactions with surface waters. Large lakes - Albert, Edward and Victoria - show increases in 18O/16O and 2H/1H ratios consistent with open water evaporation, and are shown to be distinct from nearby groundwaters, suggesting minimal recharge from large lakes to the subsurface. Salinities of eastern Ugandan groundwaters are elevated relative to samples collected from the central and western regions, suggesting that longer groundwater residence times and enhanced water-rock interactions characterize these waters. Springs from western Uganda show a shift in 18O/16O to higher values as a result of hydrothermal water-rock exchanges. Dissolved ion and noble gas concentrations show potential for use in assessing geothermal energy resources, perhaps aiding the Ugandan Ministry for Energy, Minerals and Development to meet their goal of increasing renewable energy from 4% (current) to 61% of total use by 2017 (Nyakabwa-Atwoki, 2013). Millennium Development Goals Indicators. mdgs.un.org/unsd/mdg/data.aspx Nyakabwa

  6. Equilibrium 2H/1H fractionation in organic molecules: III. Cyclic ketones and hydrocarbons

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A.

    2013-04-01

    Quantitative interpretation of stable hydrogen isotope ratios (2H/1H) in organic compounds is greatly aided by knowledge of the relevant equilibrium fractionation factors (ɛeq). Previous efforts have combined experimental measurements and hybrid Density Functional Theory (DFT) calculations to accurately predict equilibrium fractionations in linear (acyclic) organic molecules (Wang et al., 2009a,b), but the calibration produced by that study is not applicable to cyclic compounds. Here we report experimental measurements of equilibrium 2H/1H fractionation in six cyclic ketones, and use those data to evaluate DFT calculations of fractionation in diverse monocyclic and polycyclic compounds commonly found in sedimentary organic matter and petroleum. At 25, 50, and 75 °C, the experimentally measured ɛeq values for secondary and tertiary Hα in isotopic equilibrium with water are in the ranges of -130‰ to -150‰ and +10‰ to -40‰ respectively. Measured data are similar to DFT calculations of ɛeq for axial Hα but not equatorial Hα. In tertiary Cα positions with methyl substituents, this can be understood as a result of the methyl group forcing Hα atoms into a dominantly axial position. For secondary Cα positions containing both axial and equatorial Hα atoms, we propose that axial Hα exchanges with water significantly faster than the equatorial Hα does, due to the hyperconjugation-stabilized transition state. Interconversion of axial and equatorial positions via ring flipping is much faster than isotopic exchange at either position, and as a result the steady-state isotopic composition of both H's is strongly weighted toward that of axial Hα. Based on comparison with measured ɛeq values, a total uncertainty of 10-30‰ remains for theoretical ɛeq values. Using DFT, we systematically estimated the ɛeq values for individual H positions in various cyclic structures. By summing over all individual H positions, the molecular equilibrium fractionation was

  7. ESR lineshape and {sup 1}H spin-lattice relaxation dispersion in propylene glycol solutions of nitroxide radicals – Joint analysis

    SciTech Connect

    Kruk, D.; Hoffmann, S. K.; Goslar, J.; Lijewski, S.; Kubica-Misztal, A.; Korpała, A.; Oglodek, I.; Moscicki, J.; Kowalewski, J.; Rössler, E. A.

    2013-12-28

    Electron Spin Resonance (ESR) spectroscopy and Nuclear Magnetic Relaxation Dispersion (NMRD) experiments are reported for propylene glycol solutions of the nitroxide radical: 4-oxo-TEMPO-d{sub 16} containing {sup 15}N and {sup 14}N isotopes. The NMRD experiments refer to {sup 1}H spin-lattice relaxation measurements in a broad frequency range (10 kHz–20 MHz). A joint analysis of the ESR and NMRD data is performed. The ESR lineshapes give access to the nitrogen hyperfine tensor components and the rotational correlation time of the paramagnetic molecule. The NMRD data are interpreted in terms of the theory of paramagnetic relaxation enhancement in solutions of nitroxide radicals, recently presented by Kruk et al. [J. Chem. Phys. 138, 124506 (2013)]. The theory includes the effect of the electron spin relaxation on the {sup 1}H relaxation of the solvent. The {sup 1}H relaxation is caused by dipole-dipole interactions between the electron spin of the radical and the proton spins of the solvent molecules. These interactions are modulated by three dynamic processes: relative translational dynamics of the involved molecules, molecular rotation, and electron spin relaxation. The sensitivity to rotation originates from the non-central positions of the interacting spin in the molecules. The electronic relaxation is assumed to stem from the electron spin–nitrogen spin hyperfine coupling, modulated by rotation of the radical molecule. For the interpretation of the NMRD data, we use the nitrogen hyperfine coupling tensor obtained from ESR and fit the other relevant parameters. The consistency of the unified analysis of ESR and NMRD, evaluated by the agreement between the rotational correlation times obtained from ESR and NMRD, respectively, and the agreement of the translation diffusion coefficients with literature values obtained for pure propylene glycol, is demonstrated to be satisfactory.

  8. Synthesis, molecular structure and spectroscopic characterization of (E)-1-((2-hydroxynaphthalen-1-yl) methyleneamino)-5-(4-methoxybenzoyl)-4-(4-methoxyphenyl) pyrimidine-2(1H)-one with experimental techniques and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Ceylan, Ümit; Hacıyusufoğlu, Mehmet Emin; Yalçınc, Şerife Pınar; Sönmez, Mehmet; Aygün, Muhittin

    2016-04-01

    A new Schiff base compound, (E)-1-((2-hydroxynaphthalen-1-yl) methyleneamino)-5-(4-methoxybenzoyl)-4-(4-methoxyphenyl) pyrimidine-2(1H)-one, formula sum is given by C30H23N3O5, was synthesized and characterized by experimentally and theoretically. Optimized molecular structure was obtained using X-ray diffraction in the ground state. FT-IR, NMR and UV-Vis frequencies have been measured and compared with theoretically obtained data by using by DFT/B3LYP method with 6-31G(d) and 6-311++G(d,p) basis set. In addition, molecular electrostatic potential (MEP), dipole moments, NBO analysis, atomic charges, HOMO-LUMO and molecular electrostatic potential were computed. The calculated results show that the optimized geometry can well reproduce the crystal structure parameters, and the theoretical vibrational frequencies, 1H and 13C NMR chemical shifts show good agreement with experimental values.

  9. The Phaseolus vulgaris PvTRX1h gene regulates plant hormone biosynthesis in embryogenic callus from common bean.

    PubMed

    Barraza, Aarón; Cabrera-Ponce, José L; Gamboa-Becerra, Roberto; Luna-Martínez, Francisco; Winkler, Robert; Álvarez-Venegas, Raúl

    2015-01-01

    Common bean is the most important grain legume in the human diet. Bean improvement efforts have been focused on classical breeding techniques because bean is recalcitrant to both somatic embryogenesis and in vitro regeneration. This study was undertaken to better understand the process of somatic embryogenesis in the common bean. We focused on the mechanisms by which somatic embryogenesis in plants is regulated and the interaction of these mechanisms with plant hormones. Specifically, we examined the role of the gene PvTRX1h, an ortholog of a major known histone lysine methyltransferase in plants, in somatic embryo generation. Given the problems with regeneration and transformation, we chose to develop and use regeneration-competent callus that could be successively transformed. Embryogenic calli of common bean were generated and transformed with the PvTRX1hRiA construction to down-regulate, by RNA interference, expression of the PvTRX1h gene. Plant hormone content was measured by mass spectrometry and gene expression was assessed by q-PCR. Detailed histological analysis was performed on selected transgenic embryogenic calli. It was determined that down-regulation of PvTRX1h gene was accompanied by altered concentrations of plant hormones in the calli. PvTRX1h regulated the expression of genes involved in auxin biosynthesis and embryogenic calli in which PvTRX1h was down-regulated were capable of differentiation into somatic embryos. Also, down-regulation of PvTRX1h showed increased transcript abundance of a gene coding for a second histone lysine methyltransferase, PvASHH2h. Accordingly, the PvTRX1h gene is involved in the synthesis of plant hormones in common bean callus. These results shed light on the crosstalk among histone methyltransferases and plant hormone signaling and on gene regulation during somatic embryo generation.

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

    PubMed

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

    2012-12-01

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

  11. Potassium 3-oxo-2,3-dihydro-1H-inden-4-olate: Formation, molecular and electronic structure

    NASA Astrophysics Data System (ADS)

    Sigalov, Mark; Shainyan, Bagrat; Sterkhova, Irina

    2016-11-01

    Unlike 1-indanone, 7-hydroxy-1-indanone does not enter the base-catalyzed condensation reaction with 1H-pyrrole-2-carbaldehyde but, instead, gives the salt, potassium 3-oxo-2,3-dihydro-1H-inden-4-olate dihydrate. X-ray analysis, NMR, IR, UV spectroscopy, DFT and MP2 calculations allowed to prove the chelate structure of the salt and to estimate the effect of chelation on the spectral properties as well as to explain the specific reactivity.

  12. Bioactive 2(1H)-Pyrazinones and Diketopiperazine Alkaloids from a Tunicate-Derived Actinomycete Streptomyces sp.

    PubMed

    Shaala, Lamiaa A; Youssef, Diaa T A; Badr, Jihan M; Harakeh, Steve M

    2016-01-01

    As a part of our ongoing effort to allocate marine microbial bioactive leads, a tunicate-derived actinomycete, Streptomyces sp. Did-27, was investigated. Three new 2(1H)-pyrazinones derivatives, (S)-6-(sec-butyl)-3-isopropylpyrazin-2(1H)-one (1), (S)-3-(sec-butyl)-6-isopropylpyrazin-2(1H)-one (2) and (S)-6-(sec-butyl)-3-isobutylpyrazin-2(1H)-one (3), together with the known (1H)-pyrazinones analogues deoxymutaaspergillic acid (4), 3,6-diisobutyl-2(1H)-pyrazinone (5) and 3,6-di-sec-butyl-2(1H)-pyrazinone (6), and the diketopiperazine alkaloids cyclo(6-OH-d-Pro-l-Phe) (7), bacillusamide B (8), cyclo(l-Pro-l-Leu) and cyclo(l-Pro-l-Ile) (10) were isolated from this strain. The structures of the compounds were determined by study of their one- and two-dimensional NMR spectra as well as high-resolution mass spectral determinations. Compound 4 was reported previously as a synthetic product, while compound 6 was reported as 2-hydroxy-3,6-di-sec-butylpyrazine. Herein, we report the complete NMR data for compounds 4 and 6. The compounds were evaluated for their cytotoxic activities against three cell lines. Compound 5 showed potent and selective activity against HCT-116 cell line with IC50 of 1.5 μg/mL, while 1-10 showed variable cytotoxic activities against these cancer cell lines. These results provide further understanding about the chemistry and bioactivities of the alkylated 2(1H)-pyrazinone derivatives. PMID:27563872

  13. Solid-phase synthesis of the 2(1H)-pyrazinone scaffold: a new approach toward diversely substituted heterocycles.

    PubMed

    Kaval, Nadya; Dehaen, Wim; Van der Eycken, Erik

    2005-01-01

    The first solid-phase synthesis of the 2(1H)-pyrazinone scaffold is described. The diversity at position C6 of the pyrazinone ring is determined by the choice of the starting aldehyde. Microwave-enhanced transition metal-catalyzed reactions allow easy introduction of a variety of substituents at the C3 position. This opens a way for the generation of libraries of diversely substituted 2(1H)-pyrazinones that will be screened for biological activities.

  14. The Phaseolus vulgaris PvTRX1h gene regulates plant hormone biosynthesis in embryogenic callus from common bean

    PubMed Central

    Barraza, Aarón; Cabrera-Ponce, José L.; Gamboa-Becerra, Roberto; Luna-Martínez, Francisco; Winkler, Robert; Álvarez-Venegas, Raúl

    2015-01-01

    Common bean is the most important grain legume in the human diet. Bean improvement efforts have been focused on classical breeding techniques because bean is recalcitrant to both somatic embryogenesis and in vitro regeneration. This study was undertaken to better understand the process of somatic embryogenesis in the common bean. We focused on the mechanisms by which somatic embryogenesis in plants is regulated and the interaction of these mechanisms with plant hormones. Specifically, we examined the role of the gene PvTRX1h, an ortholog of a major known histone lysine methyltransferase in plants, in somatic embryo generation. Given the problems with regeneration and transformation, we chose to develop and use regeneration-competent callus that could be successively transformed. Embryogenic calli of common bean were generated and transformed with the PvTRX1hRiA construction to down-regulate, by RNA interference, expression of the PvTRX1h gene. Plant hormone content was measured by mass spectrometry and gene expression was assessed by q-PCR. Detailed histological analysis was performed on selected transgenic embryogenic calli. It was determined that down-regulation of PvTRX1h gene was accompanied by altered concentrations of plant hormones in the calli. PvTRX1h regulated the expression of genes involved in auxin biosynthesis and embryogenic calli in which PvTRX1h was down-regulated were capable of differentiation into somatic embryos. Also, down-regulation of PvTRX1h showed increased transcript abundance of a gene coding for a second histone lysine methyltransferase, PvASHH2h. Accordingly, the PvTRX1h gene is involved in the synthesis of plant hormones in common bean callus. These results shed light on the crosstalk among histone methyltransferases and plant hormone signaling and on gene regulation during somatic embryo generation. PMID:26284093

  15. Visual confrontation naming and hippocampal function: A neural network study using quantitative (1)H magnetic resonance spectroscopy.

    PubMed

    Sawrie, S M; Martin, R C; Gilliam, F G; Faught, R E; Maton, B; Hugg, J W; Bush, N; Sinclair, K; Kuzniecky, R I

    2000-04-01

    Prior research on the relationship between visual confrontation naming and hippocampal function has been inconclusive. The present study examined this relationship using quantitative (1)H magnetic resonance spectroscopy ((1)H-MRS) to operationalize the function of the left and right hippocampi. The 60-item Boston Naming Test (BNT) was used to measure naming. Our sample included 46 patients with medically intractable, focal mesial temporal lobe epilepsy who had been screened for all pathology other than mesial temporal sclerosis. Statistics included Pearson correlations and neural network analysis (multilayer perceptron and radial basis function). Baseline BNT performance correlated significantly with left (1)H-MRS hippocampal ratios. Thirty-six per cent of the variance in baseline BNT performance was explained by a neural network model using left and right (1)H-MRS ratios(creatine/N-acetylaspartate) as input. This was elevated to 49% when input from the right hippocampus was lesioned mathematically. In a second model, left (1)H-MRS hippocampal ratios were modelled using measures of semantic and episodic memory as input (including the BNT). Explained variance in left (1)H-MRS hippocampal ratios fell from 60.8 to 3.6% when input from BNT and another semantic memory measure was degraded mathematically. These results provide evidence that the speech-dominant hippocampus is a significant component of the overall neuroanatomical network of visual confrontation naming. Clinical and theoretical implications are explored.

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

    SciTech Connect

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

    1988-08-25

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

  17. MUSIC in triple-resonance experiments: amino acid type-selective (1)H-(15)N correlations

    PubMed

    Schubert; Smalla; Schmieder; Oschkinat

    1999-11-01

    Amino acid type-selective triple-resonance experiments can be of great help for the assignment of protein spectra, since they help to remove ambiguities in either manual or automated assignment procedures. Here, modified triple-resonance experiments that yield amino acid type-selective (1)H-(15)N correlations are presented. They are based on novel coherence transfer schemes, the MUSIC pulse sequence elements, that replace the initial INEPT transfer and are selective for XH(2) or XH(3) (X can be (15)N or (13)C). The desired amino acid type is thereby selected based on the topology of the side chain. Experiments for Gly (G-HSQC); Ala (A-HSQC); Thr, Val, Ile, and Ala (TAVI-HSQC); Thr and Ala (TA-HSQC), as well as Asn and Gln (N-HSQC and QN-HSQC), are described. The new experiments are recorded as two-dimensional experiments and therefore need only small amounts of spectrometer time. The performance of the experiments is demonstrated with the application to two protein domains. Copyright 1999 Academic Press. PMID:10527741

  18. Lipid profiling of developing Jatropha curcas L. seeds using (1)H NMR spectroscopy.

    PubMed

    Annarao, Sanjay; Sidhu, O P; Roy, Raja; Tuli, Rakesh; Khetrapal, C L

    2008-12-01

    Seed development in Jatropha curcas L. was studied with respect to phenology, oil content, lipid profile and concentration of sterols. Seeds were collected at various stages of development starting from one week after fertilization and in an interval of five days thereafter till maturity. These were classified as stage I to stage VII. Moisture content of the seeds ranged from 8.8 to 90.3%; the lowest in mature seeds in stage VII and highest in stage I. The seed area increased as the seed grew from stage I to stage VI (0.2-10.2mm(2) per seed), however, the seed area shrunk at stage VII. Increase in seed area corresponded to increase in fresh weight of the seeds. (1)H NMR spectroscopy of hexane extracts made at different stages of seed development revealed the presence of free fatty acids (FFA), methyl esters of fatty acids (FAME) and triglycerol esters (TAG), along with small quantity of sterols. The young seeds synthesized predominantly polar lipids. Lipid synthesis was noticed nearly three weeks after fertilization. From the fourth week the seeds actively synthesized TAG. Stage III is a turning point in seed development since at this stage, the concentration of sterols decreased to negligible, there was very little FAME formation, accumulation of TAG increased substantially, and there was a sudden decrease in FFA concentration. The findings can be helpful in understanding the biosynthesis and in efforts to improve biosynthesis of TAG and reduce FFA content in the mature seeds. PMID:18534845

  19. 1H NMR Spectroscopy and MVA Analysis of Diplodus sargus Eating the Exotic Pest Caulerpa cylindracea

    PubMed Central

    De Pascali, Sandra A.; Del Coco, Laura; Felline, Serena; Mollo, Ernesto; Terlizzi, Antonio; Fanizzi, Francesco P.

    2015-01-01

    The green alga Caulerpa cylindracea is a non-autochthonous and invasive species that is severely affecting the native communities in the Mediterranean Sea. Recent researches show that the native edible fish Diplodus sargus actively feeds on this alga and cellular and physiological alterations have been related to the novel alimentary habits. The complex effects of such a trophic exposure to the invasive pest are still poorly understood. Here we report on the metabolic profiles of plasma from D. sargus individuals exposed to C. cylindracea along the southern Italian coast, using 1H NMR spectroscopy and multivariate analysis (Principal Component Analysis, PCA, Orthogonal Partial Least Square, PLS, and Orthogonal Partial Least Square Discriminant Analysis, OPLS-DA). Fish were sampled in two seasonal periods from three different locations, each characterized by a different degree of algal abundance. The levels of the algal bisindole alkaloid caulerpin, which is accumulated in the fish tissues, was used as an indicator of the trophic exposure to the seaweed and related to the plasma metabolic profiles. The profiles appeared clearly influenced by the sampling period beside the content of caulerpin, while the analyses also supported a moderate alteration of lipid and choline metabolism related to the Caulerpa-based diet. PMID:26058009

  20. Neutron-hole states in 45Ar from 1H(46Ar, d) 45Ar reactions

    NASA Astrophysics Data System (ADS)

    Lu, F.; Lee, Jenny; Tsang, M. B.; Bazin, D.; Coupland, D.; Henzl, V.; Henzlova, D.; Kilburn, M.; Lynch, W. G.; Rogers, A. M.; Sanetullaev, A.; Sun, Z. Y.; Youngs, M.; Charity, R. J.; Sobotka, L. G.; Famiano, M.; Hudan, S.; Horoi, M.; Ye, Y. L.

    2013-07-01

    To improve the effective interactions in the pf shell, it is important to measure the single-particle and single-hole states near the N = 28 shell gap. In this paper, the neutron spectroscopic factors of hole states from the unstable neutron-rich 45Ar (Z = 18,N = 27) nucleus have been studied using the 1H(46Ar,d) 45Ar transfer reaction in inverse kinematics. Comparison of our results with the particle states of 45Ar produced in 2H(44Ar, p) 45Ar reaction shows that the two reactions populate states with different angular momenta. Using the angular distributions, we are able to confirm the spin assignments of four low-lying states of 45Ar. These are the ground state (f7/2), the first-excited state (p3/2), and the s1/2 and d3/2 states. While large basis shell-model predictions describe spectroscopic properties of the ground and p3/2 states very well, they fail to describe the s1/2 and d3/2 hole states.

  1. 1H and 13C NMR assignments of new methoxylated furanoflavonoids from Lonchocarpus araripensis.

    PubMed

    Lima, Almi F; Mileo, Paulo Graziane M; Andrade-Neto, Manoel; Braz-Filho, Raimundo; Silveira, Edilberto R; Pessoa, Otília Deusdênia L

    2009-02-01

    Two new polymethoxylated flavonoids, 2',5',6'-trimethoxy-[2'',3'' : 3',4']furano dihydrochalcone and 2,4',4,5-tetramethoxy-[2'',3'' : 6,7]-furanodihydroaurone, were isolated from the root barks of Lonchocarpus araripensis, along with the known compounds 3,4,5,6-tetramethoxy-[2'',3'' : 7,8]-furanoflavan, 3,6-dimethoxy-1'',1''-dimethylcromene-[2'',3'' : 7,8]-flavone, 3',4'-methylenodioxy-5,6-dimethoxy-[2'',3'' : 7,8]-furanoflavone, 3,5,6-trimethoxy-[2'',3'' : 7,8]-furanoflavanone, 3,5,6-trimethoxy-[2'',3'' : 7,8]-furanoflavone, and 6alpha-hydroxy-medicarpin. The complete (1)H and (13)C NMR assignments of the new furan flavonoids were performed using 1D and 2D pulse sequences, including COSY, HSQC, and HMBC experiments, and comparison with spectral data for analog compounds from the literature, particularly for the new furanodihydroaurone because of several inconsistencies on the carbonyl chemical shifts from the literature. PMID:18932264

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

    PubMed

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

    2009-02-01

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

  3. Investigation of irradiated 1H-Benzo[b]pyrrole by ESR, thermal methods and learning algorithm

    NASA Astrophysics Data System (ADS)

    Algul, Gulay; Ceylan, Yusuf; Usta, Keziban; Yumurtaci Aydogmus, Hacer; Usta, Ayhan; Asik, Biray

    2016-05-01

    1H-Benzo[b]pyrrole samples were irradiated in the air with gamma source at 0.969 kGy per hour at room temperature for 24, 48 and 72 h. After irradiation, electron spin resonance, thermogravimetry analysis (TGA) and differential thermal analysis (DTA) measurements were immediately carried out on the irradiated and unirradiated samples. The ESR measurements were performed between 320 and 400 K. ESR spectra were recorded from the samples irradiated for 48 and 72 h. The obtained spectra were observed to be dependent on temperature. Two radical-type centres were detected on the sample. Detected radiation-induced radicals were attributed to R-+•NH and R=•CC2H2. The g-values and hyperfine constants were calculated by means of the experimental spectra. It was also determined from TGA spectrum that both the unirradiated and irradiated samples were decomposed at one step with the rising temperature. Moreover, a theoretical study was presented. Success of the machine learning methods was tested. It was found that bagging techniques, which are widely used in the machine learning literature, could optimise prediction accuracy noticeably.

  4. Effects of high fructose and salt feeding on systematic metabonome probed via (1) H NMR spectroscopy.

    PubMed

    Yang, Yongxia; Zheng, Lingyun; Wang, Linlin; Wang, Shumei; Wang, Yaling; Han, Zhihui

    2015-04-01

    Diets rich in high fructose and salt are increasingly popular in our daily life. A combination consumption of excessive fructose and salt can induce insulin resistance (IR) and hypertension (HT), which are major public health problems around the world. However, the effects of high fructose and salt on systematic metabonome remain unknown, which is very important for revealing the molecular mechanism of IR and HT induced by this dietary pattern. The metabolic profiling in urine, plasma, and fecal extracts from high fructose and salt-fed rats was investigated by use of (1) H nuclear magnetic resonance (NMR)-based metabonomics approach in this study. Multivariate analysis of NMR data showed the effects of high fructose and salt on the global metabonome. The metabolite analysis in urine and fecal extracts showed the time-dependent metabolic changes, which displayed metabonomic progression axes from normal to IR and HT status. The changes of 2-oxoglutarate, creatine and creatinine, citrate, hippurate, trimethylamine N-oxide (TMAO), and betaine in urine, together with gut microbiota disorder in feces, were observed at the preliminary formation stage of IR and HT (fourth week). At the severe stage (eighth week), the previously mentioned metabolic changes were aggravated, and the changes of lipid and choline metabolism in plasma suggested the increased risk of cardiovascular diseases. These findings provide an overview of biochemistry consequences of high fructose and salt feeding and comprehensive insights into the progression of systematic metabonome for IR and HT induced by this dietary pattern.

  5. Application of diffusion ordered-1H-nuclear magnetic resonance spectroscopy to quantify sucrose in beverages.

    PubMed

    Cao, Ruge; Nonaka, Airi; Komura, Fusae; Matsui, Toshiro

    2015-03-15

    This work focuses on a quantitative analysis of sucrose using diffusion ordered-quantitative (1)H-nuclear magnetic resonance spectroscopy (DOSY-qNMR), where an analyte can be isolated from interference based on its characteristic diffusion coefficient (D) in gradient magnetic fields. The D value of sucrose in deuterium oxide at 30°C was 4.9 × 10(-10)m(2)/s at field gradient pulse from 5.0 × 10(-2) to 3.0 × 10(-1)T/m, separated from other carbohydrates (glucose and fructose). Good linearity (r(2)=0.9999) was obtained between sucrose (0.5-20.0 g/L) and the resonance area of target glucopyranosyl-α-C1 proton normalised to that of cellobiose C1 proton (100.0 g/L, as an internal standard) in 1D sliced DOSY spectrum. The DOSY-qNMR method was successfully applied to quantify sucrose in orange juice (36.1 ± 0.5 g/L), pineapple juice (53.5 ± 1.1g/L) and a sports drink (24.7 ± 0.6g/L), in good agreement with the results obtained by an F-kit method.

  6. Intrauterine fetal brain NMR spectroscopy: 1H and 31P studies in rats

    SciTech Connect

    Nakada, T.; Kwee, I.L.; Suzuki, N.; Houkin, K. )

    1989-11-01

    Fetal brain metabolism was investigated in utero noninvasively using multinuclear nuclear magnetic resonance spectroscopy in rats at two representative prenatal stages: early (17-18 days) and late (20-21 days) stages. Phosphorus-31 (31P) spectroscopy revealed that phosphocreatine is significantly lower in the early stage and increases to the level of early neonates by the late prenatal stage. Intracellular pH at the early stage was found to be strikingly high (7.52 +/- 0.21) and decreased to a level similar to that of neonates by the late stage (7.29 +/- 0.07). Phosphomonoester levels at both stages were similar to the values reported for early neonates. Water-suppressed proton (1H) spectroscopy demonstrated a distinctive in vivo fetal brain spectral pattern characterized by low levels of N-acetyl aspartate and high levels of taurine. High-resolution proton spectroscopy and homonuclear chemical-shift correlate spectroscopy of brain perchloric acid extracts confirmed these in vivo findings. In vitro 31P spectroscopy of acidified chloroform methanol extracts showed the characteristic membrane phospholipid profiles of fetal brain. The phosphatidylethanolamine (PE)-to-phosphatidylcholine (PC) ratio (PE/PC) did not show significant changes between the two stages at 0.40 +/- 0.11, a value similar to that of early neonates.

  7. Purity Assessment of Aryltetralin Lactone Lignans by Quantitative 1H Nuclear Magnetic Resonance.

    PubMed

    Sun, Yan-Jun; Zhang, Yan-Li; Wang, Yu; Wang, Jun-Min; Zhao, Xuan; Gong, Jian-Hong; Gao, Wei; Guan, Yan-Bin

    2015-01-01

    In the present work, a quantitative 1H Nuclear Magnetic Resonance (qHNMR) was established for purity assessment of six aryltetralin lactone lignans. The validation of the method was carried out, including specificity, selectivity, linearity, accuracy, precision, and robustness. Several experimental parameters were optimized, including relaxation delay (D1), scan numbers (NS), and pulse angle. 1,4-Dinitrobenzene was used as internal standard (IS), and deuterated dimethyl sulfoxide (DMSO-d6) as the NMR solvent. The purities were calculated by the area ratios of H-2,6 from target analytes vs. aromatic protons from IS. Six aryltetralin lactone lignans (deoxypodophyllotoxin, podophyllotoxin, 4-demethylpodophyllotoxin, podophyllotoxin-7'-O-β-d-glucopyranoside, 4-demethylpodophyllotoxin-7'-O-β-d-glucopyranoside, and 6''-acetyl-podophyllotoxin-7'-O-β -d-glucopyranoside) were analyzed. The analytic results of qHNMR were further validated by high performance liquid chromatography (HPLC). Therefore, the qHNMR method was a rapid, accurate, reliable tool for monitoring the purity of aryltetralin lactone lignans. PMID:26016553

  8. Sequence-specific 1H assignment and secondary structure of the bacteriocin AS-48 cyclic peptide.

    PubMed

    Langdon, G M; Bruix, M; Gálvez, A; Valdivia, E; Maqueda, M; Rico, M

    1998-07-01

    The bacteriocin AS-48 is a cationic peptide (7149 Da) having a broad antimicrobial spectrum, encoded by the 68 kb conjugative plasmid pMB2 from Enterococcus faecalis S-48. It is a unique peptide since it has a cyclic structure, which is achieved by the formation of a tail-head peptide bond after ribosomal synthesis (Gálvez et al., 1989; Martínez-Bueno et al., 1994; Samyn et al., 1994). Preliminary CD and calorimetric studies (data not shown) pointed towards a highly helical and very stable three dimensional structure. All the information gathered until now indicates that the target of AS-48 is the cytoplasmic membrane in which it opens channels or pores, leading to dissipation of the proton motive force and cell death, which in some cases is also followed by bacterial lysis (Gálvez et al., 1991). This peptide is a suitable tool for studying protein-membrane interactions, and it also offers promising perspectives for biotechnological applications. Knowledge of the 3D structure of AS-48 is a first step in the conduct of further structure-function studies. Here we report the complete 1H NMR assignment of its proton resonances together with the resulting secondary structure pattern as prerequisites for the determination of a high-resolution 3D solution structure.

  9. Serum Metabolomic Profiling of Sulphur Mustard-Exposed Individuals Using (1)H Nuclear Magnetic Resonance Spectroscopy.

    PubMed

    Zamani, Zahra; Ghanei, Mostafa; Panahi, Yunus; Arjmand, Mohammad; Sadeghi, Sedigheh; Mirkhani, Fatemeh; Parvin, Shahram; Salehi, Maryam; Sahebkar, Amirhossein; Vahabi, Farideh

    2016-01-01

    Sulphur mustard is an alkylating agent that reacts with different cellular components, causing acute and delayed complications that may remain for decades after exposure. This study aimed to identify differentially expressed metabolites between mustard-exposed individuals suffering from chronic complications compared with unexposed individuals as the control group. Serum samples were obtained from 15 mustard-exposed individuals and 15 apparently healthy unexposed individuals. Metabolomic profiling was performed using (1)H nuclear magnetic resonance spectroscopy, and analyses were carried out using Chenomex and MATLAB softwares. Metabolites were identified using Human Metabolome Database, and the main metabolic pathways were identified using MetaboAnalyst software. Chemometric analysis of serum samples identified 11 differentially expressed metabolites between mustard-exposed and unexposed groups. The main pathways that were influenced by sulphur mustard exposure were related to vitamin B6 (down-regulation), bile acid (up-regulation) and tryptophan (down-regulation) metabolism. Metabolism of vitamin B6, bile acids and tryptophan are the most severely impaired pathways in individuals suffering from chronic mustard-induced complications. These findings may find implications in the monitoring of exposed patients and identification of new therapeutic approaches.

  10. 1H NMR based metabolic profiling in Crohn's disease by random forest methodology.

    PubMed

    Fathi, Fariba; Majari-Kasmaee, Laleh; Mani-Varnosfaderani, Ahmad; Kyani, Anahita; Rostami-Nejad, Mohammad; Sohrabzadeh, Kaveh; Naderi, Nosratollah; Zali, Mohammad Reza; Rezaei-Tavirani, Mostafa; Tafazzoli, Mohsen; Arefi-Oskouie, Afsaneh

    2014-07-01

    The present study was designed to search for metabolic biomarkers and their correlation with serum zinc in Crohn's disease patients. Crohn's disease (CD) is a form of inflammatory bowel disease that may affect any part of the gastrointestinal tract and can be difficult to diagnose using the clinical tests. Thus, introduction of a novel diagnostic method would be a major step towards CD treatment. Proton nuclear magnetic resonance spectroscopy ((1)H NMR) was employed for metabolic profiling to find out which metabolites in the serum have meaningful significance in the diagnosis of CD. CD and healthy subjects were correctly classified using random forest methodology. The classification model for the external test set showed a 94% correct classification of CD and healthy subjects. The present study suggests Valine and Isoleucine as differentiating metabolites for CD diagnosis. These metabolites can be used for screening of risky samples at the early stages of CD diagnoses. Moreover, a robust random forest regression model with good prediction outcomes was developed for correlating serum zinc level and metabolite concentrations. The regression model showed the correlation (R(2)) and root mean square error values of 0.83 and 6.44, respectively. This model suggests valuable clues for understanding the mechanism of zinc deficiency in CD patients.

  11. 1H-NMR metabolite profiles of different strains of Plasmodium falciparum

    PubMed Central

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

    2014-01-01

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

  12. Phase response curve to 1 h light pulses for the European rabbit (Oryctolagus cuniculus).

    PubMed

    Kennedy, Gerard A; Hudson, Robyn

    2016-01-01

    While much is known about the circadian systems of rodents, chronobiological studies of other mammalian groups have been limited. One of the most extensively studied nonrodent species, both in the laboratory and in the wild, is the European rabbit. The aim of this study was to extend knowledge of the rabbit circadian system by examining its phasic response to light. Twelve Dutch-Himalayan cross rabbits of both sexes were allowed to free-run in constant darkness and then administered 1 h light pulses (1000 lux) at multiple predetermined circadian times. Changes in the phase of the rabbits' circadian wheel-running rhythms were measured after each light pulse and used to construct a phase-response curve (PRC). The rabbits' PRC and free-running period (τ) conformed to the empirical regularities reported for other predominantly nocturnal animals, including rodents and predatory marsupials. The results of the study are thus consistent with reports that the rabbit is essentially a nocturnal animal and show that it can entrain to light/dark (LD) cycles via discrete phase shifts. Knowledge about the rabbit's circadian range of entrainment to LD cycles gained in this study will be useful for examining the putative circadian processes believed to underlie the unusual rhythm of very brief, once-daily nest visits by nursing rabbit mothers and other nursing lagomorphs. PMID:27305519

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

    PubMed

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

    2003-01-01

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

  14. Determination of the X-ray reflection emissivity profile of 1H 0707-495

    NASA Astrophysics Data System (ADS)

    Wilkins, D. R.; Fabian, A. C.

    2011-06-01

    When considering the X-ray spectrum resulting from the reflection off the surface of accretion discs of AGN, it is necessary to account for the variation in reflected flux over the disc, i.e. the emissivity profile. This will depend on factors including the location and geometry of the X-ray source and the disc characteristics. We directly obtain the emissivity profile of the disc from the observed spectrum by considering the reflection component as the sum of contributions from successive radii in the disc and fitting to find the relative weightings of these components in a relativistically broadened emission line. This method has successfully recovered known emissivity profiles from synthetic spectra and is applied to XMM-Newton spectra of the Narrow Line Seyfert 1 galaxy 1H 0707-495. The data imply a twice-broken power-law form of the emissivity law with a steep profile in the inner regions of the disc (index 7.8) and then a flat region between 5.6 and 34.8rg before tending to a constant index of 3.3 over the outer regions of the disc. The form of the observed emissivity profile is consistent with theoretical predictions, thus reinforcing the reflection interpretation.

  15. Evidence of vintage effects on grape wines using 1H NMR-based metabolomic study.

    PubMed

    Lee, Jang-Eun; Hwang, Geum-Sook; Van Den Berg, Frans; Lee, Cherl-Ho; Hong, Young-Shick

    2009-08-19

    The chemical composition of grape wines varies with grape variety, environmental factors of climate and soil, and bacterial strains, which can each affect the wine quality. Using (1)H NMR analysis coupled with multivariate statistical data sets, we investigated the effects of grape vintage on metabolic profiles of wine and the relationship between wine metabolites and meteorological data. Principal component analysis (PCA) showed a clear differentiation between Meoru wines that were vinified with the same yeast strain and Meoru grapes harvested from the same vineyard but with a different vintage. The metabolites contributing to the differentiation were identified as 2,3-butandiol, lactic acid, alanine, proline, gamma-aminobutyric acid (GABA), choline, and polyphenols, by complementary PCA loading plot. Markedly higher levels of proline, lactic acid and polyphenols were observed in the 2006 vintage wines compared to those of 2007 vintage, showing excellent agreement with the meteorological data that the sun-exposed time and rainfall in 2006 were approximately two times more and four times less, respectively, than those in 2007. These results revealed the important role of climate during ripening period in the chemical compositions of the grape. This study highlights the reliability of NMR-based metabolomic data by integration with meteorological data in characterizing wine or grape.

  16. Localized in Vivo Isotropic-Anisotropic Correlation 1H NMR Spectroscopy Using Ultraslow Magic Angle Spinning

    SciTech Connect

    Wind, Robert A.; Hu, Jian Zhi; Majors, Paul D.

    2006-01-01

    Previous work has shown that it is possible to separate the susceptibility broadening in the 1H NMR metabolite spectrum obtained in a live mouse from the isotropic information, thus significantly increasing the spectral resolution. This was achieved using ultra-slow magic angle spinning of the animal combined with a modified phase-corrected magic angle turning (PHORMAT) pulse sequence. However, PHORMAT cannot be used for spatially selective spectroscopy. In this article a modified sequence called LOCMAT (localized magic angle turning) is introduced that makes this possible. Proton LOCMAT spectra are shown for the liver and heart of a live mouse, while spinning the animal at a speed of 4 Hz in a 2 Tesla field. It was found that even in this relatively low field LOCMAT provided isotropic line widths that are a factor 4-10 times smaller than the ones obtained in a stationary animal, and that the susceptibility broadening of the heart metabolites shows unusual features not observed for a dead animal. Finally, the limitations of LOCMAT and possible ways to improve the technique are discussed. It is concluded that in vivo LOCMAT can significantly enhance the utility of NMR spectroscopy for biomedical research.

  17. Discrimination of the geographical origin of beef by (1)H NMR-based metabolomics.

    PubMed

    Jung, Youngae; Lee, Jueun; Kwon, Joseph; Lee, Kwang-Sik; Ryu, Do Hyun; Hwang, Geum-Sook

    2010-10-13

    The geographical origin of beef is of increasing interest to consumers and producers due to "mad cow" disease and the implementation of the Free Trade Agreement (FTA). In this study, (1)H NMR spectroscopy coupled with multivariate statistical analyses was used to differentiate the geographical origin of beef samples. Principal component analysis (PCA) and orthogonal projection to latent structure-discriminant analysis (OPLS-DA) showed significant separation between extracts of beef originating from four countries: Australia, Korea, New Zealand, and the United States. The major metabolites responsible for differentiation in OPLS-DA loading plots were succinate and various amino acids including isoleucine, leucine, methionine, tyrosine, and valine. A one-way ANOVA was performed to statistically certify the difference in metabolite levels. The data suggest that NMR-based metabolomics is an efficient method to distinguish fingerprinting difference between raw beef samples, and several metabolites including various amino acids and succinate can be possible biomarkers for discriminating the geographical origin of beef. PMID:20831251

  18. 60 MHz (1)H NMR spectroscopy for the analysis of edible oils.

    PubMed

    Parker, T; Limer, E; Watson, A D; Defernez, M; Williamson, D; Kemsley, E Kate

    2014-05-01

    We report the first results from a new 60 MHz (1)H nuclear magnetic resonance (NMR) bench-top spectrometer, Pulsar, in a study simulating the adulteration of olive oil with hazelnut oil. There were qualitative differences between spectra from the two oil types. A single internal ratio of two isolated groups of peaks could detect hazelnut oil in olive oil at the level of ∼13%w/w, whereas a whole-spectrum chemometric approach brought the limit of detection down to 11.2%w/w for a set of independent test samples. The Pulsar's performance was compared to that of Fourier transform infrared (FTIR) spectroscopy. The Pulsar delivered comparable sensitivity and improved specificity, making it a superior screening tool. We also mapped NMR onto FTIR spectra using a correlation-matrix approach. Interpretation of this heat-map combined with the established annotations of the NMR spectra suggested a hitherto undocumented feature in the IR spectrum at ∼1130 cm(-1), attributable to a double-bond vibration. PMID:24850979

  19. Electron-phonon induced complex quasiparticles in the 1x1 H/W(110) surface.

    NASA Astrophysics Data System (ADS)

    Eiguren, Asier; Ambrosch-Draxl, Claudia

    2008-03-01

    We show that the solution of the complex Dyson equation for the electron-phonon problem induces several quasiparticle states for a given wave vector. The Dyson equation is considered in the full complex plane and it is solved without considering the imaginary part of the self-energy as an small parameter. By a first principle application of the formalism to the 1x1 H covered W(110) surface, we show that some aspects of the surface band splitting [Rotenberg et. al., Phys. Rev. Lett. 84, 2925 (2000)] can be traced back to electron-phonon coupling, where we present the energy and lifetimes of each quasiparticle. Despite this breakdown of the single quasi-particle picture, it is remarkable that the spectral functions are very well Represented by the predicted multiple quasi-particles. From these results, we can deduce that some of the features that previously where prescribed in ARPES spectra as incoherent structure could eventually be re-interpreted as contributions from additional quasi-particle states. Our method could also help to understand similar phenomena observed in high Tc cuprates and various other surfaces.

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

    PubMed

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

    2015-01-01

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

  1. Looking for new antileishmanial derivatives in 8-nitroquinolin-2(1H)-one series.

    PubMed

    Kieffer, Charline; Cohen, Anita; Verhaeghe, Pierre; Hutter, Sébastien; Castera-Ducros, Caroline; Laget, Michèle; Remusat, Vincent; M'Rabet, Manel Kraiem; Rault, Sylvain; Rathelot, Pascal; Azas, Nadine; Vanelle, Patrice

    2015-03-01

    From a recently identified antileishmanial pharmacophore, a structure-activity relationship study was conducted by introducing various aminated, phenoxy or thiophenoxy moieties at position 4 of the 8-nitroquinolin-2(1H)-one scaffold, using SNAr reactions. Thus a series of 47 derivatives was synthesized and evaluated in vitro on the promastigote stage of Leishmania donovani. In parallel, the cytotoxicity of the active molecules was tested on the human HepG2 cell line. The results we obtained showed that the introduction of a substituent at position 4 of the antileishmanial pharmacophore can either lead to inactive or active derivatives, depending on the nature of the substituent. Aminated moieties appear as very unfavorable toward antileishmanial activity, while phenoxy or thiophenoxy moieties were shown to maintain the in vitro antileishmanial profile, especially when the phenyl ring of these moieties was substituted at the para or ortho position by a halogen atom (except fluorine), a trifluoromethyl group or a methyl group. Most of these derivatives showed a lack of solubility in the culture media which hindered the in vitro determination of both their cytotoxicity and activity against the intracellular amastigoste stage of L. donovani.

  2. Identification of a de novo DYNC1H1 mutation via WES according to published guidelines

    PubMed Central

    Ding, Dongxue; Chen, Zhao; Li, Kai; Long, Zhe; Ye, Wei; Tang, Zhaoli; Xia, Kun; Qiu, Rong; Tang, Beisha; Jiang, Hong

    2016-01-01

    De novo mutations that contribute to rare Mendelian diseases, including neurological disorders, have been recently identified. Whole-exome sequencing (WES) has become a powerful tool for the identification of inherited and de novo mutations in Mendelian diseases. Two important guidelines were recently published regarding the investigation of causality of sequence variant in human disease and the interpretation of novel variants identified in human genome sequences. In this study, a family with supposed movement disorders was sequenced via WES (including the proband and her unaffected parents), and a standard investigation and interpretation of the identified variants was performed according to the published guidelines. We identified a novel de novo mutation (c.2327C > T, p.P776L) in DYNC1H1 gene and confirmed that it was the causal variant. The phenotype of the affected twins included delayed motor milestones, pes cavus, lower limb weakness and atrophy, and a waddling gait. Electromyographic (EMG) recordings revealed typical signs of chronic denervation. Our study demonstrates the power of WES to discover the de novo mutations associated with a neurological disease on the whole exome scale, and guidelines to conduct WES studies and interpret of identified variants are a preferable option for the exploration of the pathogenesis of rare neurological disorders. PMID:26846447

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2015-10-14

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

  5. 1H-NMR measurements of proton mobility in nano-crystalline YSZ.

    PubMed

    Hinterberg, Judith; Adams, Alina; Blümich, Bernhard; Heitjans, Paul; Kim, Sangtae; Munir, Zuhair A; Martin, Manfred

    2013-12-01

    We report nuclear magnetic resonance (NMR) results on water saturated, dense, nano-crystalline YSZ samples (9.5 mol% yttria doped zirconia) which exhibit proton conductivity at temperatures as low as room temperature. (1)H-NMR spectra recorded under static and magic angle spinning conditions show two distinct signals. Their temperature-dependent behavior and their linewidths suggest that one can be attributed to (free) water adsorbed on the surface of the sample and the other one to mobile protons within the sample. This interpretation is supported by comparison with measurements on a single-crystalline sample. For the nano-crystalline samples motional narrowing is observed for the signal originating from protons in the sample interior. For these protons, the analysis of temperature and field dependent spin-lattice relaxation time T1 points towards diffusion in a confined two-dimensional geometry. We attribute this quasi two-dimensional motion to protons that are mobile along internal interfaces or nanopores of nano-crystalline YSZ.

  6. Characterization of water-soluble organic matter in urban aerosol by 1H-NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Chalbot, Marie-Cecile G.; Chitranshi, Priyanka; Gamboa da Costa, Gonçalo; Pollock, Erik; Kavouras, Ilias G.

    2016-03-01

    The functional and 13C isotopic compositions of water-soluble organic carbon (WSOC) in atmospheric aerosol were determined by nuclear magnetic resonance (1H-NMR) and isotope ratio mass spectrometry (IRMS) in an urban location in the Southern Mississippi Valley. The origin of WSOC was resolved using the functional distribution of organic hydrogen, δ13C ratio, and positive matrix factorization (PMF). Three factors were retained based on NMR spectral bins loadings. Two factors (factors 1 and 3) demonstrated strong associations with the aliphatic region in the NMR spectra and levoglucosan resonances. Differences between the two factors included the abundance of the aromatic functional group for factor 1, indicating fresh emissions and, for factor 3, the presence of resonances attributed to secondary ammonium nitrate and low δ13C ratio values that are indicative of secondary organic aerosol. Factors 1 and 3 added 0.89 and 1.08 μgC m-3, respectively, with the highest contribution in the summer and fall. Factor 2 retained resonances consistent with saccharides and was attributed to pollen particles. Its contribution to WSOC varied from 0.22 μgC m-3 in winter to 1.04 μgC m-3 in spring.

  7. Evaluation of multiple sclerosis by 1H spectroscopic imaging at 4.1 T.

    PubMed

    Pan, J W; Hetherington, H P; Vaughan, J T; Mitchell, G; Pohost, G M; Whitaker, J N

    1996-07-01

    The authors report on high-field (4.1 T) magnetic resonance 1H spectroscopic imaging studies on eight patients with relapsing remitting multiple sclerosis (mean expanded disability status scale (EDSS) 1.0) and eight normal controls. Using T1-weighted imaging to determine lesion position, the authors found the ratios of choline/N-acetyl (NA) compounds and creatine/NA were increased significantly in the multiple sclerosis (MS) patients relative to controls in lesioned tissue, adjacent to lesion, far removed from lesions as well as in periventricular tissue. The gray matter creatine/NA was mildly increased (P < 0.01) in the MS patients, whereas the elevated gray-matter ratio of choline/NA was of borderline significance (P = 0.13). A more detailed comparison of white-matter and mean gray-matter metabolite values indicates that creatine is increased greatest in areas far from lesions. This is in contrast to choline, which was greatest in lesions, and NA, which was smallest in lesions. It is postulated that the creatine increase may reflect an astrocytic (gliotic) or oligodendrocytic remyelinating process. The increased choline most likely reflects varying levels of inflammation and membrane turnover, whereas the NA decrease is representative of axonal dysfunction or loss. PMID:8795023

  8. Characterizing monoclonal antibody formulations in arginine glutamate solutions using 1H NMR spectroscopy

    PubMed Central

    Kheddo, Priscilla; Cliff, Matthew J.; Uddin, Shahid; van der Walle, Christopher F.; Golovanov, Alexander P.

    2016-01-01

    ABSTRACT Assessing how excipients affect the self-association of monoclonal antibodies (mAbs) requires informative and direct in situ measurements for highly concentrated solutions, without sample dilution or perturbation. This study explores the application of solution nuclear magnetic resonance (NMR) spectroscopy for characterization of typical mAb behavior in formulations containing arginine glutamate. The data show that the analysis of signal intensities in 1D 1H NMR spectra, when compensated for changes in buffer viscosity, is invaluable for identifying conditions where protein-protein interactions are minimized. NMR-derived molecular translational diffusion rates for concentrated solutions are less useful than transverse relaxation rates as parameters defining optimal formulation. Furthermore, NMR reports on the solution viscosity and mAb aggregation during accelerated stability study assessment, generating data consistent with that acquired by size-exclusion chromatography. The methodology developed here offers NMR spectroscopy as a new tool providing complementary information useful to formulation development of mAbs and other large therapeutic proteins. PMID:27589351

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

    SciTech Connect

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

    1987-09-08

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

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

    NASA Astrophysics Data System (ADS)

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

    1998-11-01

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

  11. (1)H nuclear magnetic resonance-based metabolomics study of earthworm Perionyx excavatus in vermifiltration process.

    PubMed

    Wang, Lei; Huang, Xulei; Laserna, Anna Karen Carrasco; Li, Sam Fong Yau

    2016-10-01

    In this study, (1)H nuclear magnetic resonance (NMR)-based metabolomics approach was used to characterize the metabolic response of the earthworm Perionyx excavatus in continuous vermifiltration for two months under hydraulic loading rates of 1m(3)m(-2)d(-1) (VF1) and 1.5m(3)m(-2)d(-1) (VF1.5). Both VF1 and VF1.5 showed higher removal of chemical oxygen demand and total nitrogen than the biofilter without earthworms. Principal component analysis of the NMR spectra of earthworm metabolites showed significant separations between those not subjected to wastewater filtration (control) and VF1 or VF1.5. Temporal variations of earthworm biomass, and the identified metabolites that are significantly different between control, VF1 and VF1.5 revealed that worms underwent increasing metabolic activity within 20days in VF1 and 14days in VF1.5, then decreasing metabolic activity. The use of NMR-based metabolomics in monitoring earthworm metabolism was demonstrated to be a novel approach in studying engineered vermifiltration systems. PMID:27469092

  12. 1H NMR global metabolic phenotyping of acute pancreatitis in the emergency unit.

    PubMed

    Villaseñor, Alma; Kinross, James M; Li, Jia V; Penney, Nicholas; Barton, Richard H; Nicholson, Jeremy K; Darzi, Ara; Barbas, Coral; Holmes, Elaine

    2014-12-01

    We have investigated the urinary and plasma metabolic phenotype of acute pancreatitis (AP) patients presenting to the emergency room at a single center London teaching hospital with acute abdominal pain using (1)H NMR spectroscopy and multivariate modeling. Patients were allocated to either the AP (n = 15) or non-AP patients group (all other causes of abdominal pain, n = 21) on the basis of the national guidelines. Patients were assessed for three clinical outcomes: (1) diagnosis of AP, (2) etiology of AP caused by alcohol consumption and cholelithiasis, and (3) AP severity based on the Glasgow score. Samples from AP patients were characterized by high levels of urinary ketone bodies, glucose, plasma choline and lipid, and relatively low levels of urinary hippurate, creatine and plasma-branched chain amino acids. AP could be reliably identified with a high degree of sensitivity and specificity (OPLS-DA model R(2) = 0.76 and Q(2)Y = 0.59) using panel of discriminatory biomarkers consisting of guanine, hippurate and creatine (urine), and valine, alanine and lipoproteins (plasma). Metabolic phenotyping was also able to distinguish between cholelithiasis and colonic inflammation among the heterogeneous non-AP group. This work has demonstrated that combinatorial biomarkers have a strong diagnostic and prognostic potential in AP with relevance to clinical decision making in the emergency unit. PMID:25160714

  13. 1H NMR Metabolic Profiling of Biofluids from Rats with Gastric Mucosal Lesion and Electroacupuncture Treatment

    PubMed Central

    Xu, Jingjing; Cheng, Kian-Kai; Yang, Zongbao; Wang, Chao; Shen, Guiping; Wang, Yadong; Liu, Qiong; Dong, Jiyang

    2015-01-01

    Gastric mucosal lesion (GML) is a common gastrointestinal disorder with multiple pathogenic mechanisms in clinical practice. In traditional Chinese medicine (TCM), electroacupuncture (EA) treatment has been proven as an effective therapy for GML, although the underlying healing mechanism is not yet clear. Here, we used proton nuclear magnetic resonance- (1H NMR-) based metabolomic method to investigate the metabolic perturbation induced by GML and the therapeutic effect of EA treatment on stomach meridian (SM) acupoints. Clear metabolic differences were observed between GML and control groups, and related metabolic pathways were discussed by means of online metabolic network analysis toolbox. By comparing the endogenous metabolites from GML and GML-SM groups, the disturbed pathways were partly recovered towards healthy state via EA treated on SM acupoints. Further comparison of the metabolic variations induced by EA stimulated on SM and the control gallbladder meridian (GM) acupoints showed a quite similar metabolite composition except for increased phenylacetylglycine, 3,4-dihydroxymandelate, and meta-hydroxyphenylacetate and decreased N-methylnicotinamide in urine from rats with EA treated on SM acupoints. The current study showed the potential application of metabolomics in providing further insight into the molecular mechanism of acupuncture. PMID:26170882

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

    PubMed

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

    2015-10-14

    The aim of this study was to verify the authenticity of sesame oils using combined analysis of stable isotope ratio, (1)H NMR spectroscopy, and fatty acid profiles of the oils. Analytical data were obtained from 35 samples of authentic sesame oils and 29 samples of adulterated sesame oils currently distributed in Korea. The orthogonal projection to latent structure discriminant analysis technique was used to select variables that most effectively verify the sesame oil authenticity. The variables include δ(13)C value, integration values of NMR peaks that signify the CH3 of n-3 fatty acids, CH2 between two C═C, protons from sesamin/sesamolin, and 18:1n-9, 18:3n-3, 18:2t, and 18:3t content values. The authenticity of 65 of 70 blind samples was correctly verified by applying the range of the eight variables found in the authentic sesame oil samples, suggesting that triple analysis is a useful approach to verify sesame oil authenticity. PMID:26395416

  15. Composition and Quantitation of Microalgal Lipids by ERETIC 1H NMR Method

    PubMed Central

    Nuzzo, Genoveffa; Gallo, Carmela; d’Ippolito, Giuliana; Cutignano, Adele; Sardo, Angela; Fontana, Angelo

    2013-01-01

    Accurate characterization of biomass constituents is a crucial aspect of research in the biotechnological application of natural products. Here we report an efficient, fast and reproducible method for the identification and quantitation of fatty acids and complex lipids (triacylglycerols, glycolipids, phospholipids) in microalgae under investigation for the development of functional health products (probiotics, food ingredients, drugs, etc.) or third generation biofuels. The procedure consists of extraction of the biological matrix by modified Folch method and direct analysis of the resulting material by proton nuclear magnetic resonance (1H NMR). The protocol uses a reference electronic signal as external standard (ERETIC method) and allows assessment of total lipid content, saturation degree and class distribution in both high throughput screening of algal collection and metabolic analysis during genetic or culturing studies. As proof of concept, the methodology was applied to the analysis of three microalgal species (Thalassiosira weissflogii, Cyclotella cryptica and Nannochloropsis salina) which drastically differ for the qualitative and quantitative composition of their fatty acid-based lipids. PMID:24084790

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

    PubMed

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

    2010-09-01

    In quantitative NMR (qNMR) selection of an appropriate internal standard proves to be crucial. In this study, 25 candidate compounds considered to be potent internal standards were investigated with respect to the ability of providing unique signal chemical shifts, purity, solubility, and ease of use. The (1)H chemical shift (delta) values, assignments, multiplicities and number of protons (for each signal), appropriateness (as to be used as internal standards) in four different deuterated solvents (D(2)O, DMSO-d(6), CD(3)OD, CDCl(3)) were studied. Taking into account the properties of these 25 internal standards, the most versatile eight compounds (2,4,6-triiodophenol, 1,3,5-trichloro-2-nitrobenzene, 3,4,5-trichloropyridine, dimethyl terephthalate, 1,4-dinitrobenzene, 2,3,5-triiodobenzoic acid, maleic acid and fumaric acid) were qualified using both differential scanning calorimetry (DSC) and NMR spectroscopy employing highly pure acetanilide as the reference standard. The data from these two methods were compared as well as utilized in the quality assessment of the compounds as internal standards. Finally, the selected internal standards were tested and evaluated in a real case of quantitative NMR analysis of a paracetamol pharmaceutical product. PMID:20207092

  17. (1)H nuclear magnetic resonance-based metabolomics study of earthworm Perionyx excavatus in vermifiltration process.

    PubMed

    Wang, Lei; Huang, Xulei; Laserna, Anna Karen Carrasco; Li, Sam Fong Yau

    2016-10-01

    In this study, (1)H nuclear magnetic resonance (NMR)-based metabolomics approach was used to characterize the metabolic response of the earthworm Perionyx excavatus in continuous vermifiltration for two months under hydraulic loading rates of 1m(3)m(-2)d(-1) (VF1) and 1.5m(3)m(-2)d(-1) (VF1.5). Both VF1 and VF1.5 showed higher removal of chemical oxygen demand and total nitrogen than the biofilter without earthworms. Principal component analysis of the NMR spectra of earthworm metabolites showed significant separations between those not subjected to wastewater filtration (control) and VF1 or VF1.5. Temporal variations of earthworm biomass, and the identified metabolites that are significantly different between control, VF1 and VF1.5 revealed that worms underwent increasing metabolic activity within 20days in VF1 and 14days in VF1.5, then decreasing metabolic activity. The use of NMR-based metabolomics in monitoring earthworm metabolism was demonstrated to be a novel approach in studying engineered vermifiltration systems.

  18. Synthesis and molecular modeling studies of anti-inflammatory active 1H-pyrrolizine-5-carboxamides.

    PubMed

    Barsoum, Flora F

    2011-01-01

    A variety of N-aryl-7-cyano-2,3-dihydro-1H-pyrrolizine-5-carboxamides 5, 6, 8, and 9 were synthesized via reaction of the 2-amino derivatives 4 with acid chlorides and aromatic aldehydes. Meanwhile, 4a,b were obtained through the reaction of 2-pyrrolidinylidenepropanedinitrile 1 with chloroacetanilides 2a,b. In addition, the tricyclic pyrimido[5,4-a]pyrrolizines were formed through conducting the reaction of 4a,b with 90% formic acid. Anti-inflammatory activity screening of some synthesized compounds utilizing in vivo acute carrageenan-induced paw edema standard method in rats exhibited that the prepared heterocycles possess considerable pharmacological properties especially, 4a, 4b, 10a, and 10b which reveal remarkable activities relative to diclofenac sodium (reference standard). Ulcerogenic liability of the highly promising synthesized anti-inflammatory active agents were evaluated and 4a and 4b showed ulcerogenic liability lower than that of the standard used drug. Molecular modeling studies were initiated herein in order to validate the attained pharmacological data and provide understandable evidence for the observed anti-inflammatory behavior.

  19. Computerized MRS voxel registration and partial volume effects in single voxel 1H-MRS.

    PubMed

    Lee, Hedok; Caparelli, Elisabeth; Li, Haifang; Mandal, Amit; Smith, S David; Zhang, Shaonan; Bilfinger, Thomas V; Benveniste, Helene

    2013-09-01

    Partial volume effects in proton magnetic resonance spectroscopy in the brain have been studied previously in terms of proper water concentration calculations, but there is a lack of disclosure in terms of voxel placement techniques that would affect the calculations. The purpose of this study is to facilitate a fully automated MRS voxel registration method which is time efficient, accurate, and can be extended to all imaging modalities. A total of thirteen healthy adults underwent single voxel 1H-MRS scans in 3.0T MRI scanners. Transposition of a MRS voxel onto an anatomical scan is derived along with a full calculation of water concentration with a correction term to account for the partial volume effects. Five metabolites (tNAA, Glx, tCr, mI, and tCho) known to yield high reliability are studied. Pearson's correlation analyses between tissue volume fractions and metabolite concentrations were statistically significant in parietal (tCr, Glx, and tNAA) lobe and occipital lobe (tNAA). MRS voxel overlaps quantified by dice metric over repeated visits yielded 60%~70% and coefficients of variance in metabolites concentration were 4%~10%. These findings reiterate an importance of considering the partial volume effects when tissue water is used as an internal concentration reference so as to avoid misinterpreting a morphometric difference as a metabolic difference.

  20. [Development of functional 1H MRI probes based on nanoparticle design].

    PubMed

    Mizukami, Shin

    2013-01-01

    Visualization of biomolecules in living bodies has attracted increasing attention in recent years. Magnetic resonance imaging (MRI) is a noninvasive technique that yields high-resolution structural information of deep anatomical regions; therefore, it has promising applications in the development of probes to visualize biological functions. By using stimuli-responsive polymers, we developed (1)H MRI probes to measure the pH of aqueous solutions. The longitudinal relaxivity of P-Gd, a conjugate of n-octylamine-modified poly(SM-EVE) with Gd(3+) complexes, increased as the pH of the solution decreased from neutral to acidic. Fluorometric investigation confirmed that the side chains of P-Gd were more rotationally restricted in acidic pH than in neutral pH conditions. In order to improve the magnitude of relaxivity, we developed novel probes C10-Gd and C30-Gd on the basis of cross-linked polymer nanoparticles. The relaxivities of these probes were measured, and the values showed that these nanoparticle-based probes also possessed pH-responsive molecular switches. In addition, their relaxivities were much larger than those of non-cross-linked probes. These nanoparticle-based MRI probes would be useful for the diagnosis of various diseases such as cancer and inflammatory diseases.

  1. Application of diffusion ordered-1H-nuclear magnetic resonance spectroscopy to quantify sucrose in beverages.

    PubMed

    Cao, Ruge; Nonaka, Airi; Komura, Fusae; Matsui, Toshiro

    2015-03-15

    This work focuses on a quantitative analysis of sucrose using diffusion ordered-quantitative (1)H-nuclear magnetic resonance spectroscopy (DOSY-qNMR), where an analyte can be isolated from interference based on its characteristic diffusion coefficient (D) in gradient magnetic fields. The D value of sucrose in deuterium oxide at 30°C was 4.9 × 10(-10)m(2)/s at field gradient pulse from 5.0 × 10(-2) to 3.0 × 10(-1)T/m, separated from other carbohydrates (glucose and fructose). Good linearity (r(2)=0.9999) was obtained between sucrose (0.5-20.0 g/L) and the resonance area of target glucopyranosyl-α-C1 proton normalised to that of cellobiose C1 proton (100.0 g/L, as an internal standard) in 1D sliced DOSY spectrum. The DOSY-qNMR method was successfully applied to quantify sucrose in orange juice (36.1 ± 0.5 g/L), pineapple juice (53.5 ± 1.1g/L) and a sports drink (24.7 ± 0.6g/L), in good agreement with the results obtained by an F-kit method. PMID:25308635

  2. Body Composition in Premature Adrenarche by Structural MRI, 1H MRS and DXA

    PubMed Central

    Leibel, Natasha; Shen, Wei; Mao, Xiangling; Punyanitya, Mark; Gallagher, Dympna; Horlick, Mary; Shungu, Dikoma C.; Oberfield, Sharon E.

    2010-01-01

    Background Premature adrenarche (PA) is recognized to be a possible precursor of polycystic ovarian syndrome, type 2 diabetes mellitus and cardiovascular disease. Visceral adiposity and increased intramyocellular lipid (IMCL) are associated with insulin resistance and increased risk of cardiovascular disease. Aim To determine whether prepubertal girls with PA have altered visceral adiposity and/or increased muscle lipid content compared to prepubertal girls without PA using proton magnetic resonance imaging (MRI) and spectroscopy (1H MRS). Patients and Methods We performed total body dual energy X-ray absorptiometry (DXA) scans, MRI of the trunk, and MRS of the tibialis anterior muscle in the right calf on six girls with PA and eight prepubertal controls. Results Amount of visceral adipose tissue (VAT), abdominal subcutaneous adipose tissue (SAT), and VAT to SAT ratio did not differ significantly between the PA and control girls. Those with PA, however, had significantly greater IMCL than controls (p = 0.004). Conclusions This study adds further evidence that PA is not a benign condition, and future studies investigating early intervention with dietary and exercise counseling may help diminish potential risk for diabetes mellitus and/or cardiovascular disease. PMID:19554803

  3. 1H-NMR metabolite profiles of different strains of Plasmodium falciparum.

    PubMed

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

    2014-01-01

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

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

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2014-09-01

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

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

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2014-09-01

    Spin-spin coupling constants in (1)H NMR carry a wealth of structural information and offer a powerful tool for deciphering molecular structures. However, accurate ab initio or DFT calculations of spin-spin coupling constants have been very challenging and expensive. Scaling of (easy) Fermi contacts, fc, especially in the context of recent findings by Bally and Rablen (Bally, T.; Rablen, P. R. J. Org. Chem. 2011, 76, 4818), offers a framework for achieving practical evaluation of spin-spin coupling constants. We report a faster and more precise parametrization approach utilizing a new basis set for hydrogen atoms optimized in conjunction with (i) inexpensive B3LYP/6-31G(d) molecular geometries, (ii) inexpensive 4-31G basis set for carbon atoms in fc calculations, and (iii) individual parametrization for different atom types/hybridizations, not unlike a force field in molecular mechanics, but designed for the fc's. With the training set of 608 experimental constants we achieved rmsd <0.19 Hz. The methodology performs very well as we illustrate with a set of complex organic natural products, including strychnine (rmsd 0.19 Hz), morphine (rmsd 0.24 Hz), etc. This precision is achieved with much shorter computational times: accurate spin-spin coupling constants for the two conformers of strychnine were computed in parallel on two 16-core nodes of a Linux cluster within 10 min. PMID:25158224

  6. Measurement and interpretation of 15N-1H residual dipolar couplings in larger proteins.

    PubMed

    Bhattacharya, Akash; Revington, Matthew; Zuiderweg, Erik R P

    2010-03-01

    A decade ago, Dr. L.E. Kay and co-workers described an ingenious HNCO-based triple-resonance experiment from which several protein backbone RDCs can be measured simultaneously (Yang et al. (1999) [1]). They implemented a J-scaling technique in the (15)N dimension of the 3D experiment to obtain the NH RDCs. We have used this idea to carry out J-scaling in a 2D (15)N-(1)H-TROSY experiment and have found it to be an excellent method to obtain NH RDCs for larger proteins upto 70 kDa, far superior to commonly used HSQC in-phase/anti-phase and HSQC/TROSY comparisons. Here, this method, dubbed "RDC-TROSY" is discussed in detail and the limits of its utility are assessed by simulations. Prominent in the latter analysis is the evaluation of the effect of amide proton flips on the "RDC-TROSY" linewidths. The details of the technical and computational implementations of these methods for the determination of domain orientations in 45-60 kDa Hsp70 chaperone protein constructs are described. PMID:20018538

  7. 1H NMR-based metabolic profiling for evaluating poppy seed rancidity and brewing.

    PubMed

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

    2015-12-01

    Poppy seeds are widely used in household and commercial confectionery. The aim of this study was to demonstrate the application of metabolic profiling for industrial monitoring of the molecular changes which occur during minced poppy seed rancidity and brewing processes performed on raw seeds. Both forms of poppy seeds were obtained from a confectionery company. Proton nuclear magnetic resonance (1H NMR) was applied as the analytical method of choice together with multivariate statistical data analysis. Metabolic fingerprinting was applied as a bioprocess control tool to monitor rancidity with the trajectory of change and brewing progressions. Low molecular weight compounds were found to be statistically significant biomarkers of these bioprocesses. Changes in concentrations of chemical compounds were explained relative to the biochemical processes and external conditions. The obtained results provide valuable and comprehensive information to gain a better understanding of the biology of rancidity and brewing processes, while demonstrating the potential for applying NMR spectroscopy combined with multivariate data analysis tools for quality control in food industries involved in the processing of oilseeds. This precious and versatile information gives a better understanding of the biology of these processes. PMID:26540222

  8. Interplay of Nitrogen-Atom Inversion and Conformational Inversion in Enantiomerization of 1H-1-Benzazepines.

    PubMed

    Ramig, Keith; Subramaniam, Gopal; Karimi, Sasan; Szalda, David J; Ko, Allen; Lam, Aaron; Li, Jeffrey; Coaderaj, Ani; Cavdar, Leyla; Bogdan, Lukasz; Kwon, Kitae; Greer, Edyta M

    2016-04-15

    A series of 2,4-disubstituted 1H-1-benzazepines, 2a-d, 4, and 6, were studied, varying both the substituents at C2 and C4 and at the nitrogen atom. The conformational inversion (ring-flip) and nitrogen-atom inversion (N-inversion) energetics were studied by variable-temperature NMR spectroscopy and computations. The steric bulk of the nitrogen-atom substituent was found to affect both the conformation of the azepine ring and the geometry around the nitrogen atom. Also affected were the Gibbs free energy barriers for the ring-flip and the N-inversion. When the nitrogen-atom substituent was alkyl, as in 2a-c, the geometry of the nitrogen atom was nearly planar and the azepine ring was highly puckered; the result was a relatively high-energy barrier to ring-flip and a low barrier to N-inversion. Conversely, when the nitrogen-atom substituent was a hydrogen atom, as in 2d, 4, and 6, the nitrogen atom was significantly pyramidalized and the azepine ring was less puckered; the result here was a relatively high energy barrier to N-inversion and a low barrier to ring-flip. In these N-unsubstituted compounds, it was found computationally that the lowest-energy stereodynamic process was ring-flip coupled with N-inversion, as N-inversion alone had a much higher energy barrier.

  9. MUSIC in Triple-Resonance Experiments: Amino Acid Type-Selective 1H- 15N Correlations

    NASA Astrophysics Data System (ADS)

    Schubert, Mario; Smalla, Maika; Schmieder, Peter; Oschkinat, Hartmut

    1999-11-01

    Amino acid type-selective triple-resonance experiments can be of great help for the assignment of protein spectra, since they help to remove ambiguities in either manual or automated assignment procedures. Here, modified triple-resonance experiments that yield amino acid type-selective 1H-15N correlations are presented. They are based on novel coherence transfer schemes, the MUSIC pulse sequence elements, that replace the initial INEPT transfer and are selective for XH2 or XH3 (X can be 15N or 13C). The desired amino acid type is thereby selected based on the topology of the side chain. Experiments for Gly (G-HSQC); Ala (A-HSQC); Thr, Val, Ile, and Ala (TAVI-HSQC); Thr and Ala (TA-HSQC), as well as Asn and Gln (N-HSQC and QN-HSQC), are described. The new experiments are recorded as two-dimensional experiments and therefore need only small amounts of spectrometer time. The performance of the experiments is demonstrated with the application to two protein domains.

  10. MUSIC in triple-resonance experiments: amino acid type-selective (1)H-(15)N correlations

    PubMed

    Schubert; Smalla; Schmieder; Oschkinat

    1999-11-01

    Amino acid type-selective triple-resonance experiments can be of great help for the assignment of protein spectra, since they help to remove ambiguities in either manual or automated assignment procedures. Here, modified triple-resonance experiments that yield amino acid type-selective (1)H-(15)N correlations are presented. They are based on novel coherence transfer schemes, the MUSIC pulse sequence elements, that replace the initial INEPT transfer and are selective for XH(2) or XH(3) (X can be (15)N or (13)C). The desired amino acid type is thereby selected based on the topology of the side chain. Experiments for Gly (G-HSQC); Ala (A-HSQC); Thr, Val, Ile, and Ala (TAVI-HSQC); Thr and Ala (TA-HSQC), as well as Asn and Gln (N-HSQC and QN-HSQC), are described. The new experiments are recorded as two-dimensional experiments and therefore need only small amounts of spectrometer time. The performance of the experiments is demonstrated with the application to two protein domains. Copyright 1999 Academic Press.

  11. 1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

    NASA Astrophysics Data System (ADS)

    Ruggiero, P.; Interesse, F. S.; Cassidei, L.; Sciacovelli, O.

    1980-04-01

    1H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -( CH2) n - CH3 ( n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.

  12. Use of Voigt lineshape for quantification of in vivo 1H spectra.

    PubMed

    Marshall, I; Higinbotham, J; Bruce, S; Freise, A

    1997-05-01

    Quantification of NMR visible metabolites by spectral modeling usually assumes a Lorentzian or Gaussian lineshape, despite the fact that experimental lineshapes are neither. To minimize systematic fitting errors, a mixed Lorentzian-Gaussian (Voigt) lineshape model was developed. When tested with synthetic FIDs, the Voigt lineshape model gave more accurate results (maximum error 2%) than either Lorentzian (maximum error 20%) or Gaussian models (maximum error 12%). The three lineshape models gave substantially different peak areas in an in vitro experiment, with the Voigt model having a much lower chi2 (2.1 compared with 5.2 for the Lorentzian model and 6.2 for the Gaussian model). In a group of 10 healthy volunteers, fitting of 1H spectra from cerebral white matter gave significantly different peak areas between the methods. Even when area ratios were taken, the Lorentzian model gave higher values (+5% for NAA/choline and +2% for NAA/creatine) than the Voigt lineshape model, whereas the Gaussian model gave lower values (-2% and -1%, respectively). PMID:9126938

  13. 1H NMR based metabolic profiling in Crohn's disease by random forest methodology.

    PubMed

    Fathi, Fariba; Majari-Kasmaee, Laleh; Mani-Varnosfaderani, Ahmad; Kyani, Anahita; Rostami-Nejad, Mohammad; Sohrabzadeh, Kaveh; Naderi, Nosratollah; Zali, Mohammad Reza; Rezaei-Tavirani, Mostafa; Tafazzoli, Mohsen; Arefi-Oskouie, Afsaneh

    2014-07-01

    The present study was designed to search for metabolic biomarkers and their correlation with serum zinc in Crohn's disease patients. Crohn's disease (CD) is a form of inflammatory bowel disease that may affect any part of the gastrointestinal tract and can be difficult to diagnose using the clinical tests. Thus, introduction of a novel diagnostic method would be a major step towards CD treatment. Proton nuclear magnetic resonance spectroscopy ((1)H NMR) was employed for metabolic profiling to find out which metabolites in the serum have meaningful significance in the diagnosis of CD. CD and healthy subjects were correctly classified using random forest methodology. The classification model for the external test set showed a 94% correct classification of CD and healthy subjects. The present study suggests Valine and Isoleucine as differentiating metabolites for CD diagnosis. These metabolites can be used for screening of risky samples at the early stages of CD diagnoses. Moreover, a robust random forest regression model with good prediction outcomes was developed for correlating serum zinc level and metabolite concentrations. The regression model showed the correlation (R(2)) and root mean square error values of 0.83 and 6.44, respectively. This model suggests valuable clues for understanding the mechanism of zinc deficiency in CD patients. PMID:24757065

  14. Topotecan dynamics, tautomerism and reactivity--1H/13C NMR and ESI MS study.

    PubMed

    Hyz, Karolina; Kawecki, Robert; Bednarek, Elzbieta; Bocian, Wojciech; Sitkowski, Jerzy; Kozerski, Lech

    2010-08-01

    Topotecan (TPT) is in clinical use as an antitumor agent, hycamtin. Because of this, it requires both biologically and chemically useful information to be available. TPT acts by binding to the covalent complex formed by nicked DNA and topoisomerase I. This has a poisonous effect since inserted into the single-strand nick and TPT inhibits its religation. We used NMR to trace TPT dynamics, tautomerism and solvolysis products in various solvents and conditions. Chemical stability was assessed in methanol and DMSO as compared to water, and the regioselectivity of the N- and O-methylation was studied using various alkylating agents. The reaction products of quaternization of the nitrogen atom and methylation of the oxygen atom were characterized by means of ESI MS, (1)H/(13)C-HMBC and -HSQCAD NMR. We have focused on the NMR characterization of TPT with an anticipation that its aggregation, tumbling properties and the intramolecular dipolar interactions will be a common feature for other compounds described in this article. These features can also be useful in tracing the interactions of this class of topoisomerase I (TopoI) poisons with DNA. Moreover, the results explained shed light on the recently disclosed problem of lack of stability of TPT in the heart tissue homogenate samples using the analytical assays developed for this class of compounds carried out in the presence of methanol. PMID:20623719

  15. Inner jet kinematics and the viewing angle towards the γ-ray narrow-line Seyfert 1 galaxy 1H 0323+342

    NASA Astrophysics Data System (ADS)

    Fuhrmann, Lars; Karamanavis, Vassilis; Komossa, Stefanie; Angelakis, Emmanouil; Krichbaum, Thomas P.; Schulz, Robert; Kreikenbohm, Annika; Kadler, Matthias; Myserlis, Ioannis; Ros, Eduardo; Nestoras, Ioannis; Zensus, J. Anton

    2016-11-01

    Near-Eddington accretion rates onto low-mass black holes are thought to be a prime driver of the multi-wavelength properties of the narrow-line Seyfert 1 (NLS1) population of active galactic nuclei (AGNs). Orientation effects have repeatedly been considered as another important factor involved, but detailed studies have been hampered by the lack of measured viewing angles towards this type of AGN. Here we present multi-epoch, 15 GHz VLBA images (MOJAVE program) of the radio-loud and Fermi/LAT-detected NLS1 galaxy 1H 0323+342. These are combined with single-dish, multi-frequency radio monitoring of the source's variability, obtained with the Effelsberg 100-m and IRAM 30-m telescopes, in the course of the F-GAMMA program. The VLBA images reveal six components with apparent speeds of ∼ 1–7 c, and one quasi-stationary feature. Combining the obtained apparent jet speed (β app) and variability Doppler factor (D var) estimates together with other methods, we constrain the viewing angle θ towards 1H 0323+342 to θ ≤ 4°–13°. Using literature values of βapp and D var, we also deduce a viewing angle of ≤ 8°–9° towards another radio- and γ-ray-loud NLS1, namely SBS 0846+513.

  16. Toward an in Vivo Neurochemical Profile: Quantification of 18 Metabolites in Short-Echo-Time 1H NMR Spectra of the Rat Brain

    NASA Astrophysics Data System (ADS)

    Pfeuffer, Josef; Tkáč , Ivan; Provencher, Stephen W.; Gruetter, Rolf

    1999-11-01

    Localized in vivo1H NMR spectroscopy was performed with 2-ms echo time in the rat brain at 9.4 T. Frequency domain analysis with LCModel showed that the in vivo spectra can be explained by 18 metabolite model solution spectra and a highly structured background, which was attributed to resonances with fivefold shorter in vivo T1 than metabolites. The high spectral resolution (full width at half maximum approximately 0.025 ppm) and sensitivity (signal-to-noise ratio approximately 45 from a 63-μL volume, 512 scans) was used for the simultaneous measurement of the concentrations of metabolites previously difficult to quantify in 1H spectra. The strongly represented signals of N-acetylaspartate, glutamate, taurine, myo-inositol, creatine, phosphocreatine, glutamine, and lactate were quantified with Cramér-Rao lower bounds below 4%. Choline groups, phosphorylethanolamine, glucose, glutathione, γ-aminobutyric acid, N-acetylaspartylglutamate, and alanine were below 13%, whereas aspartate and scyllo-inositol were below 22%. Intra-assay variation was assessed from a time series of 3-min spectra, and the coefficient of variation was similar to the calculated Cramér-Rao lower bounds. Interassay variation was determined from 31 pooled spectra, and the coefficient of variation for total creatine was 7%. Tissue concentrations were found to be in very good agreement with neurochemical data from the literature.

  17. Vibrational and structural observations upon 3-((1H-benzo[d]imidazol-1-yl)methyl)naphthalen-2-ol from spectral and DFT computing approaches

    NASA Astrophysics Data System (ADS)

    Jone Pradeepa, S.; Tamilvendan, D.; Susai Boobalan, Maria; Sundaraganesan, N.

    2016-05-01

    An aggregate of experimental and computational study on synthesis, molecular structure, vibrational, electronic, nuclear magnetic resonance spectra, electronic structure, NLO activity and thermochemical characterization has been investigated for 3-((1H-benzo[d]imidazol-1-yl)methyl) naphthalen-2-ol (BDMN). The perspective on structural analysis includes the examination of equilibrium geometry, Natural Bond Orbital analysis (NBO), molecular electrostatic potential (MEP) analysis and frontier molecular orbital calculation. Similarly the following spectral analysis such as vibrational (FT-IR and FT-Raman), electronic (UV-Vis) and NMR (1H and 13C) has been interpreted. The FT-IR, FT-Raman spectrum were recorded in the frequency range of 4000-400 cm-1 and 4000-50 cm-1 respectively. A complete potential energy distribution (PED) was achieved to interpret the normal modes by comparing the experimental and theoretical spectral data. The simulation of NMR spectrum was performed using GIAO strategy. The NLO activity of BDMN has been calibrated using hyperpolarizability. In addition, various thermodynamic entities were predicted against different temperatures. The entire computation was executed using appropriate model chemistries such as B3LYP/Sadlej pVTZ, B3LYP/6-311G(d,p) and PBEPBE (TDDFT)/6-311G(d,p) for the respective properties. The overall hand-in-hand analysis by using both theoretical and experimental calculation on BDMN provides interesting observations and inferences.

  18. Theoretical and experimental investigations on molecular structure of 7-Chloro-9-phenyl-2,3-dihydroacridin-4(1H)-one with cytotoxic studies

    NASA Astrophysics Data System (ADS)

    Satheeshkumar, Rajendran; Shankar, Ramasamy; Kaminsky, Werner; Kalaiselvi, Sivalingam; Padma, Viswanadha Vijaya; Rajendra Prasad, Karnam Jayarampillai

    2016-04-01

    7-Chloro-9-phenyl-2,3-dihydroacridin-4(1H)-one (3) is synthesized from 2-amino-5-chlorobenzophenone (1) and 1,2-cyclohexanedione (2) in the presence of catalyst InCl3. FT-IR, FT-Raman and FT-NMR spectra of molecule 3 have been recorded and the structure was confirmed by single crystal X-ray diffraction. CDCl3 and DMSO-d6 FT-NMR spectra and 1H and 13C NMR chemical shifts have been measured in molecule 3 and calculated at the B3LYP/6-311G (d,p) and MO6-2x/6-311G (d,p) levels of theory. Similarly calculated vibrational frequencies were found in good agreement with experimental findings. The optimized geometry of molecule 3 was compared with experimental XRD values. DFT calculations of the molecular electrostatic potential (MEP) and HOMO - LUMO frontier orbitals identified chemically active sites of molecule 3 responsible for its bioactivity. The title compound, 3 exhibits higher cytotoxicity in Human breast cancer cells (MCF-7) compared to human lung adenocarcinoma cells (A549).

  19. On radio frequency current drive in the ion cyclotron range of frequencies in DEMO and large ignited plasmas

    NASA Astrophysics Data System (ADS)

    Brambilla, Marco; Bilato, Roberto

    2015-02-01

    To explore the possibility of efficient fast wave current drive in an ignited plasma in the ion cyclotron (IC) range of frequency in spite of competition from absorption by ions, we have added to the full-wave toroidal code TORIC a set of subroutines which evaluate absorption by these particles at IC harmonic resonances, using a realistic ‘slowing-down’ distribution function, and taking into account that their Larmor radius is comparable or even larger than the fast wave wavelength. The thermalized population of α-particles is not a serious competitor for power absorption as long as their number density is compatible with maintenance of ignition. By contrast, the energetic slowing down fraction, in spite of its even greater dilution, can absorb from the waves a substantial amount of power at the cyclotron resonance and its harmonics. An extensive exploration both in frequency and in toroidal wavenumbers using the parameters of one of the European versions of DEMO shows that three frequency windows exist in which damping is nevertheless predominantly on the electrons. Designing an antenna capable of shaping the launched spectrum to optimize current drive, however, will not be straightforward. Only in a narrow range when the first IC harmonic of tritium is deep inside the plasma on the high-field side of the magnetic axis, and that of deuterium and helium is still outside on the low-field side, it appears possible to achieve a satisfactory current drive efficiency with a conventional multi-strap antenna, preferentially located in the upper part of the vessel. Exploiting the other two windows at quite low and quite high frequencies is either impossible on first principles, or will demand novel ideas in antenna design.

  20. Experimental and DFT studies on the vibrational and electronic spectra of 2-(4,5-phenyl-1H-imidazole-2-yl)-phenol

    NASA Astrophysics Data System (ADS)

    Ye, Yunfeng; Tang, Guodong; Tang, Tingting; Culnane, Lance F.; Zhao, Jianyin; Zhang, Yu

    2015-02-01

    The compound 2-(4,5-phenyl-1H-imidazole-2-yl-phenol (PIP) was synthesized, followed by structure determination by X-ray diffraction, the results of which agree well with the calculated optimized, lowest energy geometrical structure. Vibrational information was obtained by FT-IR and Raman spectroscopy which also agree well with calculations (of harmonic vibration frequencies). The calculations were carried out with density functional theory B3LYP methods using 6-311++G** and LANL2DZ basis sets. Absorption UV-Vis experiments of PIP in CH3CH2OH solution reveal three maximum peaks at 245, 292 and 317 nm, which are in agreement with calculated electronic transitions using TD-B3LYP/6-311++G** in CH3CH2OH solution, and agree to the gas-phase calculations.

  1. Comparative effect of a 1 h session of electrical muscle stimulation and walking activity on energy expenditure and substrate oxidation in obese subjects.

    PubMed

    Grosset, Jean-François; Crowe, Louis; De Vito, Giuseppe; O'Shea, Donal; Caulfield, Brian

    2013-01-01

    It has previously been shown that low-frequency neuromuscular electrical stimulation (NMES) techniques can induce increases in energy expenditure similar to those associated with exercise. This study investigated the metabolic and cardiovascular effects of a 1 h session of lower limb NMES and compared cardiovascular response with that observed during walking in nine obese subjects (three males) (age = 43.8 ± 3.0 years; body mass index (BMI) = 41.5 ± 1.8 kg/m(2)). The NMES protocol consisted of delivering a complex pulse pattern to the thigh muscles for 1 h. The walking test consisted of five 4-min bouts starting at 2 km/h with 1 km/h increments up to 6 km/h. In both tests, an open-circuit gas analyser was used to assess O(2) consumption ([Formula: see text]O(2)), CO(2) production ([Formula: see text]CO(2)), respiratory exchange ratio (RER), and heart rate (HR). Rates of fat oxidation (RFO) and carbohydrate oxidation (CHO) were estimated by indirect calorimetry. One hour of NMES significantly increased [Formula: see text]O(2), HR, RER, and mean energy expenditure compared with resting values, reaching 8.7 ± 1.3 mL·min(-2)·kg(-1) (47% of [Formula: see text]O(2peak)), 114.8 ± 7.5 bpm, 0.95, and 318.5 ± 64.3 kcal/h, respectively. CHO, but not RFO, increased during 1 h of NMES. With NMES, CHO was greater and RFO was less than at all walking speeds except 6 km/h. Lactate also increased more with NMES, to 3.5 ± 0.7 mmol versus a maximum of 1.5 ± 0.3 mmol with the walking protocol. These results suggest that NMES can be used in an obese population to induce an effective cardiovascular exercise response. In fact, the observed increase in energy expenditure induced by 1 h of NMES is clinically important and comparable with that recommended in weight management programs.

  2. Synthesis, structure, photoluminescence and antitumour activity of zinc complex based on 2-(2-(1H-benzo-[d]imidazol-2-yl)benzyl)-1H-benzo-[d]imidazole

    NASA Astrophysics Data System (ADS)

    Che, Zhijian; Wang, Shaoxiang; Liu, Shenggui; Li, Guobi; Wu, Qiting; Lin, Chunyu; Kong, Linglang; Wang, Sheng

    2015-01-01

    A new complex [Zn(bbb)Cl2]·DMF, where bbb is 2-(2-(1H-benzo[d]imidazol-2-yl)benzyl)-1H-benzo[d]imidazole, was synthesized and characterized by element analysis, 1H NMR and X-ray single crystal structure analyses. For complex: crystal system, triclinic, space group, P-1, a = 9.4661(13), b = 10.3534(14), c = 13.0025(18) Å, α = 73.477(2), β = 80.743(2), γ = 88.658(2)°, V = 1205.5(3) Å3, Z = 2. In this complex, the Zn2+ distorted tetrahedron geometry is coordinated by two nitrogen atoms from 2-(2-(1H-benzo[d]imidazol-2-yl)benzyl)-1H-benzo[d]imidazole and two Cl-. The complex emits yellow green luminescence with the maximal emission peak at 550 nm in DMF solution. The complex exhibits inhibition on the growth of Eca109 cancer cell with IC50 value of 8.9 ± 1.1 μM, which was lower than that of cisplatin (14.3 ± 1.4 μM). This complex has potential application in treatment of esophageal cancer.

  3. Evidence for a dipolar-coupled AM system in carnosine in human calf muscle from in vivo 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Schröder, Leif; Bachert, Peter

    2003-10-01

    Spin systems with residual dipolar couplings such as creatine, taurine, and lactate in skeletal muscle tissue exhibit first-order spectra in in vivo 1H NMR spectroscopy at 1.5 T because the coupled protons are represented by (nearly) symmetrized eigenfunctions. The imidazole ring protons (H2, H4) of carnosine are suspected to form also a coupled system. The ring's stiffness could enable a connectivity between these anisochronous protons with the consequence of second-order spectra at low field strength. Our purpose was to study whether this deviation from the Paschen-Back condition can be used to detect the H2-H4 coupling in localized 1D 1H NMR spectra obtained at 1.5 T (64 MHz) from the human calf in a conventional whole-body scanner. As for the hydrogen hyperfine interaction, a Breit-Rabi equation was derived to describe the transition from Zeeman to Paschen-Back regime for two dipolar-coupled protons. The ratio of the measurable coupling strength ( Sk) and the difference in resonance frequencies of the coupled spins (Δ ω) induces quantum-state mixing of various degree upon definition of an appropriate eigenbase of the coupled spin system. The corresponding Clebsch-Gordan coefficients manifest in characteristic energy corrections in the Breit-Rabi formula. These additional terms were used to define an asymmetry parameter of the line positions as a function of Sk and Δ ω. The observed frequency shifts of the resonances were found to be consistent with this parameter within the accuracy achievable in in vivo NMR spectroscopy. Thus it was possible to identify the origin of satellite peaks of H2, H4 and to describe this so far not investigated type of residual dipolar coupling in vivo.

  4. Spatially resolved solid-state 1H NMR for evaluation of gradient-composition polymeric libraries.

    PubMed

    Leisen, Johannes; Gomez, Ismael J; Roper, John A; Meredith, J Carson; Beckham, Haskell W

    2012-07-01

    Polyurethane libraries consisting of films with composition gradients of aliphatic polyisocyanate and hydroxy-terminated polyacrylate resin were characterized using methods of (1)H NMR microimaging (i.e., magnetic resonance imaging, (MRI)) and solid-state NMR. Molecular mobilities and underlying structural information were extracted as a function of the relative content of each of the two components. Routine NMR microimaging using the spin-echo sequence only allows investigations of transverse relaxation of magnetization at echo times >2 ms. A single-exponential decay was found, which is likely due to free, noncross-linked polymer chains. The mobility of these chains decreases with increasing content of the aliphatic polyisocyanate. The concept of a 1D NMR profiler is introduced as a novel modality for library screening, which allows the convenient measurement of static solid-state NMR spectra as a function of spatial location along a library sample that is repositioned in the rf coil between experiments. With this setup the complete transverse relaxation function was measured using Bloch decays and spin echoes. For all positions within the gradient-composition film, relaxation data consisted of at least three components that were attributed to a rigid highly cross-linked resin, an intermediate cross-linked but mobile constituent, and the highly mobile free polymer chains (the latter is also detectable by MRI). Analysis of this overall relaxation function measured via Bloch decays and spin echoes revealed only minor changes in the mobilities of the individual fractions. Findings with respect to the most mobile components are consistent with the results obtained by NMR microimaging. The major effect is the significant increase in the rigid-component fraction with the addition of the hydroxy-terminated polyacrylate resin. PMID:22676634

  5. (1)H NMR based metabolomic profiling revealed doxorubicin-induced systematic alterations in a rat model.

    PubMed

    Niu, Qian-Yun; Li, Zhen-Yu; Du, Guan-Hua; Qin, Xue-Mei

    2016-01-25

    Doxorubicin (DOX) is used as a chemotherapy drug with severe carditoxicity. In this study, an integrated echocardiography along with pathological examination and (1)H NMR analysis of multiple biological matrices (urine, serum, heart, and kidney) was employed to systemically assess the toxicity of DOX. Echocardiographic results showed that impaired left ventricular contractility and degenerative pathology lesions in DOX group, which were in consistent with pathology. The endogenous metabolites in the urine, serum, heart and kidney was identified by comparison with the data from the literature and databases. Multivariate analysis, including PCA and OPLS, revealed 8 metabolites in urine, including succinate, 2-ketoglutarate, citrate, hippurate, methylamine, benzoate, allantion, and acetate were the potential changed biomarkers. In serum, perturbed metabolites include elevation of leucine, β-glucose, O-acetyl-glycoprotein, creatine, lysine, glycerin, dimethylglycine, trimethylamine-N-oxide, myo-inositol, and N-acetyl-glycoprotein, together with level decreases of acetone, lipid, lactate, glutamate, phosphocholine, acetoacetate and pyruvate. For heart, DOX exposure caused decline of lipid, lactate, leucine, alanine, glutamate, choline, xanthine, glycerin, carnitine, and fumarate, together with elevation of glutamine, creatine, inosine, taurine and malate. Metabolic changes of kidney were mainly involved in the accumulation of α-glucose, lactate, phosphocholine, betaine, threonine, choline, taurine, glycine, urea, hypoxanthine, glutamate, and nicotinamide, coupled with reduction of asparagine, valine, methionine, tyrosine, lysine, alanine, leucine, ornithine, creatine, lipid, and acetate. In addition, alterations of urinary metabolites exhibited a time-dependent manner. Complementary evidences by multiple matrices revealed disturbed pathways concerning energy metabolism, fatty acids oxidation, amino acids and purine metabolism, choline metabolism, and gut microbiota

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

    USGS Publications Warehouse

    Malcolm, R.L.; Hayes, T.

    1994-01-01

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

  7. 1H-NMR analysis provides a metabolomic profile of patients with multiple sclerosis

    PubMed Central

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

    2015-01-01

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

  8. 1H NMR studies of reactions of copper complexes with human blood plasma and urine.

    PubMed

    Bligh, S W; Boyle, H A; McEwen, A B; Sadler, P J; Woodham, R H

    1992-01-22

    Reactions of the copper complexes Cu(II)Cl2, [Cu(II)(EDTA)]2-, [Cu(II)2(DIPS)4] and [Cu(I)(DMP)2]+ (where DIPS is 3,5-diisopropylsalicylate and DMP is 2,9-dimethylphenanthroline) with human blood plasma and urine have been studied by 500 MHz 1H NMR spectroscopy, and CD spectroscopy has been used to monitor the transfer of Cu(II) onto albumin in plasma. The rate of transfer of Cu(II) from [Cu(II)(EDTA)]2- onto albumin as measured by CD (T1/2 26 min, 0.5 mM Cu, 21 degrees), was similar to the rate of Cu(II) binding to amino acids and citrate, and to the rate of formation of [Ca(II)(EDTA)]2- in plasma. Reactions of Cu(II)Cl2 and [Cu(II)2(DIPS)4] in plasma followed a similar course, but were more rapid. The latter complex also appeared to give rise to the displacement of lactate from protein binding. Reactions of copper complexes in plasma therefore involve a range of low Mr ligands as well as albumin, and the ligands play a major role in determining the kinetics of the reactions. These factors, as well as the partitioning of both complexes and displaced ligands into lipoproteins, are likely to play important roles in the molecular pharmacology of copper-containing drugs. In urine, His and formate were involved in EDTA and DIPS displacement from their respective copper complexes, and peaks for free DIPS and [Ca(II)(EDTA)]2- were observed. The complex (Cu(I)(DMP)2]+ appeared to be relatively stable in both plasma and urine. PMID:1739401

  9. Classification of iron-sulfur cores in ferredoxins by 1H nuclear magnetic resonance spectroscopy.

    PubMed

    Nagayama, K; Ozaki, Y; Kyogoku, Y; Hase, T; Matsubara, H

    1983-09-01

    A 1H nuclear magnetic resonance (NMR) study was carried out on various ferredoxins which possess one of three types of iron-sulfur clusters, (2Fe-2S), (3Fe-3S), or (4Fe-4S). In the isolated form, (2Fe-2S) ferredoxins from spinach (Spinacea oleracia), pokeweed (Phytolacca americana), a blue-green alga (Spirulina platensis), and a halobacterium (Halobacterium halobium) exhibited two broad resonances common in chemical shift at the region downfield of 10 ppm. In their reduced forms, seven contact-shifted resonances appeared spread over 30 ppm. Although the positions of the contact-shifted resonances in the reduced state differed among the four, a common trend in the temperature dependence of their resonance positions was recognized. Two (4Fe-4S) ferredoxins from Bacillus stearothermophilus and Bacillus thermoproteolyticus exhibited almost indistinguishable spectral patterns in both the oxidized and reduced forms. The ferricyanide-treated ferredoxins of B. stearothermophilus and B. thermoproteolyticus showed characteristic contact-shifted resonances distinct from the spectra of the original (4Fe-4S) ferredoxins. This corresponds to the recent finding of the interconversion of (4Fe-4S) and (3Fe-3S) clusters with ferricyanide in the ferredoxin. Based on our data together with reported NMR data on other ferredoxins, contact-shift resonances of three types of clusters were tabulated. The reliability of NMR classification increases when we compare the NMR spectra of a ferredoxin with the classification standards at the two redox states. Moreover, not only the absolute values of the chemical shifts of contact-shifted resonances but also their temperature dependence give distinctive information applicable to iron core identification.

  10. Conformations of a model cyclic hexapeptide, CYIQNC: (1)H-NMR and molecular dynamics studies.

    PubMed

    Kulkarni, Ashok Kumar; Ojha, Rajendra Prasad

    2015-09-01

    Solution conformation of the cyclic hexapeptide sequence, [cyclo-S-Cys-Tyr-Ile-Gln-Asn-Cys-S] (CYIQNC) - a disulfide-linked fragment of a neurohypophyseal peptide hormone oxytocin (OT) - has been investigated by high-field one-dimensional (1D) and two-dimensional (2D) NMR spectroscopic methods and compared with the results obtained from computer simulation studies. (1)H-NMR results based on temperature dependence of amide proton chemical shifts and nuclear Overhauser effect indicate that peptide in solution populates different conformations, characterized by two fused β-turns. The segment Ile(3)-Gln(4)-Asn(5)-Cys(6) yields a preferred type-III β-turn at residues 4, 5 (HB, 3HN → 6CO), while the segment Cys(6), Cys(1)-Tyr(2)-Ile(3) exhibits inherently weaker, flexible β-turn either of type I/II'/III/half-turn at residues 1, 2 (HB, 6HN → 3CO). The computer simulation studies using a mixed protocol of distance geometry-simulated annealing followed by constrained minimization, restrained molecular dynamics, and energy minimization showed the possibility of existence of additional conformations with the hydrogen bonds, (a) 5HN → 3CO and (b) 2HN → 6CO. These results, therefore, indicate that the additional conformations obtained from both NMR and simulation studies can also be possible to the peptide. These additional conformations might have very small population in the solution and did not show their signatures in these conditions. These findings will be helpful in designing more analogs with modifications in the cyclic moiety of OT.

  11. The secondary structure of echistatin from 1H-NMR, circular-dichroism and Raman spectroscopy.

    PubMed

    Saudek, V; Atkinson, R A; Lepage, P; Pelton, J T

    1991-12-01

    Detailed biophysical studies have been carried out on echistatin, a member of the disintegrin family of small, cysteine-rich, RGD-containing proteins, isolated from the venom of the saw-scaled viper Echis carinatus. Analysis of circular-dichroism spectra indicates that, at 20 degrees C, echistatin contains no alpha-helix but contains mostly beta-turns and beta-sheet. Two isobestic points are observed as the temperature is raised, the conformational changes associated with that observed between 40 degrees C and 72 degrees C being irreversible. Raman spectra also indicate considerable beta-turn and beta-sheet (20%) structure and an absence of alpha-helical structure. Three of the four disulphide bridges are shown to be in an all-gauche conformation, while the fourth adopts a trans-gauche-gauche conformation. The 1H-NMR spectrum of echistatin has been almost fully assigned. A single conformation was observed at 27 degrees C with the four proline residues adopting only the trans conformation. A large number of backbone amide protons were found to exchange slowly, but no segments of the backbone were found to be in either alpha-helical or beta-sheet conformation. A number of turns could be characterised. An irregular beta-hairpin contains the RGD sequence in a mobile loop at its tip. Two of the four disulphide cross-links have been identified from the NMR spectra. The data presented in this paper will serve to define the structure of echistatin more closely in subsequent studies. PMID:1761037

  12. Solid-State Quantitative (1)H and (31)P MRI of Cortical Bone in Humans.

    PubMed

    Seifert, Alan C; Wehrli, Felix W

    2016-06-01

    Magnetic resonance imaging (MRI) plays a pivotal role for assessment of the musculoskeletal system. It is currently the clinical modality of choice for evaluation of soft tissues including cartilage, ligaments, tendons, muscle, and bone marrow. By comparison, the study of calcified tissue by MRI is still in its infancy. In this article, we review the potential of the modality for assessment of cortical bone properties known to be affected in degenerative bone disease, with focus on parameters related to matrix and mineral densities, and porosity, by means of emerging solid-state (1)H and (31)P MRI techniques. In contrast to soft tissues, the MRI signal in calcified tissues has very short lifetime, on the order of 100 μs to a few milliseconds, demanding customized imaging approaches that allow capture of the signal almost immediately after excitation. The technologies described are suited for quantitatively imaging human cortical bone in specimens as well as in vivo in patients on standard clinical imagers, yielding either concentrations in absolute units when measured against a reference standard, or more simply, in the form of surrogate biomarkers. The two major water fractions in cortical bone are those of collagen-bound and pore water occurring at an approximately 3:1 ratio. Collagen-bound water density provides a direct quantitative measure of osteoid density. While at an earlier stage of development, quantification of mineral phosphorus by (31)P MRI yields mineral density and, together with knowledge of matrix density, should allow quantification of the degree of bone mineralization. PMID:27048472

  13. Conformations of a model cyclic hexapeptide, CYIQNC: (1)H-NMR and molecular dynamics studies.

    PubMed

    Kulkarni, Ashok Kumar; Ojha, Rajendra Prasad

    2015-09-01

    Solution conformation of the cyclic hexapeptide sequence, [cyclo-S-Cys-Tyr-Ile-Gln-Asn-Cys-S] (CYIQNC) - a disulfide-linked fragment of a neurohypophyseal peptide hormone oxytocin (OT) - has been investigated by high-field one-dimensional (1D) and two-dimensional (2D) NMR spectroscopic methods and compared with the results obtained from computer simulation studies. (1)H-NMR results based on temperature dependence of amide proton chemical shifts and nuclear Overhauser effect indicate that peptide in solution populates different conformations, characterized by two fused β-turns. The segment Ile(3)-Gln(4)-Asn(5)-Cys(6) yields a preferred type-III β-turn at residues 4, 5 (HB, 3HN → 6CO), while the segment Cys(6), Cys(1)-Tyr(2)-Ile(3) exhibits inherently weaker, flexible β-turn either of type I/II'/III/half-turn at residues 1, 2 (HB, 6HN → 3CO). The computer simulation studies using a mixed protocol of distance geometry-simulated annealing followed by constrained minimization, restrained molecular dynamics, and energy minimization showed the possibility of existence of additional conformations with the hydrogen bonds, (a) 5HN → 3CO and (b) 2HN → 6CO. These results, therefore, indicate that the additional conformations obtained from both NMR and simulation studies can also be possible to the peptide. These additional conformations might have very small population in the solution and did not show their signatures in these conditions. These findings will be helpful in designing more analogs with modifications in the cyclic moiety of OT. PMID:25375824

  14. Impact of Adenovirus infection in host cell metabolism evaluated by (1)H-NMR spectroscopy.

    PubMed

    Silva, Ana Carina; P Teixeira, Ana; M Alves, Paula

    2016-08-10

    Adenovirus-based vectors are powerful vehicles for gene transfer applications in vaccination and gene therapy. Although highly exploited in the clinical setting, key aspects of the adenovirus biology are still not well understood, in particular the subversion of host cell metabolism during viral infection and replication. The aim of this work was to gain insights on the metabolism of two human cell lines (HEK293 and an amniocyte-derived cell line, 1G3) after infection with an adenovirus serotype 5 vector (AdV5). In order to profile metabolic alterations, we used (1)H-NMR spectroscopy, which allowed the quantification of 35 metabolites in cell culture supernatants with low sample preparation and in a relatively short time. Significant differences between both cell lines in non-infected cultures were identified, namely in glutamine and acetate metabolism, as well as by-product secretion. The main response to AdV5 infection was an increase in glucose consumption and lactate production rates. Moreover, cultures performed with or without glutamine supplementation confirmed the exhaustion of this amino acid as one of the main causes of lower AdV5 production at high cell densities (10- and 1.5-fold less specific yields in HEK293 and 1G3 cells, respectively), and highlighted different degrees of glutamine dependency of adenovirus replication in each cell line. The observed metabolic alterations associated with AdV5 infection and specificity of the host cell line can be useful for targeted bioprocess optimization. PMID:27215342

  15. Synthesis, crystal structures and theoretical calculations of new 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3,5-diphenyl-4,5-dihydro-(1H)-pyrazoles

    NASA Astrophysics Data System (ADS)

    Gökşen, Umut Salgın; Alpaslan, Yelda Bingöl; Kelekçi, Nesrin Gökhan; Işık, Şamil; Ekizoğlu, Melike

    2013-05-01

    1-[2-(5-Chloro-2-benzoxazolinone-3-yl)acetyl]-3-phenyl-5-(3-methoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5a), 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3-phenyl-5-(3,4-dimethoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5b) and 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3-(4-methylphenyl)-5-(2,3-dimethoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5c) were synthesized. The crystal and molecular structures of the compounds 5a, 5b and 5c were determined by elemental analyses, IR, 1H NMR, ESI-MS and single-crystal X-ray diffraction. DFT method with 6-31G(d,p) basis set was used to calculate the optimized geometrical parameters, vibrational frequencies and chemical shift values. The calculated vibrational frequencies and chemical shift values were compared with experimental IR and 1H NMR values. The results represented that there was a good agreement between experimental and calculated values of the compounds 5a-5c. In addition, DFT calculations of the compounds, molecular electrostatic potentials (MEPs) and frontier molecular orbitals were performed at B3LYP/6-31G(d,p) level of theory. Furthermore, compounds were tested against three Gram-positive bacteria: Staphylococcus aureus ATCC 29213 (American Type Culture Collection), methicillin resistant S. aureus (MRSA) ATCC 43300 and Enterococcus faecalis ATCC 29212; two Gram negative bacteria: Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853; and three fungi: Candida albicans ATCC 90028, Candida krusei ATCC 6258 and Candida parapsilosis ATCC 90018. In general, all of the compounds were found to be slightly active against tested microorganisms.

  16. Equilibrium 2H/ 1H fractionations in organic molecules. II: Linear alkanes, alkenes, ketones, carboxylic acids, esters, alcohols and ethers

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A., III

    2009-12-01

    Equilibrium 2H/ 1H fractionation factors (α eq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for H α in ketones ( Wang et al., 2009). The total uncertainty in reported α eq values is estimated at 10-20‰. The effects of functional groups were found to increase the value of α eq for H next to electron-donating groups, e.g. sbnd OR, sbnd OH or sbnd O(C dbnd O)R, and to decrease the value of α eq for H next to electron-withdrawing groups, e.g. sbnd (C dbnd O)R or sbnd (C dbnd O)OR. Smaller but significant functional group effects are also observed for H β and sometimes H γ. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be -90‰ to -70‰ for n-alkanes and around -100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of α eq agree well with field data for thermally mature hydrocarbons (δ 2H values between -80‰ and -110‰ relative to water). Therefore the observed δ 2H increase of individual hydrocarbons and the disappearance of the biosynthetic δ 2H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with δ 2H values that are close to equilibrium with water. In these cases, constant down-core δ 2H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.

  17. Synthesis, characterization, and crystal structure of 5,5″-Difluoro-1 H,1″ H-[3,3':3',3″-terindol]-2'(1' H)-one

    NASA Astrophysics Data System (ADS)

    Sharma, Sakshi; Banerjee, Bubun; Brahmachari, Goutam; Kant, Rajni; Gupta, Vivek K.

    2016-03-01

    The new indole derivative, 5,5''-Difluoro-1 H,1'' H-[3,3':3',3''-terindol]-2'(1' H)-one C24H15F2N3O, is synthesized in 87% yield, and its crystal structure is determined by X-ray structure analysis. The crystals are monoclinic, sp. gr. P21/ n, a = 15.4563(7), b = 10.8340(6), c = 16.4718(6) Å, β = 102.403(4)°, Z = 4. Bicyclic indole moieties form dihedral angle of 61.92(5)° with each other; the oxindole ring is twisted with respect to them at angles of 85.70(5)° and 75.62(5)°. The crystal structure is stabilized by N-H···O and C-H···O hydrogen bonds involving both the DMSO solvent molecules. In addition, one C-H···π interaction is observed.

  18. Synthesis, characterization, antimicrobial, DNA-cleavage and antioxidant activities of 3-((5-chloro-2-phenyl-1H-indol-3-ylimino)methyl)quinoline-2(1H)-thione and its metal complexes

    NASA Astrophysics Data System (ADS)

    Vivekanand, B.; Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2015-01-01

    Schiff base 3-((5-chloro-2-phenyl-1H-indol-3-ylimino)methyl)quinoline-2(1H)-thione and its Cu(II), Co(II), Ni(II), Zn(II) and Fe(III), complexes have been synthesized and characterized by elemental analysis, UV-Visible, IR, 1H NMR, 13C NMR and mass spectra, molar conductance, magnetic susceptibility, ESR and TGA data. The ligand and its metal complexes have been screened for their antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa, antifungal activity against Aspergillus niger and Aspergillus flavus in minimum inhibition concentration (MIC) by cup plate method respectively, antioxidant activity using 1,1-diphenyl-2-picryl hydrazyl (DPPH), which was compared with that of standard drugs vitamin-C and vitamin-E and DNA cleavage activity using calf-thymus DNA.

  19. (Z)-3-(1H-Indol-3-yl)-2-(3-thienyl)acrylonitrile and (Z)-3-[1-(4-tert-butylbenzyl)-1H-indol-3-yl]-2-(3-thienyl)acrylonitrile.

    PubMed

    Sonar, Vijayakumar N; Parkin, Sean; Crooks, Peter A

    2005-02-01

    (Z)-3-(1H-Indol-3-yl)-2-(3-thienyl)acrylonitrile, C15H10N2S, (I), and (Z)-3-[1-(4-tert-butylbenzyl)-1H-indol-3-yl]-2-(3-thienyl)acrylonitrile, C26H24N2S, (II), were prepared by base-catalyzed reactions of the corresponding indole-3-carboxaldehyde with thiophene-3-acetonitrile. 1H/13C NMR spectral data and X-ray crystal structures of compounds (I) and (II) are presented. The olefinic bond connecting the indole and thiophene moieties has Z geometry in both cases, and the molecules crystallize in space groups P2(1)/c and C2/c for (I) and (II), respectively. Slight thienyl ring-flip disorder (ca 5.6%) was observed and modeled for (I).

  20. Excitation of the surface flute waves in electron cyclotron frequency range by internal rotating electron beam in a coaxial waveguide

    NASA Astrophysics Data System (ADS)

    Blednov, O.; Girka, I.; Girka, V.; Pavlenko, I.; Sydora, R.

    2014-12-01

    The initial stage of interaction between a gyrating beam of electrons, which move along Larmor orbits in a narrow gap between a cylindrical plasma layer and an internal screen of a metal coaxial waveguide and electromagnetic eigen waves, is studied theoretically. These waves are extraordinary polarized ones; they propagate along the azimuthal angle across an axial external steady magnetic field in the electron cyclotron frequency range. The numerical analysis shows that the excitation process is stable enough in respect to changing plasma waveguide parameters. The wider the plasma layer, the broader the range of plasma waveguide parameters within which effective wave excitation takes place. The main influence on the excitation of these modes is performed by the applied axial magnetic field, namely: its increase leads to an increase of growth rate and a broadening of the range of the waveguide parameters within which wave excitation is effective.

  1. Method for determining molar concentrations of metabolites in complex solutions from two-dimensional 1H-13C NMR spectra.

    PubMed

    Lewis, Ian A; Schommer, Seth C; Hodis, Brendan; Robb, Kate A; Tonelli, Marco; Westler, William M; Sussman, Michael R; Markley, John L

    2007-12-15

    One-dimensional (1D) (1)H nuclear magnetic resonance (NMR) spectroscopy is used extensively for high-throughput analysis of metabolites in biological fluids and tissue extracts. Typically, such spectra are treated as multivariate statistical objects rather than as collections of quantifiable metabolites. We report here a two-dimensional (2D) (1)H-(13)C NMR strategy (fast metabolite quantification, FMQ, by NMR) for identifying and quantifying the approximately 40 most abundant metabolites in biological samples. To validate this technique, we prepared mixtures of synthetic compounds and extracts from Arabidopsis thaliana, Saccharomyces cerevisiae, and Medicago sativa. We show that accurate (technical error 2.7%) molar concentrations can be determined in 12 min using our quantitative 2D (1)H-(13)C NMR strategy. In contrast, traditional 1D (1)H NMR analysis resulted in 16.2% technical error under nearly ideal conditions. We propose FMQ by NMR as a practical alternative to 1D (1)H NMR for metabolomics studies in which 50-mg (extract dry weight) samples can be obtained. PMID:17985927

  2. The role of 1-h physical activity every day in preventing obesity in adolescents in Shandong, China.

    PubMed

    Ying-Xiu, Zhang; Jing-Yang, Zhou; Jin-Shan, Zhao; Zun-Hua, Chu

    2013-03-01

    Several studies have reported that physical inactivity and sedentary lifestyle are associated with being overweight and obese in children and adults. A new policy of 1-h physical activity (PA) every day was released by the Chinese government. The present study examined the role of 1-h PA every day in preventing obesity in adolescents in Shandong, China. A total of 29,030 students (14,578 boys and 14,452 girls) aged 10-18 years participated in this study. Height, weight, waist circumference (WC), and skinfold thickness (SFT) of all subjects were measured; body mass index (BMI) of adolescents was calculated from their height and weight, and the prevalence of overweight and obesity was obtained according to the International Obesity Task Force cutoffs. All subjects were divided into two groups. Group 1 had a PA of more than 1 h/day while group 2 had less than 1 h/day. Comparisons of BMI, WC, SFT, and prevalences of overweight and obesity between the two groups were made. The overall percentages of students in group 1 were 34.29 % in boys and 30.15 % in girls. The prevalences of overweight and obesity for both boys and girls were all significantly lower in group 1 than in group 2 in all age categories. In conclusion, 1-h PA every day has a beneficial effect in preventing obesity in adolescents in Shandong, China. These observations highlight the importance of PA in the prevention of overweight and obesity in adolescents.

  3. In vitro determination by 1H-NMR studies that bile with shorter nucleation times contain cholesterol-enriched vesicles.

    PubMed

    Sequeira, S S; Parkes, H G; Ellul, J P; Murphy, G M

    1995-06-01

    Although biliary vesicles are considered to be the primary source of cholesterol found in cholesterol gallstones, difficulties in quantitatively separating the different cholesterol transport modes in bile still remain. Proton nuclear magnetic resonance spectroscopy (1H-NMR) offers an alternative approach. Investigations were carried out on both model biles and human gallbladder bile samples: (i) to follow the effect of increasing sodium glycocholate concentrations on the 1H-NMR spectra of arachidonic acid rich-phospholipid, and cholesterol-lecithin vesicles, (ii) to compare the concentrations of total phospholipids in bile determined enzymatically with those obtained by integration of the phospholipid choline head group resonance peak, and (iii) to examine the relationship between biliary cholesterol nucleation time (NT) and the areas of the biliary lipid 1H-NMR peaks. It was found that the molecular motions of vesicle phospholipid, as determined by 1H-NMR, were restricted by saturation with cholesterol. In bile from patients with cholesterol gallstones, the reduced NMR fluidity of the phospholipid choline-head group indicated that the proportion of cholesterol-phospholipid vesicles containing more than 50% cholesterol, on a molar basis, was increased. The ratios of the N+(CH3)3 and = CH proton resonance peaks showed no overlap between samples with cholesterol gallstones and shorter NT and those with either no gallstones or pigment stones and longer NT. 1H-NMR spectroscopy indicates in a non-invasive manner those biles which are prone to cholesterol crystal formation.

  4. Method for determining molar concentrations of metabolites in complex solutions from two-dimensional 1H-13C NMR spectra.

    PubMed

    Lewis, Ian A; Schommer, Seth C; Hodis, Brendan; Robb, Kate A; Tonelli, Marco; Westler, William M; Sussman, Michael R; Markley, John L

    2007-12-15

    One-dimensional (1D) (1)H nuclear magnetic resonance (NMR) spectroscopy is used extensively for high-throughput analysis of metabolites in biological fluids and tissue extracts. Typically, such spectra are treated as multivariate statistical objects rather than as collections of quantifiable metabolites. We report here a two-dimensional (2D) (1)H-(13)C NMR strategy (fast metabolite quantification, FMQ, by NMR) for identifying and quantifying the approximately 40 most abundant metabolites in biological samples. To validate this technique, we prepared mixtures of synthetic compounds and extracts from Arabidopsis thaliana, Saccharomyces cerevisiae, and Medicago sativa. We show that accurate (technical error 2.7%) molar concentrations can be determined in 12 min using our quantitative 2D (1)H-(13)C NMR strategy. In contrast, traditional 1D (1)H NMR analysis resulted in 16.2% technical error under nearly ideal conditions. We propose FMQ by NMR as a practical alternative to 1D (1)H NMR for metabolomics studies in which 50-mg (extract dry weight) samples can be obtained.

  5. Metabolic profile of normal glucose-tolerant subjects with elevated 1-h plasma glucose values

    PubMed Central

    Pramodkumar, Thyparambil Aravindakshan; Priya, Miranda; Jebarani, Saravanan; Anjana, Ranjit Mohan; Mohan, Viswanathan; Pradeepa, Rajendra

    2016-01-01

    Aim: The aim of this study was to compare the metabolic profiles of subjects with normal glucose tolerance (NGT) with and without elevated 1-h postglucose (1HrPG) values during an oral glucose tolerance test (OGTT). Methodology: The study group comprised 996 subjects without known diabetes seen at tertiary diabetes center between 2010 and 2014. NGT was defined as fasting plasma glucose <100 mg/dl (5.5 mmol/L) and 2-h plasma glucose <140 mg/dl (7.8 mmol/L) after an 82.5 g oral glucose (equivalent to 75 g of anhydrous glucose) OGTT. Anthropometric measurements and biochemical investigations were done using standardized methods. The prevalence rate of generalized and central obesity, hypertension, dyslipidemia, and metabolic syndrome (MS) was determined among the NGT subjects stratified based on their 1HrPG values as <143 mg/dl, ≥143–<155 mg/dl, and ≥155 mg/dl, after adjusting for age, sex, body mass index (BMI), waist circumference, alcohol consumption, smoking, and family history of diabetes. Results: The mean age of the 996 NGT subjects was 48 ± 12 years and 53.5% were male. The mean glycated hemoglobin for subjects with 1HrPG <143 mg/dl was 5.5%, for those with 1HrPG ≥143–<155 mg/dl, 5.6% and for those with 1HrPG ≥155 mg/dl, 5.7%. NGT subjects with 1HrPG ≥143–<155 mg/dl and ≥155 mg/dl had significantly higher BMI, waist circumference, systolic and diastolic blood pressure, triglyceride, total cholesterol/high-density lipoprotein (HDL) ratio, triglyceride/HDL ratio, leukocyte count, and gamma glutamyl aminotransferase (P < 0.05) compared to subjects with 1HrPG <143 mg/dl. The odds ratio for MS for subjects with 1HrPG ≥143 mg/dl was 1.84 times higher compared to subjects with 1HrPG <143 mg/dl taken as the reference. Conclusion: NGT subjects with elevated 1HrPG values have a worse metabolic profile than those with normal 1HrPG during an OGTT. PMID:27730069

  6. 1H 1752 + 081: an eclipsing cataclysmic variable with a small accretion disk

    NASA Astrophysics Data System (ADS)

    Silber, Andrew D.; Remillard, Ronald A.; Horne, Keith; Bradt, Hale V.

    1994-04-01

    We announce the discovery of an eclipsing nova-like cataclysmic variable (CV) as the optical counterpart to the HEAO 1 X-ray source 1H1752 + 081. This CV has an orbital period of 1.882801 hr, a high equivalent width of H-beta, and an average mv of 16.4 out of the eclipse. A geometric model is constructed from observations of the eclipse ingress and egress in many optical bandpasses. The broad-band emission originates primarily in two regions; the disk/accretion stream 'hot spot' and a compact central component, which may be a spot on the white dwarf surface, the entire white dwarf surface or the boundary layer between the accretion disk and the white dwarf surface. Based on the durations and offsets of the two eclipses we determined the mass ratio q = 2.5 +/- 0.6 and the angle of inclination i = 77 deg +/- 2 deg. If the central component is the entire white dwarf surface the masses of the stars are M1 = 0.80 +/- 0.06 solar masses and M2 = 0.32 +/- 0.06 solar masses. The disk is faint and small (RD = 0.25 +/- 0.05 rL1, where rL1 is the distance from the primary to the L1 point), compared to other eclipsing CVs. The small disk may result from the removal of angular momentum from the accretion disk by the magnetic field of the white dwarf; this CV may be a DQ Her type with a slowly rotating white dwarf. The emission-line velocities do not show the 'Z-wave' expected from the eclipse of a Keplerian accretion disk, nor do they have the correct phasing to originate near the white dwarf. The most likely origin of the line emission is the hot spot. The secondary star is visible at wavelengths greater than or equal to 6000 A during eclipse. We estimate a spectral type approximately M6 which, together with the observed m1 = 16.94 during eclipse, results in a distance estimate of 150 +/- 27 pc.

  7. Structure and properties of bis(1-phenyl-1h-tetrazole-5-thiolate)diiron tetranitrosyl

    NASA Astrophysics Data System (ADS)

    Sanina, N. A.; Kozub, G. I.; Kondrat'eva, T. A.; Shilov, G. V.; Korchagin, D. V.; Emel'yanova, N. S.; Poleshchuk, O. Kh.; Chernyak, A. V.; Kulikov, A. V.; Mushenok, F. B.; Ovanesyan, N. S.; Aldoshin, S. M.

    2013-06-01

    New tetranitrosyl binuclear iron complex [Fe2(SС7H5N4)2(NO)4] (I) has been synthesized by interaction of aqueous solutions of anionic salts [Fе(S2O3)2(NO)2]3- and [SС7H5N4]-. The latter one was synthesized by reduction of bis-(1-phenyl-1H-tetrazole-5-yl) disulfide with hydrazine hydrate in ethanol at T = 25 °C. Molecular and crystalline structure of I was determined by X-ray analysis; the complex has binuclear structure of "μ-SCN" type with ˜4.02 Å between the iron atoms. Shortened О⋯О contacts (2.81 Å) between the NO groups of similar type are observed. Parameters of Mössbauer spectrum for I are: isomer shift δFe = 0.311(1) mm/s, quadrupole splitting ΔEQ = 1.044(1) mm/s, line width Γ = 0.267(1) mm/s at 85 K. From SQUID magnetometry data, the temperature and field dependences of the magnetic moment of I are well described in the frame of a simple model of binuclear iron complex with magnetic centers S1 = S2 = ½. In solution, binuclear structure of the complex remains, though the NO groups are non-equivalent. For solutions of I five-line hyperfine structure of spectrum (HFS) is observed, g-factor = 2.03. For polycrystals of I, no HFS was observed due to averaged exchange interaction between the electron spins of adjacent complexes. In polycrystals of I, the number of spins per one binuclear complex is <2, this being the evidence of antiferromagnetic exchange interaction of unpaired electrons of two iron atoms. The average number of spins in crystals (0.65) and solutions (0.55) are close. The maximum amount of NO generated by I in 1% dimethylsulfoxide (DMSO) aqueous solution is ˜13.8 nM, it halves in 8 min after decomposition starts, and reaches ˜3.8 nM in anaerobic conditions at Т = 25 °С, pH 7.0. This is due, according to quantum-chemical calculations, to the presence of a more stable Fesbnd NO bond in I than in its isostructural analog - nitrosyl iron complex with 1-methyltetrazole-5-yl (II).

  8. Study of Reversed Shear Alfvén Eigenmodes with Down Sweeping Frequency in HL-2A Experiment at qmin ˜ 1

    NASA Astrophysics Data System (ADS)

    Zhang, Xianmei; Chen, Wei; Yu, Limin; Sheng, Zheng-Mao; Xue, Erbing

    2016-09-01

    The reserved shear Alfvén eigenmodes (RSAEs) whose frequencies sweep down have been observed in HL-2A plasmas at qmin ˜ 1 during current ramp-up and NBI+ECRH recently. The kinetic Alfvén eigenmode code (KAEC), which is a non-perturbative kinetic/magnetohydrodynamic eigenvalue code for calculating kinetic damping of shear Alfvén eigenmodes, is used to investigate the modes according to the experimental data. It is found that the kinetic reversed shear Alfvén eigenmodes (KRSAEs) with downsweeping frequency and localized radial structure would appear, which are consistent with the observations. The theoretical analysis for the existence of the mode and the scaling of the mode width are provided. It is shown that the mode width of KRSAEs is proportional to the square root of thermal ion Larmor radius.

  9. Solid state 1H NMR studies of cell wall materials of potatoes

    NASA Astrophysics Data System (ADS)

    Tang, Huiru; Belton, Peter S.; Ng, Annie; Waldron, Keith W.; Ryden, Peter

    1999-04-01

    Cell wall materials from potatoes ( Solanum tuberosum) prepared by two different methods have been studied using NMR proton relaxation times. Spin lattice relaxation in both the rotating and laboratory frames as well as transverse relaxation have been measured over a range of temperatures and hydration levels. It was observed that the sample prepared using a DMSO extraction showed anomalous behaviour of spin lattice relaxation in the laboratory frame probably due to residual solvent in the sample. Spin lattice relaxation in the laboratory frame is the result of hydroxymethyl rotation and another unidentified high frequency motion. In the rotating frame relaxation is adequately explained by hydroxymethyl rotation alone. In neither experiment is methyl group rotation observed, calculation suggests that this is due to the low density of methyl groups in the sample. Non-freezing water in potato cell walls, α-cellulose and pectin was found about 0.2, 0.04 and 0.18 g per gram dry matter, indicating preferable hydration of pectin compared to cellulose. The effects of hydration are most noticeable in the measurements that reflect low frequency motions, particularly transverse relaxation, where both second moments and the relative intensity of signals arising from immobile material are reduced by hydration.

  10. Petrologic studies of drill cores USW-G2 and UE25b-1H, Yucca Mountain, Nevada

    SciTech Connect

    Caporuscio, F.; Vaniman, D.; Bish, D.; Broxton, D.; Arney, B.; Heiken, G.; Byers, F.; Gooley, R.; Semarge, E.

    1982-07-01

    The tuffs of the Nevada Test Site are currently under investigation as a possible deep geologic site for high-level radioactive waste disposal. This report characterizes tuff retrieved in core from two drill holes, USW-G2 and UE25b-1H, at the Yucca Mountain block. The USW-G2 drill core is from the northernmost extent of the block, whereas UE25b-1H is adjacent to an earlier drill hole, UE25a-1. The drill cores USW-G2 and UE25b-1H bottomed at 6000 and 4200 ft, respectively. Petrographic and x-ray diffraction studies of the two drill cores are presented in this report and indicate that tuffs (composed primarily of variably welded ash flows) are partially recrystallized to secondary minerals. Correlations of stratigraphy are also made with previous drill cores from Yucca Mountain.

  11. (1)H and (13)C magic-angle spinning nuclear magnetic resonance studies of the chicken eggshell.

    PubMed

    Pisklak, Dariusz Maciej; Szeleszczuk, Lukasz; Wawer, Iwona

    2012-12-19

    The chicken eggshell, a product of biomineralization, contains inorganic and organic substances whose content changes during the incubation process. Bloch-decay (BD) (1)H, (13)C, and cross-polarization (CP) (13)C nuclear magnetic resonance (NMR) spectra of chicken eggshells were acquired under magic-angle spinning (MAS). Variable contact time (13)C CP MAS NMR experiments revealed the signals of carbonyl groups from organic and inorganic compounds. In the (13)C BD NMR spectra, a single peak at 168.1 ppm was detected, whereas in the (1)H BD spectra, the signals from water and the bicarbonate ion were assigned. A simultaneous decrease of the water signal in the (1)H MAS NMR spectra and an increase of the carbonate ion signal in the (13)C CP MAS NMR spectra of eggshells collected during the incubation period indicate the substitution of calcium ions by hydrogen ions in the calcium carbonate crystalline phase during the incubation of an egg.

  12. Critical Effect of Segmental Dynamics in Polybutadiene / Clay Nanocomposites Characterized by Solid State 1H NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoliang; Zhang, Rongchun; Sun, Pingchuan; Winter, H. Henning; Xue, Gi

    2014-03-01

    The segmental dynamics of rigid, intermediate, and mobile molecular components in end-functionalized polybutadiene (PB) / organo-clay systems was characterized by fully refocused 1H NMR FID. In addition, 1H DQ NMR experiments allowed to semi- quantitatively monitor changes in segmental dynamics near the interface. Both methods suggested a critical concentration of end-functionalized polybutadiene, indicating a saturation effect for the surface-adsorbed polymer. The critical concentration depended on molecular weight of PB and PB-clay interaction. Based on the 1H NMR results, a tentative model was proposed to illustrate the evolution of the structure and segmental dynamics in PB/organo-clay nanocomposites. This work was supported by National Natural Science Foundation of China (Grants: 21174062).

  13. The application of "click chemistry" for the decoration of 2(1H)-pyrazinone scaffold: generation of templates.

    PubMed

    Kaval, Nadya; Ermolat'ev, Denis; Appukkuttan, Prasad; Dehaen, Wim; Kappe, C Oliver; Van der Eycken, Erik

    2005-01-01

    The "click chemistry" approach has been explored on the 2-(1H)-pyrazinone scaffold for the generation of pharmacologically interesting heterocyclic moieties. Huisgen 1,3-dipolar cycloaddition has been evaluated as the key step for the construction of the 1,2,3-triazole ring at the C-3 position of 2-(1H)-pyrazinones. Two different pathways have been successfully evaluated: (1) via C-C or C-O linkage of the acetylenic part to the C-3 position of the 2-(1H)-pyrazinone scaffold or (2) via azide introduction in the C-3 position. The subsequent application of "click chemistry" resulted in the formation of hitherto unknown skeletons. Microwave irradiation has successfully been applied in different steps of the sequence.

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

    PubMed

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

    2015-08-15

    This study aimed at the characterization of blends of Sacha Inchi oil (SIO) with different ratios of SO (soybean oil) and CO (corn oil) by nuclear magnetic resonance ((1)H NMR), compared with the data obtained by gas chromatography with a flame ionization detector (GC-FID). The (1)H NMR and GC-FID data from different ratios of SIO were adjusted by a second order polynomial equation. The two techniques were highly correlated (R(2) values ranged from 0.995 to 0.999), revealing that (1)H NMR is an efficient methodology for the quantification of omega-3 fatty acids in oils rich in omega-6 fatty acids or vice versa such as SO and CO and, on the other hand, can be used to quantify ω-6 in oils rich in ω-3, such as SIO. PMID:25794742

  15. Improved 1H amide resonance line narrowing in oriented sample solid-state NMR of membrane proteins in phospholipid bilayers

    NASA Astrophysics Data System (ADS)

    Lu, George J.; Park, Sang Ho; Opella, Stanley J.

    2012-07-01

    We demonstrate 1H amide resonance line widths <300 Hz in 1H/15N heteronuclear correlation (HETCOR) spectra of membrane proteins in aligned phospholipid bilayers. This represents a substantial improvement over typically observed line widths of ˜1 kHz. Furthermore, in a proton detected local field (PDLF) version of the experiment that measures heteronuclear dipolar couplings, line widths <130 Hz are observed. This dramatic line narrowing of 1H amide resonances enables many more individual signals to be resolved and assigned from uniformly 15N labeled membrane proteins in phospholipid bilayers under physiological conditions of temperature and pH. Finding that the decrease in line widths occurs only for membrane proteins that undergo fast rotational diffusion around the bilayer normal, but not immobile molecules, such as peptide single crystals, identifies a potential new direction for pulse sequence development that includes overall molecular dynamics in their design.

  16. The use of IRMS, (1)H NMR and chemical analysis to characterise Italian and imported Tunisian olive oils.

    PubMed

    Camin, Federica; Pavone, Anita; Bontempo, Luana; Wehrens, Ron; Paolini, Mauro; Faberi, Angelo; Marianella, Rosa Maria; Capitani, Donatella; Vista, Silvia; Mannina, Luisa

    2016-04-01

    Isotope Ratio Mass Spectrometry (IRMS), (1)H Nuclear Magnetic Resonance ((1)H NMR), conventional chemical analysis and chemometric elaboration were used to assess quality and to define and confirm the geographical origin of 177 Italian PDO (Protected Denomination of Origin) olive oils and 86 samples imported from Tunisia. Italian olive oils were richer in squalene and unsaturated fatty acids, whereas Tunisian olive oils showed higher δ(18)O, δ(2)H, linoleic acid, saturated fatty acids β-sitosterol, sn-1 and 3 diglyceride values. Furthermore, all the Tunisian samples imported were of poor quality, with a K232 and/or acidity values above the limits established for extra virgin olive oils. By combining isotopic composition with (1)H NMR data using a multivariate statistical approach, a statistical model able to discriminate olive oil from Italy and those imported from Tunisia was obtained, with an optimal differentiation ability arriving at around 98%.

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

    PubMed

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

    2014-08-15

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

  18. The interaction of small molecules with phospholipid membranes studied by 1H NOESY NMR under magic-angle spinning.

    PubMed

    Scheidt, Holger A; Huster, Daniel

    2008-01-01

    The interaction of small molecules with lipid membranes and the exact knowledge of their binding site and bilayer distribution is of great pharmacological importance and represents an active field of current biophysical research. Over the last decade, a highly resolved 1H solid-state NMR method has been developed that allows measuring localization and distribution of small molecules in membranes. The classical solution 1H NMR NOESY technique is applied to lipid membrane samples under magic-angle spinning (MAS) and NOESY cross-relaxation rates are determined quantitatively. These rates are proportional to the contact probability between molecular segments and therefore an ideal tool to study intermolecular interactions in membranes. Here, we review recent 1H MAS NOESY applications that were carried out to study lateral lipid organization in mixed membranes and the interaction of membranes with water, ethanol, small aromatic compounds, peptides, fluorescence labels, and lipophilic nucleosides.

  19. Investigation of electrostatic waves in the ion cyclotron range of frequencies in L-4 and ACT-1

    SciTech Connect

    Ono, Masayuki.

    1993-05-01

    Electrostatic waves in the ion cyclotron range of frequencies (ICRF) were studied in the Princeton L-4 and ACT-1 devices for approximately ten years, from 1975 to 1985. The investigation began in the L-4 linear device, looking for the parametric excitation of electrostatic ion cyclotron waves in multi-ion-species plasmas. In addition, this investigation verified multi-ion-species effects on the electrostatic ion cyclotron wave dispersion religion including the ion-ion hybrid resonance. Finite-Larmor-radius modification of the wave dispersion relation was also observed, even for ion temperatures of T[sub i] [approx] 1/40 eV. Taking advantage of the relatively high field and long device length of L-4, the existence of the cold electrostatic ion cyclotron wave (CES ICW) was verified. With the arrival of the ACT-1 toroidal device, finite-Larmor-radius (FLR) waves were studied in a relatively collisionless warm-ion hydrogen plasma. Detailed investigations of ion Bernstein waves (IBW) included the verification of mode-transformation in their launching, their wave propagation characteristics, their absorption, and the resulting ion heating. This basic physics activity played a crucial role in developing a new reactor heating concept termed ion Bernstein wave heating. Experimental research in the lower hybrid frequency range confirmed the existence of FLR effects near the lower hybrid resonance, predicted by Stix in 1965. In a neon plasma with a carefully placed phased wave exciter, the neutralized ion Bernstein wave was observed for the first time. Using a fastwave ICRF antenna, two parasitic excitation processes for IBW -- parametric instability and density-gradient-driven excitation -- were also discovered. In the concluding section of this paper, a possible application of externally launched electrostatic waves is suggested for helium ash removal from fusion reactor plasmas.

  20. Investigation of electrostatic waves in the ion cyclotron range of frequencies in L-4 and ACT-1

    SciTech Connect

    Ono, Masayuki

    1993-05-01

    Electrostatic waves in the ion cyclotron range of frequencies (ICRF) were studied in the Princeton L-4 and ACT-1 devices for approximately ten years, from 1975 to 1985. The investigation began in the L-4 linear device, looking for the parametric excitation of electrostatic ion cyclotron waves in multi-ion-species plasmas. In addition, this investigation verified multi-ion-species effects on the electrostatic ion cyclotron wave dispersion religion including the ion-ion hybrid resonance. Finite-Larmor-radius modification of the wave dispersion relation was also observed, even for ion temperatures of T{sub i} {approx} 1/40 eV. Taking advantage of the relatively high field and long device length of L-4, the existence of the cold electrostatic ion cyclotron wave (CES ICW) was verified. With the arrival of the ACT-1 toroidal device, finite-Larmor-radius (FLR) waves were studied in a relatively collisionless warm-ion hydrogen plasma. Detailed investigations of ion Bernstein waves (IBW) included the verification of mode-transformation in their launching, their wave propagation characteristics, their absorption, and the resulting ion heating. This basic physics activity played a crucial role in developing a new reactor heating concept termed ion Bernstein wave heating. Experimental research in the lower hybrid frequency range confirmed the existence of FLR effects near the lower hybrid resonance, predicted by Stix in 1965. In a neon plasma with a carefully placed phased wave exciter, the neutralized ion Bernstein wave was observed for the first time. Using a fastwave ICRF antenna, two parasitic excitation processes for IBW -- parametric instability and density-gradient-driven excitation -- were also discovered. In the concluding section of this paper, a possible application of externally launched electrostatic waves is suggested for helium ash removal from fusion reactor plasmas.

  1. Observation by flow sup 1 H NMR and dimerization kinetics and products of reactive ortho-quinodimethanes and benzocyclobutadiene

    SciTech Connect

    Fischer, D.

    1990-09-21

    The reactive o-quinodimethanes, 1,2-dimethylene-1,2-dihydronaphthalene (9) and o-xylylene (1) were observed by flow {sup 1}H NMR spectroscopy at room temperature. The {sup 1}H NMR spectrum of 9 was obtained in the absence of precursor and dimers. However, the {sup 1}H NMR spectrum of the more reactive 1, generated in a similar manner from (o-((trimethylsilyl)methyl)benzyl)trimethylammonium iodide (5.) could be obtained only in the presence of its stable (4 + 2) and (4 + 4) dimers. The dimerization kinetics of 3-methyl- (5{prime}), 3,6-dimethyl- (11), 3-isopropyl- (12), and 3,6-diisoproply-1,2-xylylene (13) in acetonitrile (CH{sub 3}CN) were studied by stopped-flow UV-visible spectroscopy. Fluoride ion induced 1,2-elimination from 2-elimination from 2-trimethylsilylbenzocyclobutenyl-1 mesylate (26) was used to generate the reactive molecule benzocyclobutadiene (1{prime}) in CD{sub 3}CN, which was observed by flow {sup 1}H NMR spectroscopy at room temperature. The {sup 1}H NMR spectrum (in CD{sub 3}CN) of 1,2-dimethylene-1,2-dihydrothiophene (1{double prime}), obtained by fluoride ion induced 1,4-elimination from 3-(trimethylammoniummethyl)-2-(trimethylsilylmethyl)thiophene iodine was observed by flow {sup 1}H NMR spectroscopy at room temperature. The dimerization rate of 1{double prime} in CH{sub 3}CN, generated in the same manner, was measured by UV-visible spectroscopy. 166 refs., 7 figs., 7 tabs.

  2. 1H NMR metabonomics of plasma lipoprotein subclasses: elucidation of metabolic clustering by self-organising maps.

    PubMed

    Suna, Teemu; Salminen, Aino; Soininen, Pasi; Laatikainen, Reino; Ingman, Petri; Mäkelä, Sanna; Savolainen, Markku J; Hannuksela, Minna L; Jauhiainen, Matti; Taskinen, Marja-Riitta; Kaski, Kimmo; Ala-Korpela, Mika

    2007-11-01

    (1)H NMR spectra of plasma are known to provide specific information on lipoprotein subclasses in the form of complex overlapping resonances. A combination of (1)H NMR and self-organising map (SOM) analysis was applied to investigate if automated characterisation of subclass-related metabolic interactions can be achieved. To reliably assess the intrinsic capability of (1)H NMR for resolving lipoprotein subclass profiles, sum spectra representing the pure lipoprotein subclass part of actual plasma were simulated with the aid of experimentally derived model signals for 11 distinct lipoprotein subclasses. Two biochemically characteristic categories of spectra, representing normolipidaemic and metabolic syndrome status, were generated with corresponding lipoprotein subclass profiles. A set of spectra representing a metabolic pathway between the two categories was also generated. The SOM analysis, based solely on the aliphatic resonances of these simulated spectra, clearly revealed the lipoprotein subclass profiles and their changes. Comparable SOM analysis in a group of 69 experimental (1)H NMR spectra of serum samples, which according to biochemical analyses represented a wide range of lipoprotein lipid concentrations, corroborated the findings based on the simulated data. Interestingly, the choline-N(CH(3))(3) region seems to provide more resolved clustering of lipoprotein subclasses in the SOM analyses than the methyl-CH(3) region commonly used for subclass quantification. The results illustrate the inherent suitability of (1)H NMR metabonomics for automated studies of lipoprotein subclass-related metabolism and demonstrate the power of SOM analysis in an extensive and representative case of (1)H NMR metabonomics.

  3. Controls on compound specific 2H/1H of leaf waxes along a North American monsoonal transect

    NASA Astrophysics Data System (ADS)

    Berke, M. A.; Tipple, B. J.; Hambach, B.; Ehleringer, J. R.

    2013-12-01

    The use of hydrogen isotope ratios of sedimentary n-alkanes from leaf waxes has become an important method for the reconstruction of paleohydrologic conditions. Ideally, the relationship between lipid 2H/1H values and source water is one-to-one. But the extent to which the 2H/1H values are altered between initial source water and lipid 2H/1H values varies by plant type and environment. Additionally, these variables may be confounded by use of varied source waters by plants in the same ecosystem. Here, we use a transect study across the arid southwestern landscape of the United States, which is heavily influenced by the North American Monsoon, to study the variability in 2H/1H values of leaf waxes in co-occurring plants from Tucson, Arizona to Salt Lake City, Utah. Perennials, including rabbit brush (Chrysothamnus nauseosus), sagebrush (Artemisia tridentata), and gambel oak (Quercus gambelii) and an annual plant, sunflower (Helianthus annuus), were chosen for their wide geographic distribution along the entire transect. Our results indicate that n-alkane distribution for each plant was similar and generally showed no relationship to environmental variables (elevation, mean annual precipitation, latitude, and temperature). However, we find evidence of n-alkane 2H/1H value relating to transect latitude, a relationship that is weaker for all samples combined than the strong individual correlation for each plant species. Further, these 2H/1H values suggest that not all plants in the monsoon region utilize monsoon-delivered precipitation. These results imply an adaptation to discontinuous spatial coverage and amount of monsoonal precipitation and suggest care must be taken when assuming consistent source water for different plants, particularly in regions with highly seasonal precipitation delivery.

  4. (1)H-detected solid-state NMR of proteins entrapped in bioinspired silica: a new tool for biomaterials characterization.

    PubMed

    Ravera, Enrico; Cerofolini, Linda; Martelli, Tommaso; Louka, Alexandra; Fragai, Marco; Luchinat, Claudio

    2016-01-01

    Proton-detection in solid-state NMR, enabled by high magnetic fields (>18 T) and fast magic angle spinning (>50 kHz), allows for the acquisition of traditional (1)H-(15)N experiments on systems that are too big to be observed in solution. Among those, proteins entrapped in a bioinspired silica matrix are an attractive target that is receiving a large share of attention. We demonstrate that (1)H-detected SSNMR provides a novel approach to the rapid assessment of structural integrity in proteins entrapped in bioinspired silica. PMID:27279168

  5. Dehydrozingerone based 1-acetyl-5-aryl-4,5-dihydro-1H-pyrazoles: Synthesis, characterization and anticancer activity

    NASA Astrophysics Data System (ADS)

    Ratković, Zoran; Muškinja, Jovana; Burmudžija, Adrijana; Ranković, Branislav; Kosanić, Marijana; Bogdanović, Goran A.; Marković, Bojana Simović; Nikolić, Aleksandar; Arsenijević, Nebojša; Đorđevic, Snežana; Vukićević, Rastko D.

    2016-04-01

    A small series of 1-acetyl-5-aryl-4,5-dihydro-1H-pyrazoles (aryl = 4-hydroxy-3-methoxyphenyl and 4-alkoxy-3-methoxyphenyl) was prepared, starting from 4-(4-hydroxy-3-methoxyphenyl)-3-buten-2-one, dehydrozingerone, and its alkyl derivatives. Their in vitro cytotoxic activity against some cancer cell lines was tested, showing significant anticancer activity. All the new compounds were well characterized by IR, 1H, 13C NMR and ESI-MS spectroscopy and physical data, whereas structures of two of them were determined by single crystal X-ray analysis.

  6. Interaction of antiaggregant molecule ajoene with membranes. An ESR and 1H, 2H, 31P-NMR study.

    PubMed

    Debouzy, J C; Neumann, J M; Hervé, M; Daveloose, D; Viret, J; Apitz-Castro, R

    1989-01-01

    The structure of ajoene, a molecule extracted from garlic, has been studied by 1H-NMR and its interaction with model membranes by 1H-, 2H-, 31-P-NMR and ESR experiments. This study clearly shows that the ajoene molecule is located deep in the layer and is close to the interlayer medium. Moreover while NMR experiments show that the membrane structure is only slightly affected by the presence of ajoene, ESR experiments reveal significant modifications in phospholipid dynamics. This interaction, observed before with the phenothiazine derivative, promazine, results in an increase of the membrane fluidity in its hydrophobic part and could be related to clinical properties of ajoene.

  7. 1H-detected solid-state NMR of proteins entrapped in bioinspired silica: a new tool for biomaterials characterization

    NASA Astrophysics Data System (ADS)

    Ravera, Enrico; Cerofolini, Linda; Martelli, Tommaso; Louka, Alexandra; Fragai, Marco; Luchinat, Claudio

    2016-06-01

    Proton-detection in solid-state NMR, enabled by high magnetic fields (>18 T) and fast magic angle spinning (>50 kHz), allows for the acquisition of traditional 1H-15N experiments on systems that are too big to be observed in solution. Among those, proteins entrapped in a bioinspired silica matrix are an attractive target that is receiving a large share of attention. We demonstrate that 1H-detected SSNMR provides a novel approach to the rapid assessment of structural integrity in proteins entrapped in bioinspired silica.

  8. Characterization of nitrogen compound types in shale oils using /sup 1/H NMR and high resolution mass spectral analyses

    SciTech Connect

    Thompson, L.F.; Netzel, D.A.

    1984-12-01

    The /sup 1/H nuclear magnetic resonance (NMR) spectra were obtained for nitrogen compound-type fractions from a Geokinetics shale oil distillate and a Caribou intermediately refined oil obtained during catalytic hydroprocessing of the Geokinetics distillate. These fractions were generated using alumina and silica chromatography. The NMR spectra of the fractions were analyzed for hydrogen types and for individual compounds and the results compared with mass spectral data. The observed differences in resonance intensities in the /sup 1/H NMR spectra of the nitrogen fractions from the distillate and intermediately refined oil are also discussed in relationship to hydroprocessing. 17 refs., 17 figs., 5 tabs.

  9. 1H-detected solid-state NMR of proteins entrapped in bioinspired silica: a new tool for biomaterials characterization

    PubMed Central

    Ravera, Enrico; Cerofolini, Linda; Martelli, Tommaso; Louka, Alexandra; Fragai, Marco; Luchinat, Claudio

    2016-01-01

    Proton-detection in solid-state NMR, enabled by high magnetic fields (>18 T) and fast magic angle spinning (>50 kHz), allows for the acquisition of traditional 1H-15N experiments on systems that are too big to be observed in solution. Among those, proteins entrapped in a bioinspired silica matrix are an attractive target that is receiving a large share of attention. We demonstrate that 1H-detected SSNMR provides a novel approach to the rapid assessment of structural integrity in proteins entrapped in bioinspired silica. PMID:27279168

  10. A general Pd/Cu-catalyzed C-H heteroarylation of 3-bromoquinolin-2(1H)-ones.

    PubMed

    Bruneau, Alexandre; Brion, Jean-Daniel; Messaoudi, Samir; Alami, Mouad

    2014-11-14

    3-(Heteroaryl)quinolin-2(1H)-ones were synthesized in good to excellent yields using a bimetallic catalytic system through the C-H heteroarylation strategy. Starting from 3-bromoquinolin-2(1H)-ones, various azoles have been successfully used. In all cases, the reactions take place rapidly in dioxane and efficiently proceed in the presence of a bimetallic Pd(OAc)2/CuI as the catalyst, PPh3 as the ligand and LiOtBu or KOAc as the base. PMID:25237986

  11. The "long tail" of the protein tumbling correlation function: observation by (1)H NMR relaxometry in a wide frequency and concentration range.

    PubMed

    Roos, Matthias; Hofmann, Marius; Link, Susanne; Ott, Maria; Balbach, Jochen; Rössler, Ernst; Saalwächter, Kay; Krushelnitsky, Alexey

    2015-12-01

    Inter-protein interactions in solution affect the auto-correlation function of Brownian tumbling not only in terms of a simple increase of the correlation time, they also lead to the appearance of a weak slow component ("long tail") of the correlation function due to a slowly changing local anisotropy of the microenvironment. The conventional protocol of correlation time estimation from the relaxation rate ratio R1/R2 assumes a single-component tumbling correlation function, and thus can provide incorrect results as soon as the "long tail" is of relevance. This effect, however, has been underestimated in many instances. In this work we present a detailed systematic study of the tumbling correlation function of two proteins, lysozyme and bovine serum albumin, at different concentrations and temperatures using proton field-cycling relaxometry combined with R1ρ and R2 measurements. Unlike high-field NMR relaxation methods, these techniques enable a detailed study of dynamics on a time scale longer than the normal protein tumbling correlation time and, thus, a reliable estimate of the parameters of the "long tail". In this work we analyze the concentration dependence of the intensity and correlation time of the slow component and perform simulations of high-field (15)N NMR relaxation data demonstrating the importance of taking the "long tail" in the analysis into account. PMID:26582718

  12. The "long tail" of the protein tumbling correlation function: observation by (1)H NMR relaxometry in a wide frequency and concentration range.

    PubMed

    Roos, Matthias; Hofmann, Marius; Link, Susanne; Ott, Maria; Balbach, Jochen; Rössler, Ernst; Saalwächter, Kay; Krushelnitsky, Alexey

    2015-12-01

    Inter-protein interactions in solution affect the auto-correlation function of Brownian tumbling not only in terms of a simple increase of the correlation time, they also lead to the appearance of a weak slow component ("long tail") of the correlation function due to a slowly changing local anisotropy of the microenvironment. The conventional protocol of correlation time estimation from the relaxation rate ratio R1/R2 assumes a single-component tumbling correlation function, and thus can provide incorrect results as soon as the "long tail" is of relevance. This effect, however, has been underestimated in many instances. In this work we present a detailed systematic study of the tumbling correlation function of two proteins, lysozyme and bovine serum albumin, at different concentrations and temperatures using proton field-cycling relaxometry combined with R1ρ and R2 measurements. Unlike high-field NMR relaxation methods, these techniques enable a detailed study of dynamics on a time scale longer than the normal protein tumbling correlation time and, thus, a reliable estimate of the parameters of the "long tail". In this work we analyze the concentration dependence of the intensity and correlation time of the slow component and perform simulations of high-field (15)N NMR relaxation data demonstrating the importance of taking the "long tail" in the analysis into account.

  13. Evaluation of short-TE 1H MRSI for quantification of metabolites in the prostate

    PubMed Central

    Basharat, Meer; Jafar, Maysam; deSouza, Nandita M; Payne, Geoffrey S

    2014-01-01

    Back-to-back 1H MRSI scans, using an endorectal and phased-array coil combination, were performed on 18 low-risk patients with prostate cancer at 3 T, employing TEs of 32 and 100 ms in order to compare metabolite visualization at each TE. Outer-volume suppression of lipid signals was performed using regional saturation (REST) slabs and the quantification of spectra at both TEs was achieved with the quantitation using quantum estimation (QUEST) routine. Metabolite nulling experiments in an additional five patients found that there were negligible macromolecule background signals in prostate spectra at TE = 32 ms. Metabolite visibility was judged using the criterion Cramér–Rao lower bound (CRLB)/amplitude < 20%, and metabolite concentrations were corrected for relaxation effects and referenced to the data acquired in corresponding water-unsuppressed MRSI scans. For the first time, the prostate metabolites spermine and myo-inositol were quantified individually in vivo, together with citrate, choline and creatine. All five metabolite visibilities were higher in TE = 32 ms MRSI than in TE = 100 ms MRSI. At TE = 32 ms, citrate was visible in 99.0% of lipid-free spectra, whereas, at TE = 100 ms, no metabolite simulation of citrate matched the in vivo peaks. Spermine, choline and creatine were visualised separately in 30.4% more spectra at TE = 32 ms than at TE = 100 ms, and myo-inositol in 72.5% more spectra. T2 values were calculated for spermine (53 ± 16 ms), choline (62 ± 17 ms) and myo-inositol (90 ± 48 ms). Data from the TE = 32 ms spectra showed that the concentrations of citrate and spermine secretions were positively correlated in both the peripheral zone and central gland (R2 = 0.73 and R2 = 0.43, respectively), and that the citrate content was significantly higher in the former at 64 ± 22 mm than in the latter at 32 ± 16 mm (p = 0.01). However, lipid

  14. Amine-free melanin-concentrating hormone receptor 1 antagonists: Novel 1-(1H-benzimidazol-6-yl)pyridin-2(1H)-one derivatives and design to avoid CYP3A4 time-dependent inhibition.

    PubMed

    Igawa, Hideyuki; Takahashi, Masashi; Shirasaki, Mikio; Kakegawa, Keiko; Kina, Asato; Ikoma, Minoru; Aida, Jumpei; Yasuma, Tsuneo; Okuda, Shoki; Kawata, Yayoi; Noguchi, Toshihiro; Yamamoto, Syunsuke; Fujioka, Yasushi; Kundu, Mrinalkanti; Khamrai, Uttam; Nakayama, Masaharu; Nagisa, Yasutaka; Kasai, Shizuo; Maekawa, Tsuyoshi

    2016-06-01

    Melanin-concentrating hormone (MCH) is an attractive target for antiobesity agents, and numerous drug discovery programs are dedicated to finding small-molecule MCH receptor 1 (MCHR1) antagonists. We recently reported novel pyridine-2(1H)-ones as aliphatic amine-free MCHR1 antagonists that structurally featured an imidazo[1,2-a]pyridine-based bicyclic motif. To investigate imidazopyridine variants with lower basicity and less potential to inhibit cytochrome P450 3A4 (CYP3A4), we designed pyridine-2(1H)-ones bearing various less basic bicyclic motifs. Among these, a lead compound 6a bearing a 1H-benzimidazole motif showed comparable binding affinity to MCHR1 to the corresponding imidazopyridine derivative 1. Optimization of 6a afforded a series of potent thiophene derivatives (6q-u); however, most of these were found to cause time-dependent inhibition (TDI) of CYP3A4. As bioactivation of thiophenes to form sulfoxide or epoxide species was considered to be a major cause of CYP3A4 TDI, we introduced electron withdrawing groups on the thiophene and found that a CF3 group on the ring or a Cl adjacent to the sulfur atom helped prevent CYP3A4 TDI. Consequently, 4-[(5-chlorothiophen-2-yl)methoxy]-1-(2-cyclopropyl-1-methyl-1H-benzimidazol-6-yl)pyridin-2(1H)-one (6s) was identified as a potent MCHR1 antagonist without the risk of CYP3A4 TDI, which exhibited a promising safety profile including low CYP3A4 inhibition and exerted significant antiobesity effects in diet-induced obese F344 rats. PMID:27112449

  15. Amine-free melanin-concentrating hormone receptor 1 antagonists: Novel 1-(1H-benzimidazol-6-yl)pyridin-2(1H)-one derivatives and design to avoid CYP3A4 time-dependent inhibition.

    PubMed

    Igawa, Hideyuki; Takahashi, Masashi; Shirasaki, Mikio; Kakegawa, Keiko; Kina, Asato; Ikoma, Minoru; Aida, Jumpei; Yasuma, Tsuneo; Okuda, Shoki; Kawata, Yayoi; Noguchi, Toshihiro; Yamamoto, Syunsuke; Fujioka, Yasushi; Kundu, Mrinalkanti; Khamrai, Uttam; Nakayama, Masaharu; Nagisa, Yasutaka; Kasai, Shizuo; Maekawa, Tsuyoshi

    2016-06-01

    Melanin-concentrating hormone (MCH) is an attractive target for antiobesity agents, and numerous drug discovery programs are dedicated to finding small-molecule MCH receptor 1 (MCHR1) antagonists. We recently reported novel pyridine-2(1H)-ones as aliphatic amine-free MCHR1 antagonists that structurally featured an imidazo[1,2-a]pyridine-based bicyclic motif. To investigate imidazopyridine variants with lower basicity and less potential to inhibit cytochrome P450 3A4 (CYP3A4), we designed pyridine-2(1H)-ones bearing various less basic bicyclic motifs. Among these, a lead compound 6a bearing a 1H-benzimidazole motif showed comparable binding affinity to MCHR1 to the corresponding imidazopyridine derivative 1. Optimization of 6a afforded a series of potent thiophene derivatives (6q-u); however, most of these were found to cause time-dependent inhibition (TDI) of CYP3A4. As bioactivation of thiophenes to form sulfoxide or epoxide species was considered to be a major cause of CYP3A4 TDI, we introduced electron withdrawing groups on the thiophene and found that a CF3 group on the ring or a Cl adjacent to the sulfur atom helped prevent CYP3A4 TDI. Consequently, 4-[(5-chlorothiophen-2-yl)methoxy]-1-(2-cyclopropyl-1-methyl-1H-benzimidazol-6-yl)pyridin-2(1H)-one (6s) was identified as a potent MCHR1 antagonist without the risk of CYP3A4 TDI, which exhibited a promising safety profile including low CYP3A4 inhibition and exerted significant antiobesity effects in diet-induced obese F344 rats.

  16. 26 CFR 1.1(h)-1 - Capital gains look-through rule for sales or exchanges of interests in a partnership, S...

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... exchanges of interests in a partnership, S corporation, or trust. 1.1(h)-1 Section 1.1(h)-1 Internal Revenue....1(h)-1 Capital gains look-through rule for sales or exchanges of interests in a partnership, S... transaction in which all realized gain is recognized, there shall be taken into account under section...

  17. Low-Frequency Electromagnetic Sounding for Planetary Volatiles (Invited)

    NASA Astrophysics Data System (ADS)

    Grimm, R. E.

    2013-12-01

    EM sounding is divided by loss tangent << 1 (surface-penetrating radars) and >> 1 (inductive methods). The former have high resolution and responses dominated by dielectric permittivity. They have been useful for sounding the polar caps of Mars and are very promising to image the shells of icy satellites as well as the uppermost crusts of silicate bodies. The latter have poorer resolution but greater penetration depth, responses dominated by electrical conductivity, and are the subject of this talk. Low-frequency inductive methods are further divided by comparing the source-receiver separation to the skin depth. Large separations are parametric in frequency so that the variation of EM response with frequency is translated to change in conductivity with depth. Parametric soundings can exploit natural sources from the solar wind, magnetosphere, ionosphere, or atmosphere. Small source-sensor separations are geometric with transmitter-receiver positions: both conductivity and permittivity can be recovered as a function of frequency (a dielectric spectrum), but at greater resource requirements. Subsurface liquid water is an optimal low-frequency EM target because even small quantities of dissolved ions make it a powerful electrical conductor compared to dry, resistive, silicate crusts. Water at kms or even tens of kms can be detected using the magnetotelluric, geomagnetic-depth sounding, or wave-tilt methods: these are all natural-source soundings using different combinations of field components and receiver geometries. If natural sources are weak or absent, a transmitter can be used to obtain high SNR; the time-domain EM (TDEM) method has been used extensively for terrestrial groundwater exploration. Using a ballistically deployed 200-m diameter transmitter loop, TDEM can detect groundwater at depths of several km. If landed in a region of strong local crustal magnetism, the characteristic Larmor frequency of liquid water can be detected with a TDEM-like setup using

  18. Extraction and [superscript 1]H NMR Analysis of Fats from Convenience Foods: A Laboratory Experiment for Organic Chemistry

    ERIC Educational Resources Information Center

    Hartel, Aaron M.; Moore, Amy C.

    2014-01-01

    The extraction and analysis of fats from convenience foods (crackers, cookies, chips, candies) has been developed as an experiment for a second-year undergraduate organic chemistry laboratory course. Students gravimetrically determine the fat content per serving and then perform a [superscript 1]H NMR analysis of the recovered fat to determine the…

  19. 1H and 15N nuclear magnetic resonance assignment and secondary structure of the cytotoxic ribonuclease alpha-Sarcin.

    PubMed Central

    Campos-Olivas, R.; Bruix, M.; Santoro, J.; Martínez del Pozo, A.; Lacadena, J.; Gavilanes, J. G.; Rico, M.

    1996-01-01

    The ribosome-inactivating protein alpha-Sarcin (alpha S) is a 150-residue fungal ribonuclease that, after entering sensitive cells, selectively cleaves a single phosphodiester bond in an universally conserved sequence of the major rRNA to inactivate the ribosome and thus exert its cytotoxic action. As a first step toward establishing the structure-dynamics-function relationships in this system, we have carried out the assignment of the 1H and 15N NMR spectrum of alpha S on the basis of homonuclear (1H-1H) and heteronuclear (1H-15N) two-dimensional correlation spectra of a uniformly 15N-labeled sample, and two selectively 15N-labeled (Tyr and Phe) samples, as well as a single three-dimensional experiment. The secondary structure of alpha S, as derived from the characteristic patterns of dipolar connectivities between backbone protons, conformational chemical shifts, and the protection of backbone amide protons against exchange, consists of a long N-terminal beta-hairpin, a short alpha-helical segment, and a C-terminal beta-sheet of five short strands arranged in a + 1, + 1, + 1, + 1 topology, connected by long loops in which the 13 Pro residues are located. PMID:8732769

  20. 1H and 13C NMR characterization and secondary structure of the K2 polysaccharide of Klebsiella pneumoniae strain 52145.

    PubMed

    Corsaro, Maria Michela; De Castro, Cristina; Naldi, Teresa; Parrilli, Michelangelo; Tomás, Juan M; Regué, Miguel

    2005-09-26

    The complete (1)H and (13)C NMR characterization of the tetrasaccharide repeating unit from the K2 polysaccharide of Klebsiella pneumoniae strain 52145 is reported. [chemical structure] In addition a model for its secondary structure was suggested on the basis of dynamic and molecular calculations.