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Sample records for nmr spectra spi

  1. Highlighting cavities in proteins by NMR using sulfur hexafluoride as a spy molecule.

    Science.gov (United States)

    Fusaro, Luca; Locci, Emanuela; Lai, Adolfo; Luhmer, Michel

    2010-03-11

    Cavities in proteins can be studied experimentally by using some detectable atoms, such as xenon, or molecules which act as reporter, such as a spy. The interest of sulfur hexafluoride (SF(6)) for probing hydrophobic cavities by solution-state NMR is investigated. The wheat nonspecific lipid transfer protein (LTP) was selected as a model system for this purpose. The binding of SF(6) is straightforwardly detected by the (19)F chemical shift, line width, or longitudinal relaxation time measurements, which can be carried out at low SF(6) concentration without interference from resonances of the protein. Most interestingly, the binding of SF(6) gives rise to selective intermolecular (1)H{(19)F} heteronuclear Overhauser effects (HOEs). Molecular dynamics simulation and NMR spectrum modeling show that the experimental HOESY spectra are consistent with (1)H{(19)F} HOEs arising from SF(6) in the cavity of LTP. SF(6) is found to be an advantageous alternative to hyperpolarized (129)Xe and small organic compounds for probing cavities in proteins by solution-state NMR.

  2. Structure of high-resolution NMR spectra

    CERN Document Server

    Corio, PL

    2012-01-01

    Structure of High-Resolution NMR Spectra provides the principles, theories, and mathematical and physical concepts of high-resolution nuclear magnetic resonance spectra.The book presents the elementary theory of magnetic resonance; the quantum mechanical theory of angular momentum; the general theory of steady state spectra; and multiple quantum transitions, double resonance and spin echo experiments.Physicists, chemists, and researchers will find the book a valuable reference text.

  3. Probing systems in solution by NMR using sulfur hexafluoride as a spy molecule.

    Science.gov (United States)

    Fusaro, Luca; Locci, Emanuela; Lai, Adolfo; Luhmer, Michel

    2009-05-28

    The use of SF6 as a spy molecule in solution-state NMR is investigated as an alternative to 129Xe NMR. 19F chemical shift, longitudinal relaxation time, and integral measurements, as well as intermolecular nuclear Overhauser effects, are reported for SF6 dissolved in simple deuterated solvents and/or in various solutions among which are aqueous solutions of cucurbit[6]uril (CB) and alpha-cyclodextrin (alphaCD). Both CB and alphaCD form a 1:1 inclusion complex with SF6. In a 0.2 M D2SO4-D2O solution, the affinity of CB for SF6 is 2.9x10(5) L mol(-1) at 298 K; it is the largest value ever found for the inclusion of a neutral guest into the CB cavity. It is one order of magnitude larger than in a 0.2 M Na2SO4-D2O solution, and the role of the cation is evidenced. In D2O, the affinity of alphaCD for SF6 is about 25 L mol(-1). With CB, the kinetics is slow on both the 1H and 19F chemical shift time scales, while with alphaCD fast exchange is observed. The 19F chemical shift of SF6 is much less sensitive to medium effects than the chemical shift of 129Xe. This might be a limitation if minute structural changes are to be investigated but, in the present study, turned out to be an advantage for determining the affinity of alphaCD for SF6. With CB, the 19F chemical shift of included SF6 is found to be sensitive to the nature of the cation bound at the portals. The 19F relaxation time of SF6 dissolved in deuterated solvents is dominated by the spin-rotation mechanism and is orders of magnitude shorter that the 129Xe relaxation time. It is found to be rather sensitive to the environment and was used to determine the affinity of alphaCD for SF6. The detection limit of SF6 by 19F NMR is lower than the NMR detection limit of thermally polarized 129Xe by more than three orders of magnitude. It lies in the micromolar range, and SF6 concentrations of the order of 10 microM were determined by 19F NMR signal integral measurements and used to quantify the affinity of CB for SF6

  4. Bayesian peak picking for NMR spectra.

    Science.gov (United States)

    Cheng, Yichen; Gao, Xin; Liang, Faming

    2014-02-01

    Protein structure determination is a very important topic in structural genomics, which helps people to understand varieties of biological functions such as protein-protein interactions, protein-DNA interactions and so on. Nowadays, nuclear magnetic resonance (NMR) has often been used to determine the three-dimensional structures of protein in vivo. This study aims to automate the peak picking step, the most important and tricky step in NMR structure determination. We propose to model the NMR spectrum by a mixture of bivariate Gaussian densities and use the stochastic approximation Monte Carlo algorithm as the computational tool to solve the problem. Under the Bayesian framework, the peak picking problem is casted as a variable selection problem. The proposed method can automatically distinguish true peaks from false ones without preprocessing the data. To the best of our knowledge, this is the first effort in the literature that tackles the peak picking problem for NMR spectrum data using Bayesian method.

  5. Bayesian Peak Picking for NMR Spectra

    KAUST Repository

    Cheng, Yichen

    2014-02-01

    Protein structure determination is a very important topic in structural genomics, which helps people to understand varieties of biological functions such as protein-protein interactions, protein–DNA interactions and so on. Nowadays, nuclear magnetic resonance (NMR) has often been used to determine the three-dimensional structures of protein in vivo. This study aims to automate the peak picking step, the most important and tricky step in NMR structure determination. We propose to model the NMR spectrum by a mixture of bivariate Gaussian densities and use the stochastic approximation Monte Carlo algorithm as the computational tool to solve the problem. Under the Bayesian framework, the peak picking problem is casted as a variable selection problem. The proposed method can automatically distinguish true peaks from false ones without preprocessing the data. To the best of our knowledge, this is the first effort in the literature that tackles the peak picking problem for NMR spectrum data using Bayesian method.

  6. First look at Gamma-ray background lines in the SPI Ge detector spectra

    Science.gov (United States)

    Wunderer, C. B.; Weidenspointner, G.; Cordier, B.; Diehl, R.; Jean, P.; v. Kienlin, A.; Knoedlseder, J.; Leleux, P.; Lichti, G.; Roques, J.-P.; Schanne, S.; Schoenfelder, V.; Shrader, C.; Skinner, G.; Strong, A.; Sturner, S.; Teegarden, B.; Vedrenne, G.

    2003-03-01

    ESA's INTEGRAL observatory has been launched successfully on October 17, 2002. Since November 2002, the 19 Ge detectors comprising the camera of one of its main instruments, the Spectrometer SPI, have been recording data. They cover the energy range from ˜ 20 keV to ˜ 8 MeV. The spectrometer is particularly suited to the observations of gamma-ray line emission from astrophysical objects of interest. However, since many astrophysically interesting lines have energies very close to energies of some instrumental background lines, and since some astrophysically interesting radioactive isotopes are also produced within spacecraft and instrument materials by cosmic-ray activation, a detailed study of the gamma-ray background lines seen with the SPI Ge detectors is necessary. We present the first steps taken towards understanding the line components of the gamma-ray background observed with SPI. This includes both isotope identification and preliminary studies of temporal variations. Emphasis is placed on the energy regions of particular interest to astrophysics, especially around the 60Fe and 26Al lines. Preliminary sensitivity estimates for some astrophysically interesting lines will also be presented. This work has been supported by the DLR.

  7. Causality principle in reconstruction of sparse NMR spectra

    CERN Document Server

    Mayzel, Maxim; Orekhov, Vladislav Yu

    2014-01-01

    Rapid development of sparse sampling methodology offers dramatic increase in power and efficiency of magnetic resonance techniques in medicine, chemistry, molecular structural biology, and other fields. We show that harnessing causality of the sparsely detected NMR signal is a general approach for a major improvement of the spectra quality. The work gives a theoretical framework of the method and demonstrates notable improvement of the spectra reconstructed with two state-of-the-art signal processing algorithms, compressed sensing and SIFT.

  8. Handbook of proton-NMR spectra and data index

    CERN Document Server

    Asahi Research Center Co, Ltd

    2013-01-01

    Handbook of Proton-NMR Spectra and Data: Index to Volumes 1-10 compiles four types of indexes used in charting the proton-NMR spectral database -Chemical Name Index, Molecular Formula Index, Substructure Index, and Chemical Shift Index. The Chemical Name Index compiles all chemical names in alphabetical order, followed by a spectrum number. When the desired organic compound cannot be found in the Chemical Name Index or its nomenclature is unclear, it becomes necessary to look for a compound by means of its molecular formula, hence the Molecular Formula Index. A unique notation system for repre

  9. ImatraNMR: Novel software for batch integration and analysis of quantitative NMR spectra

    Science.gov (United States)

    Mäkelä, A. V.; Heikkilä, O.; Kilpeläinen, I.; Heikkinen, S.

    2011-08-01

    Quantitative NMR spectroscopy is a useful and important tool for analysis of various mixtures. Recently, in addition of traditional quantitative 1D 1H and 13C NMR methods, a variety of pulse sequences aimed for quantitative or semiquantitative analysis have been developed. To obtain actual usable results from quantitative spectra, they must be processed and analyzed with suitable software. Currently, there are many processing packages available from spectrometer manufacturers and third party developers, and most of them are capable of analyzing and integration of quantitative spectra. However, they are mainly aimed for processing single or few spectra, and are slow and difficult to use when large numbers of spectra and signals are being analyzed, even when using pre-saved integration areas or custom scripting features. In this article, we present a novel software, ImatraNMR, designed for batch analysis of quantitative spectra. In addition to capability of analyzing large number of spectra, it provides results in text and CSV formats, allowing further data-analysis using spreadsheet programs or general analysis programs, such as Matlab. The software is written with Java, and thus it should run in any platform capable of providing Java Runtime Environment version 1.6 or newer, however, currently it has only been tested with Windows and Linux (Ubuntu 10.04). The software is free for non-commercial use, and is provided with source code upon request.

  10. NMR quadruopole spectra of PZT from first-principles

    Science.gov (United States)

    Mao, Dandan; Walter, Eric J.; Krakauer, Henry

    2006-03-01

    High performance piezoelectric materials are disordered alloys, so it can be difficult to determine the local atomic geometry. Recently, high field NMR measurements have shown great promise as a microscopic probe of ABO3 perovskite-based alloys by their ability to resolve line-splittings due to nuclear quadrupolar coupling with the electric field gradient (EFG) at the nucleus. We report first-principles LDA calculations of the EFG's in monoclinic and tetragonal Pb(Zr0.5Ti0.5)O3 systems using the linear augmented planewave (LAPW) method, and we compute NMR static powder spectra for ^91Zr, ^47Ti, and ^17O atoms as a function of applied strain. With decreasing c/a ratio PZT converts from tetragonal to monoclinic symmetry. We observe that the calculated NMR spectra show dramatic deviations with decreasing c/a from that in tetragonal P4mm well before the electric polarization begins to rotate away from the [001] direction. This indicates that NMR measurements can be a very accurate probe of local structural changes in perovskite piezoelectrics. G. L. Hoatson, D. H. Zhou, F. Fayon, D. Massiot, and R. L. Vold, Phys. Rev. B, 66, 224103 (2002).

  11. Parallel acquisition of multi-dimensional spectra in protein NMR

    Energy Technology Data Exchange (ETDEWEB)

    Kupce, Eriks [Agilent Technologies (United Kingdom); Kay, Lewis E., E-mail: kay@pound.med.utoronto.ca [University of Toronto, Departments of Molecular Genetics, Biochemistry and Chemistry (Canada)

    2012-09-15

    We introduce the use of multiple receivers applied in parallel for simultaneously recording multi-dimensional data sets of proteins in a single experiment. The utility of the approach is established through the introduction of the 2D {sup 15}N,{sup 1}H{sup N} vertical bar vertical bar {sup 13}CO HSQC experiment in which a pair of two-dimensional {sup 15}N,{sup 1}H{sup N} and {sup 15}N,{sup 13}CO spectra are recorded. The methodology is further extended to higher dimensionality via the 3D {sup 1}H{sup N} vertical bar vertical bar {sup 13}CO HNCA in which a pair of data sets recording {sup 13}C{sup {alpha}},{sup 15}N,{sup 1}H{sup N} and {sup 13}C{sup {alpha}},{sup 15}N,{sup 13}CO chemical shifts are acquired. With the anticipated increases in probe sensitivity it is expected that multiple receiver experiments will become an important approach for efficient recording of NMR data.

  12. Access to experimentally infeasible spectra by pure-shift NMR covariance

    Science.gov (United States)

    Fredi, André; Nolis, Pau; Cobas, Carlos; Parella, Teodor

    2016-09-01

    Covariance processing is a versatile processing tool to generate synthetic NMR spectral representations without the need to acquire time-consuming experimental datasets. Here we show that even experimentally prohibited NMR spectra can be reconstructed by introducing key features of a reference 1D CHn-edited spectrum into standard 2D spectra. This general procedure is illustrated with the calculation of experimentally infeasible multiplicity-edited pure-shift NMR spectra of some very popular homonuclear (ME-psCOSY and ME-psTOCSY) and heteronuclear (ME-psHSQC-TOCSY and ME-psHMBC) experiments.

  13. Total lineshape analysis of high-resolution NMR spectra powered by simulated annealing

    Science.gov (United States)

    Cheshkov, D. A.; Sinitsyn, D. O.; Sheberstov, K. F.; Chertkov, V. A.

    2016-11-01

    The novel algorithm for a total lineshape analysis of high-resolution NMR spectra has been developed. A global optimization by simulated annealing has been applied that has allowed to overcome the main trouble of common approaches which had frequently returned solutions for local minima rather than for global ones. The algorithm has been verified for the four-spin test systems ABCD, and has been successfully used for analysis of experimental NMR spectra of proline. The approach has allowed to avoid a sophisticated manual setup of initial parameters and to conduct the analysis of complicated high-resolution NMR spectra nearly automatically.

  14. The acquisition of multidimensional NMR spectra within a single scan

    Science.gov (United States)

    Frydman, Lucio; Scherf, Tali; Lupulescu, Adonis

    2002-01-01

    A scheme enabling the complete sampling of multidimensional NMR domains within a single continuous acquisition is introduced and exemplified. Provided that an analyte's signal is sufficiently strong, the acquisition time of multidimensional NMR experiments can thus be shortened by orders of magnitude. This could enable the characterization of transient events such as proteins folding, 2D NMR experiments on samples being chromatographed, bring the duration of higher dimensional experiments (e.g., 4D NMR) into the lifetime of most proteins under physiological conditions, and facilitate the incorporation of spectroscopic 2D sequences into in vivo imaging investigations. The protocol is compatible with existing multidimensional pulse sequences and can be implemented by using conventional hardware; its performance is exemplified here with a variety of homonuclear 2D NMR acquisitions. PMID:12461169

  15. On the {sup 1}H NMR spectra of 2-substituted benzoquinones

    Energy Technology Data Exchange (ETDEWEB)

    Tedeschi, E.; Rezende, D.B. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica; Arruda Campos, I.P. de, E-mail: ipdacamp@uol.com.br [Universidade Paulista, Sao Paulo, SP (Brazil). Inst. de Ciencias Exatas e Tecnologia. Programa de Pos-Graduacao em Engenharia de Producao

    2009-07-01

    The novel complete analysis of the {sup 1}H NMR spectra of six monosubstituted benzoquinones is reported herein, together with a brief but complete review of the scanty previously published data on benzoquinone and its monosubstituded derivatives. (author)

  16. NMR Spectra through the Eyes of a Student: Eye Tracking Applied to NMR Items

    Science.gov (United States)

    Topczewski, Joseph J.; Topczewski, Anna M.; Tang, Hui; Kendhammer, Lisa K.; Pienta, Norbert J.

    2017-01-01

    Nuclear magnetic resonance spectroscopy (NMR) plays a key role in introductory organic chemistry, spanning theory, concepts, and experimentation. Therefore, it is imperative that the instruction methods for NMR are both efficient and effective. By utilizing eye tracking equipment, the researchers were able to monitor how second-semester organic…

  17. NMR Spectra through the Eyes of a Student: Eye Tracking Applied to NMR Items

    Science.gov (United States)

    Topczewski, Joseph J.; Topczewski, Anna M.; Tang, Hui; Kendhammer, Lisa K.; Pienta, Norbert J.

    2017-01-01

    Nuclear magnetic resonance spectroscopy (NMR) plays a key role in introductory organic chemistry, spanning theory, concepts, and experimentation. Therefore, it is imperative that the instruction methods for NMR are both efficient and effective. By utilizing eye tracking equipment, the researchers were able to monitor how second-semester organic…

  18. Vibrational spectra, NMR and theoretical studies of the enantiomers and rotamers of alpha-cypermethrin

    Science.gov (United States)

    Jubert, Alicia H.; Alegre, María L.; Diez, Reinaldo Pis; Pomilio, Alicia B.; Szewczuk, Víctor D.

    2007-04-01

    NMR, infrared and Raman vibrational spectra of alpha-cypermethrin have been measured at room temperature. Infrared spectra were also recorded to low temperature. The spectra were analyzed by means of ab initio calculations. The conformational space of both enantiomers and some rotamers A, B and C of alpha-cypermethrin has been scanned using molecular dynamics and complemented with functional density calculations that optimize the geometry of the lowest-energy conformers of each species as obtained in the simulations. The vibrational frequencies and the 1H and 13C NMR chemical shifts were assigned using functional density calculations. The molecular electrostatic potential maps were obtained and analyzed.

  19. Quadrupolar magic angle spinning NMR spectra fitted using the Pearson IV function.

    Science.gov (United States)

    Mironenko, Roman M; Belskaya, Olga B; Talsi, Valentin P; Likholobov, Vladimir A

    2014-01-01

    The Pearson IV function was used to fit the asymmetric solid-state (27)Al NMR spectra of alumina based catalysts. A high convergence (correlation coefficient is no less than 0.997) between experimental and simulated spectra was achieved. The decomposition of the (27)Al NMR spectra of zinc/aluminum mixed oxides with different Zn/Al molar ratio revealed an increased fraction (6-9%) of pentacoordinated aluminum atoms in these oxides as compared to γ-Al2O3. As the Zn/Al ratio is raised, the fraction of [AlO6] octahedral units decreases, while the fraction of [AlO4] tetrahedra increases.

  20. Median Modified Wiener Filter for nonlinear adaptive spatial denoising of protein NMR multidimensional spectra

    KAUST Repository

    Cannistraci, Carlo Vittorio

    2015-01-26

    Denoising multidimensional NMR-spectra is a fundamental step in NMR protein structure determination. The state-of-the-art method uses wavelet-denoising, which may suffer when applied to non-stationary signals affected by Gaussian-white-noise mixed with strong impulsive artifacts, like those in multi-dimensional NMR-spectra. Regrettably, Wavelet\\'s performance depends on a combinatorial search of wavelet shapes and parameters; and multi-dimensional extension of wavelet-denoising is highly non-trivial, which hampers its application to multidimensional NMR-spectra. Here, we endorse a diverse philosophy of denoising NMR-spectra: less is more! We consider spatial filters that have only one parameter to tune: the window-size. We propose, for the first time, the 3D extension of the median-modified-Wiener-filter (MMWF), an adaptive variant of the median-filter, and also its novel variation named MMWF*. We test the proposed filters and the Wiener-filter, an adaptive variant of the mean-filter, on a benchmark set that contains 16 two-dimensional and three-dimensional NMR-spectra extracted from eight proteins. Our results demonstrate that the adaptive spatial filters significantly outperform their non-adaptive versions. The performance of the new MMWF* on 2D/3D-spectra is even better than wavelet-denoising. Noticeably, MMWF* produces stable high performance almost invariant for diverse window-size settings: this signifies a consistent advantage in the implementation of automatic pipelines for protein NMR-spectra analysis.

  1. 1H NMR spectra dataset and solid-state NMR data of cowpea (Vigna unguiculata)

    DEFF Research Database (Denmark)

    Alves Filho, Elenilson G.; Silva, Lorena M. A.; Teofilo, Elizita M.

    2017-01-01

    In this article the NMR data from chemical shifts, coupling constants, and structures of all the characterized compounds were provided, beyond a complementary PCA evaluation for the corresponding manuscript (E.G. Alves Filho, L.M.A. Silva, E.M. Teofilo, F.H. Larsen, E.S. de Brito, 2017) [3......]. In addition, a complementary assessment from solid-state NMR data was provided. For further chemometric analysis, numerical matrices from the raw 1H NMR data were made available in Microsoft Excel workbook format (.xls)....

  2. (1)H NMR spectra dataset and solid-state NMR data of cowpea (Vigna unguiculata).

    Science.gov (United States)

    Alves Filho, Elenilson G; Silva, Lorena M A; Teofilo, Elizita M; Larsen, Flemming H; de Brito, Edy S

    2017-04-01

    In this article the NMR data from chemical shifts, coupling constants, and structures of all the characterized compounds were provided, beyond a complementary PCA evaluation for the corresponding manuscript (E.G. Alves Filho, L.M.A. Silva, E.M. Teofilo, F.H. Larsen, E.S. de Brito, 2017) [3]. In addition, a complementary assessment from solid-state NMR data was provided. For further chemometric analysis, numerical matrices from the raw (1)H NMR data were made available in Microsoft Excel workbook format (.xls).

  3. Development of a method for reconstruction of crowded NMR spectra from undersampled time-domain data

    Energy Technology Data Exchange (ETDEWEB)

    Ueda, Takumi; Yoshiura, Chie; Matsumoto, Masahiko; Kofuku, Yutaka; Okude, Junya; Kondo, Keita; Shiraishi, Yutaro [The University of Tokyo, Graduate School of Pharmaceutical Sciences (Japan); Takeuchi, Koh [Japan Science and Technology Agency, Precursory Research for Embryonic Science and Technology (Japan); Shimada, Ichio, E-mail: shimada@iw-nmr.f.u-tokyo.ac.jp [The University of Tokyo, Graduate School of Pharmaceutical Sciences (Japan)

    2015-05-15

    NMR is a unique methodology for obtaining information about the conformational dynamics of proteins in heterogeneous biomolecular systems. In various NMR methods, such as transferred cross-saturation, relaxation dispersion, and paramagnetic relaxation enhancement experiments, fast determination of the signal intensity ratios in the NMR spectra with high accuracy is required for analyses of targets with low yields and stabilities. However, conventional methods for the reconstruction of spectra from undersampled time-domain data, such as linear prediction, spectroscopy with integration of frequency and time domain, and analysis of Fourier, and compressed sensing were not effective for the accurate determination of the signal intensity ratios of the crowded two-dimensional spectra of proteins. Here, we developed an NMR spectra reconstruction method, “conservation of experimental data in analysis of Fourier” (Co-ANAFOR), to reconstruct the crowded spectra from the undersampled time-domain data. The number of sampling points required for the transferred cross-saturation experiments between membrane proteins, photosystem I and cytochrome b{sub 6}f, and their ligand, plastocyanin, with Co-ANAFOR was half of that needed for linear prediction, and the peak height reduction ratios of the spectra reconstructed from truncated time-domain data by Co-ANAFOR were more accurate than those reconstructed from non-uniformly sampled data by compressed sensing.

  4. Bulk magnetization and {sup 1}H NMR spectra of magnetically heterogeneous model systems

    Energy Technology Data Exchange (ETDEWEB)

    Levin, E.M., E-mail: levin@iastate.edu [Division of Materials Sciences and Engineering, Ames Laboratory of US DOE (United States); Department of Physics and Astronomy, Iowa State University, Iowa, IA 50011-3020 (United States); Bud' ko, S.L. [Division of Materials Sciences and Engineering, Ames Laboratory of US DOE (United States); Department of Physics and Astronomy, Iowa State University, Iowa, IA 50011-3020 (United States)

    2011-10-15

    Bulk magnetization and {sup 1}H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe{sub 2}O{sub 3} nano- or micro-particles have been studied. In LAP+Fe{sub 2}O{sub 3}, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe{sub 2}O{sub 3}, due to the higher proton concentration in polystyrene and stronger proton-proton dipolar coupling, an additional broadening is observed, i.e. {sup 1}H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton-magnetic particles and proton-proton dipolar couplings. An increase of the volume magnetization by {approx}1 emu/cm{sup 3} affects the {sup 1}H NMR signal width in a way that is similar to an increase of the proton concentration by {approx}2x10{sup 22}/cm{sup 3}. {sup 1}H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems. - Highlights: > {sup 1}H NMR and magnetization allow study of dipolar interactions in magnetically heterogeneous systems. > Both the proton-proton and proton-magnetic particle dipolar interactions affect {sup 1}H NMR spectra. > {sup 1}H NMR and magnetization can be used for the accurate determination of the hydrogen concentration.

  5. Bayesian deconvolution and quantification of metabolites in complex 1D NMR spectra using BATMAN.

    Science.gov (United States)

    Hao, Jie; Liebeke, Manuel; Astle, William; De Iorio, Maria; Bundy, Jacob G; Ebbels, Timothy M D

    2014-01-01

    Data processing for 1D NMR spectra is a key bottleneck for metabolomic and other complex-mixture studies, particularly where quantitative data on individual metabolites are required. We present a protocol for automated metabolite deconvolution and quantification from complex NMR spectra by using the Bayesian automated metabolite analyzer for NMR (BATMAN) R package. BATMAN models resonances on the basis of a user-controllable set of templates, each of which specifies the chemical shifts, J-couplings and relative peak intensities for a single metabolite. Peaks are allowed to shift position slightly between spectra, and peak widths are allowed to vary by user-specified amounts. NMR signals not captured by the templates are modeled non-parametrically by using wavelets. The protocol covers setting up user template libraries, optimizing algorithmic input parameters, improving prior information on peak positions, quality control and evaluation of outputs. The outputs include relative concentration estimates for named metabolites together with associated Bayesian uncertainty estimates, as well as the fit of the remainder of the spectrum using wavelets. Graphical diagnostics allow the user to examine the quality of the fit for multiple spectra simultaneously. This approach offers a workflow to analyze large numbers of spectra and is expected to be useful in a wide range of metabolomics studies.

  6. Simultaneous acquisition of three NMR spectra in a single experiment for rapid resonance assignments in metabolomics

    Indian Academy of Sciences (India)

    Shivanand M Pudakalakatti; Abhinav Dubey; Hanudatta S Atreya

    2015-06-01

    NMR-based approach to metabolomics typically involves the collection of two-dimensional (2D) heteronuclear correlation spectra for identification and assignment of metabolites. In case of spectral overlap, a 3D spectrum becomes necessary, which is hampered by slow data acquisition for achieving sufficient resolution. We describe here a method to simultaneously acquire three spectra (one 3D and two 2D) in a single data set, which is based on a combination of different fast data acquisition techniques such as G-matrix Fourier transform (GFT) NMR spectroscopy, parallel data acquisition and non-uniform sampling. The following spectra are acquired simultaneously: (1) 13C multiplicity edited GFT (3,2)D HSQC-TOCSY, (2) 2D [1H-1H] TOCSY and (3) 2D [13C-1H] HETCOR. The spectra are obtained at high resolution and provide high-dimensional spectral information for resolving ambiguities. While the GFT spectrum has been shown previously to provide good resolution, the editing of spin systems based on their CH multiplicities further resolves the ambiguities for resonance assignments. The experiment is demonstrated on a mixture of 21 metabolites commonly observed in metabolomics. The spectra were acquired at natural abundance of 13C. This is the first application of a combination of three fast NMR methods for small molecules and opens up new avenues for high-throughput approaches for NMR-based metabolomics.

  7. NMR-based metabolic profiling of rice wines by F(2)-selective total correlation spectra.

    Science.gov (United States)

    Koda, Masanori; Furihata, Kazuo; Wei, Feifei; Miyakawa, Takuya; Tanokura, Masaru

    2012-05-16

    In this study, we performed NMR-based metabolic profiling of major rice wines (Japanese sake, Chinese Shaoxing wine, and Korean makgeolli). In the (1)H NMR spectra, the rice wines showed broad resonances in the region of about 7.9-9.0 ppm. These resonances showed many and complex correlations with approximately 0.5-4.5 ppm in the F(2)-selective TOCSY (total correlation spectroscopy) spectra, and these correlations were attributed mainly to peptides. These spectral patterns were characteristic of individual rice wines, and the combination of F(2)-selective TOCSY spectra and principal component analysis enabled us to classify the rice wine species. Furthermore, it also provided information about raw materials, namely, what type of koji (rice koji or wheat koji) was used. These spectra may be useful as a new "fingerprint" for quality control or food authentication.

  8. Factor analysis of 27Al MAS NMR spectra for identifying nanocrystalline phases in amorphous geopolymers.

    Science.gov (United States)

    Urbanova, Martina; Kobera, Libor; Brus, Jiri

    2013-11-01

    Nanostructured materials offer enhanced physicochemical properties because of the large interfacial area. Typically, geopolymers with specifically synthesized nanosized zeolites are a promising material for the sorption of pollutants. The structural characterization of these aluminosilicates, however, continues to be a challenge. To circumvent complications resulting from the amorphous character of the aluminosilicate matrix and from the low concentrations of nanosized crystallites, we have proposed a procedure based on factor analysis of (27)Al MAS NMR spectra. The capability of the proposed method was tested on geopolymers that exhibited various tendencies to crystallize (i) completely amorphous systems, (ii) X-ray amorphous systems with nanocrystalline phases, and (iii) highly crystalline systems. Although the recorded (27)Al MAS NMR spectra did not show visible differences between the amorphous systems (i) and the geopolymers with the nanocrystalline phase (ii), the applied factor analysis unambiguously distinguished these materials. The samples were separated into the well-defined clusters, and the systems with the evolving crystalline phase were identified even before any crystalline fraction was detected by X-ray powder diffraction. Reliability of the proposed procedure was verified by comparing it with (29)Si MAS NMR spectra. Factor analysis of (27)Al MAS NMR spectra thus has the ability to reveal spectroscopic features corresponding to the nanocrystalline phases. Because the measurement time of (27)Al MAS NMR spectra is significantly shorter than that of (29)Si MAS NMR data, the proposed procedure is particularly suitable for the analysis of large sets of specifically synthesized geopolymers in which the formation of the limited fractions of nanocrystalline phases is desired. Copyright © 2013 John Wiley & Sons, Ltd.

  9. Bulk magnetization and 1H NMR spectra of magnetically heterogeneous model systems

    Energy Technology Data Exchange (ETDEWEB)

    Levin, E M; Bud& #x27; ko, S L

    2011-04-28

    Bulk magnetization and ¹H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe₂O₃ nano- or micro-particles have been studied. In LAP+Fe₂O₃, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe₂O₃, due to the higher proton concentration in polystyrene and stronger proton–proton dipolar coupling, an additional broadening is observed, i.e. ¹H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton–magnetic particles and proton–proton dipolar couplings. An increase of the volume magnetization by ~1 emu/cm³ affects the ¹H NMR signal width in a way that is similar to an increase of the proton concentration by ~2×10²²/cm³. ¹H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems.

  10. Bulk magnetization and 1H NMR spectra of magnetically heterogeneous model systems

    Science.gov (United States)

    Levin, E. M.; Bud'ko, S. L.

    2011-10-01

    Bulk magnetization and 1H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe2O3 nano- or micro-particles have been studied. In LAP+Fe2O3, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe2O3, due to the higher proton concentration in polystyrene and stronger proton-proton dipolar coupling, an additional broadening is observed, i.e. 1H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton-magnetic particles and proton-proton dipolar couplings. An increase of the volume magnetization by ∼1 emu/cm3 affects the 1H NMR signal width in a way that is similar to an increase of the proton concentration by ∼2×1022/cm3. 1H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems.

  11. Data of 1H/13C NMR spectra and degree of substitution for chitosan alkyl urea

    Directory of Open Access Journals (Sweden)

    Jing Wang

    2016-06-01

    Full Text Available The data shown in this article are related to the subject of an article in Carbohydrate Polymers, entitled “Synthesis and characterization of chitosan alkyl urea” [1]. 1H NMR and 13C NMR spectra of chitosan n-octyl urea, chitosan n-dodecyl urea and chitosan cyclohexyl urea are displayed. The chemical shifts of proton and carbon of glucose skeleton in these chitosan derivatives are designated in detail. Besides, 1H NMR spectra of chitosan cyclopropyl urea, chitosan tert-butyl urea, chitosan phenyl urea and chitosan N,N-diethyl urea and the estimation of the degree of substitution are also presented. The corresponding explanations can be found in the above-mentioned article.

  12. Fully automatic assignment of small molecules' NMR spectra without relying on chemical shift predictions.

    Science.gov (United States)

    Castillo, Andrés M; Bernal, Andrés; Patiny, Luc; Wist, Julien

    2015-08-01

    We present a method for the automatic assignment of small molecules' NMR spectra. The method includes an automatic and novel self-consistent peak-picking routine that validates NMR peaks in each spectrum against peaks in the same or other spectra that are due to the same resonances. The auto-assignment routine used is based on branch-and-bound optimization and relies predominantly on integration and correlation data; chemical shift information may be included when available to fasten the search and shorten the list of viable assignments, but in most cases tested, it is not required in order to find the correct assignment. This automatic assignment method is implemented as a web-based tool that runs without any user input other than the acquired spectra. Copyright © 2015 John Wiley & Sons, Ltd.

  13. Solid-state NMR spectra of lipid-anchored proteins under magic angle spinning.

    Science.gov (United States)

    Nomura, Kaoru; Harada, Erisa; Sugase, Kenji; Shimamoto, Keiko

    2014-03-01

    Solid-state NMR is a promising tool for elucidating membrane-related biological phenomena. We achieved the measurement of high-resolution solid-state NMR spectra for a lipid-anchored protein embedded in lipid bilayers under magic angle spinning (MAS). To date, solid-state NMR measurements of lipid-anchored proteins have not been accomplished due to the difficulty in supplying sufficient amount of stable isotope labeled samples in the overexpression of lipid-anchored proteins requiring complex posttranslational modification. We designed a pseudo lipid-anchored protein in which the protein component was expressed in E. coli and attached to a chemically synthesized lipid-anchor mimic. Using two types of membranes, liposomes and bicelles, we demonstrated different types of insertion procedures for lipid-anchored protein into membranes. In the liposome sample, we were able to observe the cross-polarization and the (13)C-(13)C chemical shift correlation spectra under MAS, indicating that the liposome sample can be used to analyze molecular interactions using dipolar-based NMR experiments. In contrast, the bicelle sample showed sufficient quality of spectra through scalar-based experiments. The relaxation times and protein-membrane interaction were capable of being analyzed in the bicelle sample. These results demonstrated the applicability of two types of sample system to elucidate the roles of lipid-anchors in regulating diverse biological phenomena.

  14. Anatomising proton NMR spectra with pure shift 2D J-spectroscopy: A cautionary tale

    Science.gov (United States)

    Kiraly, Peter; Foroozandeh, Mohammadali; Nilsson, Mathias; Morris, Gareth A.

    2017-09-01

    Analysis of proton NMR spectra has been a key tool in structure determination for over 60 years. A classic tool is 2D J-spectroscopy, but common problems are the difficulty of obtaining the absorption mode lineshapes needed for accurate results, and the need for a 45° shear of the final 2D spectrum. A novel 2D NMR method is reported here that allows straightforward determination of homonuclear couplings, using a modified version of the PSYCHE method to suppress couplings in the direct dimension. The method illustrates the need for care when combining pure shift data acquisition with multiple pulse methods.

  15. Theoretical and experimental IR, Raman and NMR spectra in studying the electronic structure of 2-nitrobenzoates

    Science.gov (United States)

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

    2007-05-01

    The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-nitrobenzoic acid (2-NBA) was studied. Optimized geometrical structures of studied compounds were calculated by HF, B3PW91, B3LYP methods using 6-311++G ∗∗ basis set. The theoretical IR and NMR spectra were obtained. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-nitrobenzoic acid salts of alkali metals were also recorded. The assignment of vibrational spectra was done. Characteristic shifts of band wavenumbers and changes in band intensities along the metal series were observed. Good correlation between the wavenumbers of the vibrational bands in the IR and Raman spectra for 2-nitrobenzoates (2-NB) and ionic potential, electronegativity, atomic mass and affinity of metals were found. The chemical shifts of protons and carbons ( 1H, 13C NMR) in the series of studied alkali metal 2-nitrobenzoates were observed too. The calculated parameters were compared to experimental characteristic of studied compounds.

  16. CASD-NMR 2: robust and accurate unsupervised analysis of raw NOESY spectra and protein structure determination with UNIO

    Energy Technology Data Exchange (ETDEWEB)

    Guerry, Paul; Duong, Viet Dung; Herrmann, Torsten, E-mail: torsten.herrmann@ens-lyon.fr [Université de Lyon (UMR 5280 CNRS, Ecole Normale Supérieure de Lyon, Université Claude Bernard Lyon 1), Institut des Sciences Analytiques, Centre de RMN à très Hauts Champs (France)

    2015-08-15

    UNIO is a comprehensive software suite for protein NMR structure determination that enables full automation of all NMR data analysis steps involved—including signal identification in NMR spectra, sequence-specific backbone and side-chain resonance assignment, NOE assignment and structure calculation. Within the framework of the second round of the community-wide stringent blind NMR structure determination challenge (CASD-NMR 2), we participated in two categories of CASD-NMR 2, namely using either raw NMR spectra or unrefined NOE peak lists as input. A total of 15 resulting NMR structure bundles were submitted for 9 out of 10 blind protein targets. All submitted UNIO structures accurately coincided with the corresponding blind targets as documented by an average backbone root mean-square deviation to the reference proteins of only 1.2 Å. Also, the precision of the UNIO structure bundles was virtually identical to the ensemble of reference structures. By assessing the quality of all UNIO structures submitted to the two categories, we find throughout that only the UNIO–ATNOS/CANDID approach using raw NMR spectra consistently yielded structure bundles of high quality for direct deposition in the Protein Data Bank. In conclusion, the results obtained in CASD-NMR 2 are another vital proof for robust, accurate and unsupervised NMR data analysis by UNIO for real-world applications.

  17. PICKY: a novel SVD-based NMR spectra peak picking method.

    Science.gov (United States)

    Alipanahi, Babak; Gao, Xin; Karakoc, Emre; Donaldson, Logan; Li, Ming

    2009-06-15

    Picking peaks from experimental NMR spectra is a key unsolved problem for automated NMR protein structure determination. Such a process is a prerequisite for resonance assignment, nuclear overhauser enhancement (NOE) distance restraint assignment, and structure calculation tasks. Manual or semi-automatic peak picking, which is currently the prominent way used in NMR labs, is tedious, time consuming and costly. We introduce new ideas, including noise-level estimation, component forming and sub-division, singular value decomposition (SVD)-based peak picking and peak pruning and refinement. PICKY is developed as an automated peak picking method. Different from the previous research on peak picking, we provide a systematic study of the proposed method. PICKY is tested on 32 real 2D and 3D spectra of eight target proteins, and achieves an average of 88% recall and 74% precision. PICKY is efficient. It takes PICKY on average 15.7 s to process an NMR spectrum. More important than these numbers, PICKY actually works in practice. We feed peak lists generated by PICKY to IPASS for resonance assignment, feed IPASS assignment to SPARTA for fragments generation, and feed SPARTA fragments to FALCON for structure calculation. This results in high-resolution structures of several proteins, for example, TM1112, at 1.25 A. PICKY is available upon request. The peak lists of PICKY can be easily loaded by SPARKY to enable a better interactive strategy for rapid peak picking.

  18. Characterization of E and Z isomers in macrocyclic lactones and acyclic pheromones by NMR spectra

    Energy Technology Data Exchange (ETDEWEB)

    Mahajan, J.R.; Resck, I.S. [Brasilia Univ., DF (Brazil). Dept. de Quimica; Braz Filho, R. [Universidade Estadual do Norte Fluminense (UENF), Campos, RJ (Brazil). Dept. de Produtos Quimicos Naturais; Carvalho, M.G. de [Universidade Federal Rural do Rio de Janeiro, Seropedica, RJ (Brazil). Dept. de Quimica

    1995-12-31

    A large proportion of pheromones, isolated from a variety of insects, constitutes a big list of diversely functionalized acyclic compounds, which have been synthesized by several routes. Catalytic or chemical methods were examined for the Z to E isomerization and their efficiency checked by {sup 1} H and {sup 13} C NMR spectra. Nuclear magnetic resonance has been used to identify and characterize molecular structure of the compounds, besides chemical shifts was analysed 11 refs., 4 figs., 5 tabs.

  19. 13C high resolution solid state NMR spectra of Chinese coals

    Institute of Scientific and Technical Information of China (English)

    陈德玉; 胡建治; 叶朝辉

    1997-01-01

    Several typical exinites in China including alginite, cultinite, suberinite and bituminite are analysed by means of 13C high solution solid state CP MAS TOSS NMR spectra to determine their chemical structures and hydrocarbon potential. Thermal simulation solid products (TSSP) of hydrogen-rich coals arc studied to discuss the generation and expulsion mechanism of coal-generating hydrocarbon. The preliminary results are quite encouraging, containing useful information about genesis of coal-generating oil and gases.

  20. MetaboMiner – semi-automated identification of metabolites from 2D NMR spectra of complex biofluids

    Directory of Open Access Journals (Sweden)

    Tang Peter

    2008-11-01

    Full Text Available Abstract Background One-dimensional (1D 1H nuclear magnetic resonance (NMR spectroscopy is widely used in metabolomic studies involving biofluids and tissue extracts. There are several software packages that support compound identification and quantification via 1D 1H NMR by spectral fitting techniques. Because 1D 1H NMR spectra are characterized by extensive peak overlap or spectral congestion, two-dimensional (2D NMR, with its increased spectral resolution, could potentially improve and even automate compound identification or quantification. However, the lack of dedicated software for this purpose significantly restricts the application of 2D NMR methods to most metabolomic studies. Results We describe a standalone graphics software tool, called MetaboMiner, which can be used to automatically or semi-automatically identify metabolites in complex biofluids from 2D NMR spectra. MetaboMiner is able to handle both 1H-1H total correlation spectroscopy (TOCSY and 1H-13C heteronuclear single quantum correlation (HSQC data. It identifies compounds by comparing 2D spectral patterns in the NMR spectrum of the biofluid mixture with specially constructed libraries containing reference spectra of ~500 pure compounds. Tests using a variety of synthetic and real spectra of compound mixtures showed that MetaboMiner is able to identify >80% of detectable metabolites from good quality NMR spectra. Conclusion MetaboMiner is a freely available, easy-to-use, NMR-based metabolomics tool that facilitates automatic peak processing, rapid compound identification, and facile spectrum annotation from either 2D TOCSY or HSQC spectra. Using comprehensive reference libraries coupled with robust algorithms for peak matching and compound identification, the program greatly simplifies the process of metabolite identification in complex 2D NMR spectra.

  1. Fast acquisition of multidimensional NMR spectra of solids and mesophases using alternative sampling methods.

    Science.gov (United States)

    Lesot, Philippe; Kazimierczuk, Krzysztof; Trébosc, Julien; Amoureux, Jean-Paul; Lafon, Olivier

    2015-11-01

    Unique information about the atom-level structure and dynamics of solids and mesophases can be obtained by the use of multidimensional nuclear magnetic resonance (NMR) experiments. Nevertheless, the acquisition of these experiments often requires long acquisition times. We review here alternative sampling methods, which have been proposed to circumvent this issue in the case of solids and mesophases. Compared to the spectra of solutions, those of solids and mesophases present some specificities because they usually display lower signal-to-noise ratios, non-Lorentzian line shapes, lower spectral resolutions and wider spectral widths. We highlight herein the advantages and limitations of these alternative sampling methods. A first route to accelerate the acquisition time of multidimensional NMR spectra consists in the use of sparse sampling schemes, such as truncated, radial or random sampling ones. These sparsely sampled datasets are generally processed by reconstruction methods differing from the Discrete Fourier Transform (DFT). A host of non-DFT methods have been applied for solids and mesophases, including the G-matrix Fourier transform, the linear least-square procedures, the covariance transform, the maximum entropy and the compressed sensing. A second class of alternative sampling consists in departing from the Jeener paradigm for multidimensional NMR experiments. These non-Jeener methods include Hadamard spectroscopy as well as spatial or orientational encoding of the evolution frequencies. The increasing number of high field NMR magnets and the development of techniques to enhance NMR sensitivity will contribute to widen the use of these alternative sampling methods for the study of solids and mesophases in the coming years.

  2. Distinguishing Vaccinium species by chemical fingerprinting based on NMR spectra, validated with spectra collected in different laboratories.

    Science.gov (United States)

    Markus, Michelle A; Ferrier, Jonathan; Luchsinger, Sarah M; Yuk, Jimmy; Cuerrier, Alain; Balick, Michael J; Hicks, Joshua M; Killday, K Brian; Kirby, Christopher W; Berrue, Fabrice; Kerr, Russell G; Knagge, Kevin; Gödecke, Tanja; Ramirez, Benjamin E; Lankin, David C; Pauli, Guido F; Burton, Ian; Karakach, Tobias K; Arnason, John T; Colson, Kimberly L

    2014-06-01

    A method was developed to distinguish Vaccinium species based on leaf extracts using nuclear magnetic resonance spectroscopy. Reference spectra were measured on leaf extracts from several species, including lowbush blueberry (Vaccinium angustifolium), oval leaf huckleberry (Vaccinium ovalifolium), and cranberry (Vaccinium macrocarpon). Using principal component analysis, these leaf extracts were resolved in the scores plot. Analysis of variance statistical tests demonstrated that the three groups differ significantly on PC2, establishing that the three species can be distinguished by nuclear magnetic resonance. Soft independent modeling of class analogies models for each species also showed discrimination between species. To demonstrate the robustness of nuclear magnetic resonance spectroscopy for botanical identification, spectra of a sample of lowbush blueberry leaf extract were measured at five different sites, with different field strengths (600 versus 700 MHz), different probe types (cryogenic versus room temperature probes), different sample diameters (1.7 mm versus 5 mm), and different consoles (Avance I versus Avance III). Each laboratory independently demonstrated the linearity of their NMR measurements by acquiring a standard curve for chlorogenic acid (R(2) = 0.9782 to 0.9998). Spectra acquired on different spectrometers at different sites classifed into the expected group for the Vaccinium spp., confirming the utility of the method to distinguish Vaccinium species and demonstrating nuclear magnetic resonance fingerprinting for material validation of a natural health product. Georg Thieme Verlag KG Stuttgart · New York.

  3. Study on UV, IR and NMR Spectra of Double Hydrogen-bonded Complexes

    Institute of Scientific and Technical Information of China (English)

    ZHU Liang-Liang; TENG Qi-Wen; WU Shi

    2006-01-01

    AM1, PM3 and DFT methods were used to study on the hydrogen-bonded dimer of melamine and [1,3] dioxane-2,4,6-trione. The electronic spectra, IR and NMR spectra of some complexes were calculated with INDO/SCI, AM1 and B3LYP/6-31G(d) methods, respectively. It is demonstrated that the negative stability energy is responsible for the formation of the complexes. Stabilization energies of these complexes were altered among the variations of electric property and steric effects of the monomers. HOMO-LUMO energy gaps were shrunk and the blue-shift of absorptions in the electronic spectra occurred. The vibrations of N-H bonds and chemical shifts of the protons changed with the formation of hydrogen bonds.

  4. Exploring the use of Generalized Indirect Covariance to reconstruct pure shift NMR spectra: Current Pros and Cons

    Science.gov (United States)

    Fredi, André; Nolis, Pau; Cobas, Carlos; Martin, Gary E.; Parella, Teodor

    2016-05-01

    The current Pros and Cons of a processing protocol to generate pure chemical shift NMR spectra using Generalized Indirect Covariance are presented and discussed. The transformation of any standard 2D homonuclear and heteronuclear spectrum to its pure shift counterpart by using a reference DIAG spectrum is described. Reconstructed pure shift NMR spectra of NOESY, HSQC, HSQC-TOCSY and HSQMBC experiments are reported for the target molecule strychnine.

  5. Exploring the use of Generalized Indirect Covariance to reconstruct pure shift NMR spectra: Current Pros and Cons.

    Science.gov (United States)

    Fredi, André; Nolis, Pau; Cobas, Carlos; Martin, Gary E; Parella, Teodor

    2016-05-01

    The current Pros and Cons of a processing protocol to generate pure chemical shift NMR spectra using Generalized Indirect Covariance are presented and discussed. The transformation of any standard 2D homonuclear and heteronuclear spectrum to its pure shift counterpart by using a reference DIAG spectrum is described. Reconstructed pure shift NMR spectra of NOESY, HSQC, HSQC-TOCSY and HSQMBC experiments are reported for the target molecule strychnine.

  6. (129) Xe and (131) Xe nuclear magnetic dipole moments from gas phase NMR spectra.

    Science.gov (United States)

    Makulski, Włodzimierz

    2015-04-01

    (3) He, (129) Xe and (131) Xe NMR measurements of resonance frequencies in the magnetic field B0=11.7586 T in different gas phase mixtures have been reported. Precise radiofrequency values were extrapolated to the zero gas pressure limit. These results combined with new quantum chemical values of helium and xenon nuclear magnetic shielding constants were used to determine new accurate nuclear magnetic moments of (129) Xe and (131) Xe in terms of that of the (3) He nucleus. They are as follows: μ((129) Xe) = -0.7779607(158)μN and μ((131) Xe) = +0.6918451(70)μN . By this means, the new 'helium method' for estimations of nuclear dipole moments was successfully tested. Gas phase NMR spectra demonstrate the weak intermolecular interactions observed on the (3) He and (129) Xe and (131) Xe shielding in the gaseous mixtures with Xe, CO2 and SF6 .

  7. Automation of peak-tracking analysis of stepwise perturbed NMR spectra.

    Science.gov (United States)

    Banelli, Tommaso; Vuano, Marco; Fogolari, Federico; Fusiello, Andrea; Esposito, Gennaro; Corazza, Alessandra

    2017-02-01

    We describe a new algorithmic approach able to automatically pick and track the NMR resonances of a large number of 2D NMR spectra acquired during a stepwise variation of a physical parameter. The method has been named Trace in Track (TINT), referring to the idea that a gaussian decomposition traces peaks within the tracks recognised through 3D mathematical morphology. It is capable of determining the evolution of the chemical shifts, intensity and linewidths of each tracked peak.The performances obtained in term of track reconstruction and correct assignment on realistic synthetic spectra were high above 90% when a noise level similar to that of experimental data were considered. TINT was applied successfully to several protein systems during a temperature ramp in isotope exchange experiments. A comparison with a state-of-the-art algorithm showed promising results for great numbers of spectra and low signal to noise ratios, when the graduality of the perturbation is appropriate. TINT can be applied to different kinds of high throughput chemical shift mapping experiments, with quasi-continuous variations, in which a quantitative automated recognition is crucial.

  8. Assignment strategies in homonuclear three-dimensional 1H NMR spectra of proteins.

    Science.gov (United States)

    Vuister, G W; Boelens, R; Padilla, A; Kleywegt, G J; Kaptein, R

    1990-02-20

    The increase in dimensionality of three-dimensional (3D) NMR greatly enhances the spectral resolution in comparison to 2D NMR. It alleviates the problem of resonance overlap and may extend the range of molecules amenable to structure determination by high-resolution NRM spectroscopy. Here, we present strategies for the assignment of protein resonances from homonuclear nonselective 3D NOE-HOHAHA spectra. A notation for connectivities between protons, corresponding to cross peaks in 3D spectra, is introduced. We show how spin systems can be identified by tracing cross-peak patterns in cross sections perpendicular to the three frequency axes. The observable 3D sequential connectivities in proteins are tabulated, and estimates for the relative intensities of the corresponding cross peaks are given for alpha-helical and beta-sheet conformations. Intensities of the cross peaks in the 3D spectrum of pike III parvalbumin follow the predictions. The sequential-assignment procedure is illustrated for loop regions, extended and alpha-helical conformations for the residues Ala 54-Leu 63 of parvalbumin. NOEs that were not previously identified in 2D spectra of parvalbumin due to overlap are found.

  9. Proton detection of MAS solid-state NMR spectra of half-integer quadrupolar nuclei.

    Science.gov (United States)

    Venkatesh, Amrit; Hanrahan, Michael P; Rossini, Aaron J

    Fast magic angle spinning (MAS) and proton detection has found widespread application to enhance the sensitivity of solid-state NMR experiments with spin-1/2 nuclei such as (13)C, (15)N and (29)Si, however, this approach is not yet routinely applied to half-integer quadrupolar nuclei. Here we have investigated the feasibility of using fast MAS and proton detection to enhance the sensitivity of solid-state NMR experiments with half-integer quadrupolar nuclei. The previously described dipolar hetero-nuclear multiple quantum correlation (D-HMQC) and dipolar refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT) pulse sequences were used for proton detection of half-integer quadrupolar nuclei. Quantitative comparisons of signal-to-noise ratios and the sensitivity of proton detected D-HMQC and D-RINEPT and direct detection spin echo and quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) solid-state NMR spectra, demonstrate that one dimensional proton detected experiments can provide sensitivity similar to or exceeding that obtainable with direct detection QCPMG experiments. 2D D-HMQC and D-RINEPT experiments provide less sensitivity than QCPMG experiments but proton detected 2D hetero-nuclear correlation solid-state NMR spectra of half-integer nuclei can still be acquired in about the same time as a 1D spin echo spectrum. Notably, the rarely used D-RINEPT pulse sequence is found to provide similar, or better sensitivity than D-HMQC in some cases. Proton detected D-RINEPT benefits from the short longitudinal relaxation times (T1) normally associated with half-integer quadrupolar nuclei, it can be combined with existing signal enhancement methods for quadrupolar nuclei, and t1-noise in the indirect dimension can easily be removed by pre-saturation of the (1)H nuclei. The rapid acquisition of proton detected 2D HETCOR solid-state NMR spectra of a range of half-integer quadrupolar nuclei such as (17)O, (27)Al, (35)Cl and (71)Ga is demonstrated. Copyright

  10. Rapid acquisition of 14N solid-state NMR spectra with broadband cross polarization.

    Science.gov (United States)

    Harris, Kristopher J; Veinberg, Stanislav L; Mireault, Christopher R; Lupulescu, Adonis; Frydman, Lucio; Schurko, Robert W

    2013-11-25

    Nitrogen is an element of utmost importance in chemistry, biology and materials science. Of its two NMR-active isotopes, (14)N and (15)N, solid-state NMR (SSNMR) experiments are rarely conducted upon the former, due to its low gyromagnetic ratio (γ) and broad powder patterns arising from first-order quadrupolar interactions. In this work, we propose a methodology for the rapid acquisition of high quality (14)N SSNMR spectra that is easy to implement, and can be used for a variety of nitrogen-containing systems. We demonstrate that it is possible to dramatically enhance (14)N NMR signals in spectra of stationary, polycrystalline samples (i.e., amino acids and active pharmaceutical ingredients) by means of broadband cross polarization (CP) from abundant nuclei (e.g., (1)H). The BRoadband Adiabatic INversion Cross-Polarization (BRAIN-CP) pulse sequence is combined with other elements for efficient acquisition of ultra-wideline SSNMR spectra, including Wideband Uniform-Rate Smooth-Truncation (WURST) pulses for broadband refocusing, Carr-Purcell Meiboom-Gill (CPMG) echo trains for T2-driven S/N enhancement, and frequency-stepped acquisitions. The feasibility of utilizing the BRAIN-CP/WURST-CPMG sequence is tested for (14)N, with special consideration given to (i) spin-locking integer spin nuclei and maintaining adiabatic polarization transfer, and (ii) the effects of broadband polarization transfer on the overlapping satellite transition patterns. The BRAIN-CP experiments are shown to provide increases in signal-to-noise ranging from four to ten times and reductions of experimental times from one to two orders of magnitude compared to analogous experiments where (14)N nuclei are directly excited. Furthermore, patterns acquired with this method are generally more uniform than those acquired with direct excitation methods. We also discuss the proposed method and its potential for probing a variety of chemically distinct nitrogen environments.

  11. Gas phase NMR spectra of N,N-dimethylnitrosamine. Environmental effects on kinetic parameters

    Science.gov (United States)

    Chauvel, J. Paul; Leung, Doris Y.; True, Nancy S.

    1984-04-01

    Gas phase 1H NMR spectra of N,N-dimethylnitrosamine are consistent with first order chemical exchange rate constants which are ca. 25 times faster than those observed in neat liquids at corresponding temperatures. The associated kinetic parameters: Eact(∞), 20.5(1.1) kcal mol -1, Δ H‡, 19.7(1.0) kcal mol -1 and Δ G‡, 21.1(0.4) kcal mol -1 are approximately 2.5 kcal mol -1 lower than the most recently reported values for the neat liquid. The observed phase dependence is consistent with a process proceeding via a freely rotating transition state.

  12. High-resolution NMR spectra of n-alkanes penetrating into carbon fibers and of protons in carbon fibers.

    Science.gov (United States)

    Yamazaki, Yuya; Kobayashi, Nobuaki; Nikki, Kunio; Kuwahara, Daisuke

    2008-08-01

    We present a simple NMR method for microscopically exploring the local environment in carbon fibers. The method utilizes n-alkanes as probe molecules, where the n-alkanes penetrate carbon fibers of interest. The high-resolution (1)H NMR spectra for a mixture of a carbon fiber and n-alkanes acquired by this method show a shift of the resonance line, which is due to the local structure of the fiber. The utility of this method is discussed on the basis of the (1)H NMR spectra obtained. In addition, the (1)H distribution and the local motion in the structure of the carbon fiber are revealed in view of the (1)H NMR spectra.

  13. Modified oligosaccharides. Pt. 1. Analysis of the /sup 13/C NMR spectra of some keto derivatives of disaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Temeriusz, A.; Piekarska, B.; Radomski, J.; Stepinski, J. (Warsaw Univ. (Poland). Inst. Podstawowych Problemow Chemii)

    1980-01-01

    The /sup 13/C-NMR spectra of substituted disaccharides and their keto derivatives are analyzed and discussed. The peaks have been assigned by correlating the spectra of disaccharides with those of the constituent monosaccharides. Substituent effects caused by the formation of a new glycosyl bond are described.

  14. Synthesis, mechanism and NMR spectra of lanthanide complexes with a novel unsymmetrical Schiff base

    Institute of Scientific and Technical Information of China (English)

    姚克敏; 周文; 鲁桂; 沈联芳

    1999-01-01

    Owing to its two unsymmetrical-NH2 groups sited on different terminals, 2, 6-diaminocaproic acid (lysine) was used as a reactant for synthesizing a novel unsymmetrical Schiff base with salicylaldehyde on one side and ovanillin on the other for the first time. It is a new way to synthesize such a special unsymmetrical Schiff base. It is named "hetero bis-Schiff base" for distinguishing it from others. The synthesis method, formation mechanism as well as twelve new lanthanide complexes with the above ligand are reported and discussed herein. They were characterized by elementary analysis, molar conductivity, IR-spectra and especially by 1H and 13C NMR spectra. The results obtained may provide a new promising method for synthesizing similar unsymmetrical Schiff bases and their complexes.

  15. Practical SPI Planning

    Science.gov (United States)

    Landaeta, José Francisco; García, Javier; Amescua, Antonio

    This paper presents a practical procedure named P4SPI for planning, monitoring and closing an SPI. Planning activities are performed using PMBOK's process areas as a reference; monitoring activities using Six Sigma tools and techniques and closing activities using gathering qualitative and quantitative information about the SPI Implementation. These activities are supported by office templates.

  16. Spectral investigations of 2,5-difluoroaniline by using mass, electronic absorption, NMR, and vibrational spectra

    Science.gov (United States)

    Kose, Etem; Karabacak, Mehmet; Bardak, Fehmi; Atac, Ahmet

    2016-11-01

    One of the most significant aromatic amines is aniline, a primary aromatic amine replacing one hydrogen atom of a benzene molecule with an amino group (NH2). This study reports experimental and theoretical investigation of 2,5-difluoroaniline molecule (2,5-DFA) by using mass, ultraviolet-visible (UV-vis), 1H and 13C nuclear magnetic resonance (NMR), Fourier transform infrared and Raman (FT-IR and FT-Raman) spectra, and supported with theoretical calculations. Mass spectrum (MS) of 2,5-DFA is presented with their stabilities. The UV-vis spectra of the molecule are recorded in the range of 190-400 nm in water and ethanol solvents. The 1H and 13C NMR chemical shifts are recorded in CDCl3 solution. The vibrational spectra are recorded in the region 4000-400 cm-1 (FT-IR) and 4000-10 cm-1 (FT-Raman), respectively. Theoretical studies are underpinned the experimental results as described below; 2,5-DFA molecule is optimized by using B3LYP/6-311++G(d,p) basis set. The mass spectrum is evaluated and possible fragmentations are proposed based on the stable structure. The electronic properties, such as excitation energies, oscillator strengths, wavelengths, frontier molecular orbitals (FMO), HOMO and LUMO energies, are determined by time-dependent density functional theory (TD-DFT). The electrostatic potential surface (ESPs), density of state (DOS) diagrams are also prepared and evaluated. In addition to these, reduced density gradient (RDG) analysis is performed, and thermodynamic features are carried out theoretically. The NMR spectra (1H and 13C) are calculated by using the gauge-invariant atomic orbital (GIAO) method. The vibrational spectra of 2,5-DFA molecule are obtained by using DFT/B3LYP method with 6-311++G(d,p) basis set. Fundamental vibrations are assigned based on the potential energy distribution (PED) of the vibrational modes. The nonlinear optical properties (NLO) are also investigated. The theoretical and experimental results give a detailed description of

  17. Superresolution of FT-NMR Spectra by the Maximum Entropy Method and AR Model Fitting with Singular Value Decomposition

    Science.gov (United States)

    Uchiyama, Takanori; Minamitani, Haruyuki; Sakata, Makoto

    1990-01-01

    The complex maximum entropy method and complex autoregressive model fitting with the singular value decomposition method (SVD) were applied to the free induction decay signal data obtained with a Fourier transform nuclear magnetic resonance spectrometer to estimate superresolved NMR spectra. The practical estimation of superresolved NMR spectra are shown on the data of phosphorus-31 nuclear magnetic resonance spectra. These methods provide sharp peaks and high signal-to-noise ratio compared with conventional fast Fourier transform. The SVD method was more suitable for estimating superresolved NMR spectra than the MEM because the SVD method allowed high-order estimation without spurious peaks, and it was easy to determine the order and the rank.

  18. Supercharging SpyCatcher toward an intrinsically disordered protein with stimuli-responsive chemical reactivity.

    Science.gov (United States)

    Cao, Yang; Liu, Dong; Zhang, Wen-Bin

    2017-08-03

    We report a supercharged, intrinsically disordered protein, SpyCatcher(-), possessing stimuli-responsive reactivity toward SpyTag with tunable yields ranging from 4% to 98% depending on pH, temperature, ionic strength, etc. The CD and NMR studies reveal that the reaction occurs through a folded intermediate formed probably via a different mechanism from that of SpyCatcher.

  19. Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Atsushi; Oku, Takeo [Department of Materials Science, The University of Shiga Prefecture 2500 Hassaka, Hikone, Shiga, 522-8533 (Japan)

    2016-02-01

    Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of {sup 13}C, {sup 14}N and {sup 1}H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in {sup 13}C, {sup 14}N and {sup 1}H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

  20. Deconvolution of Complex 1D NMR Spectra Using Objective Model Selection.

    Directory of Open Access Journals (Sweden)

    Travis S Hughes

    Full Text Available Fluorine (19F NMR has emerged as a useful tool for characterization of slow dynamics in 19F-labeled proteins. One-dimensional (1D 19F NMR spectra of proteins can be broad, irregular and complex, due to exchange of probe nuclei between distinct electrostatic environments; and therefore cannot be deconvoluted and analyzed in an objective way using currently available software. We have developed a Python-based deconvolution program, decon1d, which uses Bayesian information criteria (BIC to objectively determine which model (number of peaks would most likely produce the experimentally obtained data. The method also allows for fitting of intermediate exchange spectra, which is not supported by current software in the absence of a specific kinetic model. In current methods, determination of the deconvolution model best supported by the data is done manually through comparison of residual error values, which can be time consuming and requires model selection by the user. In contrast, the BIC method used by decond1d provides a quantitative method for model comparison that penalizes for model complexity helping to prevent over-fitting of the data and allows identification of the most parsimonious model. The decon1d program is freely available as a downloadable Python script at the project website (https://github.com/hughests/decon1d/.

  1. Separation of 2H MAS NMR Spectra by Two-Dimensional Spectroscopy

    Science.gov (United States)

    Kristensen, J. H.; Bildsøe, H.; Jakobsen, H. J.; Nielsen, N. C.

    1999-08-01

    New methods for optimum separation of 2H MAS NMR spectra are presented. The approach is based on hypercomplex spectroscopy that is useful for sign discrimination and phase separation. A new theoretical formalism is developed for the description of hypercomplex experiments. This exploits the properties of Lie algebras and hypercomplex numbers to obtain a solution to the Liouville-von Neumann equation. The solution is expressed in terms of coherence transfer functions that describe the allowed coherence transfer pathways in the system. The theoretical formalism is essential in order to understand all the features of hypercomplex experiments. The method is applied to the development of two-dimensional quadrupole-resolved 2H MAS NMR spectroscopy. The important features of this technique are discussed and two different versions are presented with widely different characteristics. An improved version of two-dimensional double-quantum 2H MAS NMR spectroscopy is developed. The conditions under which the double-quantum experiment is useful are discussed and its performance is compared with that observed for the quadrupole-resolved experiments. A general method is presented for evaluating the optimum pulse sequence parameters consistent with maximum sensitivity and resolution. This approach improves the performance of the experiments and is essential for any further development of the techniques. The effects of finite pulse width and hypercomplex data processing may lead to both intensity and phase distortions in the spectra. These effects are analyzed and general correction procedures are suggested. The techniques are applied to polycrystalline malonic-acid-2H4 for which the spinning sideband manifolds from the carboxyl and methylene deuterons are separated. The spinning sideband manifolds are simulated to determine the quadrupole parameters. The values are consistent with previous results, indicating that the techniques are both accurate and reliable.

  2. Assignment of congested NMR spectra: Carbonyl backbone enrichment via the Entner Doudoroff pathway

    Science.gov (United States)

    Goldbourt, Amir; Day, Loren A.; McDermott, Ann E.

    2007-12-01

    In NMR spectra of complex proteins, sparse isotope enrichment can be important, in that the removal of many 13C- 13C homonuclear J-couplings can narrow the lines and thereby facilitate the process of spectral assignment and structure elucidation. We present a simple scheme for selective yet extensive isotopic enrichment applicable for production of proteins in organisms utilizing the Entner-Doudoroff (ED) metabolic pathway. An enrichment scheme so derived is demonstrated in the context of a magic-angle spinning solid-state NMR (MAS SSNMR) study of Pf1 bacteriophage, the host of which is Pseudomonas aeruginosa, strain K (PAK), an organism that uses the ED pathway for glucose catabolism. The intact and infectious Pf1 phage in this study was produced by infected PAK cells grown on a minimal medium containing 1- 13C D-glucose ( 13C in position 1) as the sole carbon source, as well as 15NH 4Cl as the only nitrogen source. The 37 MDa Pf1 phage consists of about 93% major coat protein, 1% minor coat proteins, and 6% single-stranded, circular DNA. As a consequence of this composition and the enrichment scheme, the resonances in the MAS SSNMR spectra of the Pf1 sample were almost exclusively due to carbonyl carbons in the major coat protein. Moreover, 3D heteronuclear NCOCX correlation experiments also show that the amino acids leucine, serine, glycine, and tyrosine were not isotopically enriched in their carbonyl positions (although most other amino acids were), which is as expected based upon considerations of the ED metabolic pathway. 3D NCOCX NMR data and 2D 15N- 15N data provided strong verification of many previous assignments of 15N amide and 13C carbonyl shifts in this highly congested spectrum; both the semi-selective enrichment patterns and the narrowed linewidths allowed for greater certainty in the assignments as compared with use of uniformly enriched samples alone.

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

    NARCIS (Netherlands)

    de Peinder, P.|info:eu-repo/dai/nl/325810818; Visser, T.|info:eu-repo/dai/nl/110288327; Petrauskas, D.D.; Salvatori, F.; Soulimani, F.|info:eu-repo/dai/nl/313889449; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2009-01-01

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

  4. Near-silence of isothiocyanate carbon in (13)C NMR spectra: a case study of allyl isothiocyanate.

    Science.gov (United States)

    Glaser, Rainer; Hillebrand, Roman; Wycoff, Wei; Camasta, Cory; Gates, Kent S

    2015-05-01

    (1)H and (13)C NMR spectra of allyl isothiocyanate (AITC) were measured, and the exchange dynamics were studied to explain the near-silence of the ITC carbon in (13)C NMR spectra. The dihedral angles α = ∠(C1-C2-C3-N4) and β = ∠(C2-C3-N4-C5) describe the conformational dynamics (conformation change), and the bond angles γ = ∠(C3-N4-C5) and ε = ∠(N4-C5-S6) dominate the molecular dynamics (conformer flexibility). The conformation space of AITC contains three minima, Cs-M1 and enantiomers M2 and M2'; the exchange between conformers is very fast, and conformational effects on (13)C chemical shifts are small (νM1 - νM2 silence of the ITC carbon in (13)C NMR spectra of organic isothiocyanates.

  5. Yeast-expressed human membrane protein aquaporin-1 yields excellent resolution of solid-state MAS NMR spectra

    Energy Technology Data Exchange (ETDEWEB)

    Emami, Sanaz; Fan Ying; Munro, Rachel; Ladizhansky, Vladimir; Brown, Leonid S., E-mail: lebrown@uoguelph.ca [University of Guelph, Departments of Physics, and Biophysics Interdepartmental Group (Canada)

    2013-02-15

    One of the biggest challenges in solid-state NMR studies of membrane proteins is to obtain a homogeneous natively folded sample giving high spectral resolution sufficient for structural studies. Eukaryotic membrane proteins are especially difficult and expensive targets in this respect. Methylotrophic yeast Pichia pastoris is a reliable producer of eukaryotic membrane proteins for crystallography and a promising economical source of isotopically labeled proteins for NMR. We show that eukaryotic membrane protein human aquaporin 1 can be doubly ({sup 13}C/{sup 15}N) isotopically labeled in this system and functionally reconstituted into phospholipids, giving excellent resolution of solid-state magic angle spinning NMR spectra.

  6. Lipid Dynamics Studied by Calculation of 31P Solid-State NMR Spectra Using Ensembles from Molecular Dynamics Simulations

    DEFF Research Database (Denmark)

    Hansen, Sara Krogh; Vestergaard, Mikkel; Thøgersen, Lea;

    2014-01-01

    We present a method to calculate 31P solid-state NMR spectra based on the dynamic input from extended molecular dynamics (MD) simulations. The dynamic information confered by MD simulations is much more comprehensive than the information provided by traditional NMR dynamics models based on......, for example, order parameters. Therefore, valuable insight into the dynamics of biomolecules may be achieved by the present method. We have applied this method to study the dynamics of lipid bilayers containing the antimicrobial peptide alamethicin, and we show that the calculated 31P spectra obtained...

  7. Interpretation of lanthanide-induced shifts in NMR spectra. The case of nonaxial symmetry

    Science.gov (United States)

    Babushkina, T. A.; Zolin, V. F.; Koreneva, L. G.

    The approach to the treatment of low-symmetry systems by the method of lanthanide shift reagents (LSR) is considered. Analysis of the results obtained by optical spectroscopy (mostly by luminescense spectroscopy of Eu 3+ ion) is used for this purpose. From the spectra mentioned, a model of the LSR adduct and parameters describing anisotropy of magnetic susceptibility are obtained. The method is applied to several rare-earth complexes of nonaxial symmetry. Bleaney's theory connecting pseudocontact NMR shifts to crystal field parameters of the second order is verified and shown to be correct if the crystal field splittings are of the order of kT. The systems Ln(dpm) 3 and Ln(fod) 3 are discussed.

  8. Non-linear signal detection improvement by radiation damping in single-pulse NMR spectra.

    Science.gov (United States)

    Schlagnitweit, Judith; Morgan, Steven W; Nausner, Martin; Müller, Norbert; Desvaux, Hervé

    2012-02-01

    When NMR lines overlap and at least one of them is affected by radiation damping, the resonance line shapes of all lines are no longer Lorentzian. We report the appearance of narrow signal distortions, which resemble hole-burnt spectra. This new experimental phenomenon facilitates the detection of tiny signals hidden below the main resonance. Theoretical analysis based on modified Maxwell-Bloch equations shows that the presence of strong transverse magnetization creates a feedback through the coil, which influences the magnetization of all spins with overlapping resonance lines. In the time domain this leads to cross-precession terms between magnetization densities, which ultimately cause non-linear behavior. Numerical simulations corroborate this interpretation.

  9. Peak picking multidimensional NMR spectra with the contour geometry based algorithm CYPICK.

    Science.gov (United States)

    Würz, Julia M; Güntert, Peter

    2017-01-01

    The automated identification of signals in multidimensional NMR spectra is a challenging task, complicated by signal overlap, noise, and spectral artifacts, for which no universally accepted method is available. Here, we present a new peak picking algorithm, CYPICK, that follows, as far as possible, the manual approach taken by a spectroscopist who analyzes peak patterns in contour plots of the spectrum, but is fully automated. Human visual inspection is replaced by the evaluation of geometric criteria applied to contour lines, such as local extremality, approximate circularity (after appropriate scaling of the spectrum axes), and convexity. The performance of CYPICK was evaluated for a variety of spectra from different proteins by systematic comparison with peak lists obtained by other, manual or automated, peak picking methods, as well as by analyzing the results of automated chemical shift assignment and structure calculation based on input peak lists from CYPICK. The results show that CYPICK yielded peak lists that compare in most cases favorably to those obtained by other automated peak pickers with respect to the criteria of finding a maximal number of real signals, a minimal number of artifact peaks, and maximal correctness of the chemical shift assignments and the three-dimensional structure obtained by fully automated assignment and structure calculation.

  10. 1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

    Science.gov (United States)

    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.

  11. Indirect detection of infinite-speed MAS solid-state NMR spectra

    Science.gov (United States)

    Perras, Frédéric A.; Venkatesh, Amrit; Hanrahan, Michael P.; Goh, Tian Wei; Huang, Wenyu; Rossini, Aaron J.; Pruski, Marek

    2017-03-01

    Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. To address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1H chemical shifts to the indirectly detected isotropic "infinite-MAS" spectra of heavy spin-1/2 nuclides. For these nuclides, the combination of fast MAS and 1H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands.

  12. NMR spectra of sup 5 sup 9 Co and sup 1 sup 4 N in CoN

    CERN Document Server

    Suzuki, K; Wagatsuma, F; Kaneko, T; Yoshida, H; Obi, Y; Tomiyoshi, S

    2003-01-01

    Nuclear magnetic resonance (NMR) measurements of sup 5 sup 9 Co and sup 1 sup 4 N in CoN with a zincblende type structure were carried out in the temperature range from 4.2 K to room temperature. NMR Spectra of sup 5 sup 9 Co are obtained from Free Induction Decay (FID) signals in a static field of 6.3068 T. NMR Spectra of sup 1 sup 4 N are obtained by spin-echo method in the same static field. The temperature variations of Knight shifts are derived from resonance peak positions at various temperatures. In this experiment, it is found that the temperature variations of Knight shifts are very small. Therefore, it is concluded that the compound CoN has Pauli paramagnetism. This is consistent with the result of the temperature-independent susceptibility. (author)

  13. A systematic approach to obtain validated partial least square models for predicting lipoprotein subclasses from serum NMR spectra

    NARCIS (Netherlands)

    Mihaleva, V.V.; Schalkwijk, van D.B.; Graaf, de A.A.; Duynhoven, van J.P.M.; Dorsten, van F.A.; Vervoort, J.J.M.; Smilde, A.K.; Westerhuis, J.A.; Jacobs, D.M.

    2014-01-01

    A systematic approach is described for building validated PLS models that predict cholesterol and triglyceride concentrations in lipoprotein subclasses in fasting serum from a normolipidemic, healthy population. The PLS models were built on diffusion-edited (1)H NMR spectra and calibrated on HPLC-de

  14. A systematic approach to obtain validated partial least square models for predicting lipoprotein subclasses from serum nmr spectra

    NARCIS (Netherlands)

    Mihaleva, V.V.; Schalkwijk, D.B. van; Graaf, A.A. de; Duynhoven, J. van; Dorsten, F.A. van; Vervoort, J.; Smilde, A.; Westerhuis, J.A.; Jacobs, D.M.

    2014-01-01

    A systematic approach is described for building validated PLS models that predict cholesterol and triglyceride concentrations in lipoprotein subclasses in fasting serum from a normolipidemic, healthy population. The PLS models were built on diffusion-edited 1H NMR spectra and calibrated on HPLC-deri

  15. Conformation of antifreeze glycoproteins as determined from conformational energy calculations and fully assigned proton NMR spectra

    Energy Technology Data Exchange (ETDEWEB)

    Bush, C.A.; Rao, B.N.N.

    1986-05-01

    The /sup 1/H NMR spectra of AFGP's ranging in molecular weight from 2600 to 30,000 Daltons isolated from several different species of polar fish have been measured. The spectrum of AFGP 1-4 from Pagothenia borchgrevinki with an average of 30 repeating subunits has a single resonance for each proton of the glycotripeptide repeating unit, (ala-(gal-(..beta..-1..-->..3) galNAc-(..cap alpha..--O-)thr-ala)/sub n/. Its /sup 1/H NMR spectrum including resonances of the amide protons has been completely assigned. Coupling constants and nuclear Overhauser enhancements (n.O.e.) between protons on distant residues imply conformational order. The 2600 dalton molecular weight glycopeptides (AFGP-8) have pro in place of ala at certain specific points in the sequence and AFGP-8R of Eleginus gracilis has arg in place of one thr. The resonances of pro and arg were assigned by decoupling. The resonances of the carboxy and amino terminals have distinct chemical shifts and were assigned in AFGP-8 of Boreogadus saida by titration. n.O.e. between ..cap alpha..--protons and amide protons of the adjacent residue (sequential n.O.e.) were used in assignments of additional resonances and to assign the distinctive resonances of thr followed by pro. Conformational energy calculations on the repeating glycotripeptide subunit of AFGP show that the ..cap alpha..--glucosidic linkage has a fixed conformation while the ..beta..--linkage is less rigid. A conformational model for AFGP 1-4, which is based on the calculations has the peptide in an extended left-handed helix with three residues per turn similar to polyproline II. The model is consistent with CD data, amide proton coupling constants, temperature dependence of amide proton chemical shifts.

  16. 13C NMR spectra of tectonic coals and the effects of stress on structural components

    Institute of Scientific and Technical Information of China (English)

    JU Yiwen; JIANG Bo; HOU Quanlin; WANG Guiliang; NI Shanqin

    2005-01-01

    High-resolution 13C Nuclear Magnetic Resonance (NMR) spectra of different kinds of tectonic coals were obtained using the NMR (CP/MAS+TOSS) method. On the basis of this, after simulation synthesis and division of spectra, the relative contents of carbon functional groups were calculated. Combined with results of Ro, max, XRD testing and element analysis, stress effects on the composition of macromolecular structures in tectonic coals were studied further. The results showed that Ro, max was not only the important index for describing coal rank, but was also effective for estimating the stress effect of tectonic coals. Under tectonic stress action, Ro, max was the most direct indicator of the coal structure and chemical components. Changes in the stacking Lc of the coal basic structure unit (BSU) and La/Lc parameters could distinguish the temperature and stress effects on metamorphic-deformed environments, and reflected the degree of structural deformation. Therefore, on the whole, Lc and La/Lc can be used to index of the degree of structural deformation of tectonic coals. In different metamorphic and deformed environments, different kinds of tectonic coals are formed under structural stress. The changes in characteristics of the macromolecular structure and chemical composition are such that as the increase in structural deformation becomes stronger, from the brittle deformation coal to ductile deformation coal, the ratio of width at the half height of the aromatic carbon and aliphatic carbon peaks (Hfa/Hfal ) was increased. As carbon aromaticity was raised further, carbon aliphaticity reduced obviously and different compositions of macromolecular structure appeared as a jump and wave pattern except for in wrinkle structure coal, which might result chiefly from stress effects on the macromolecular structure of different kinds of tectonic coals. The macromoecular changes of wrinkle structure coal are reflected mainly on physical structure. In the metamorphic and

  17. Resolution Improvements in in Vivo1H NMR Spectra with Increased Magnetic Field Strength

    Science.gov (United States)

    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.

  18. Theoretical Studies on Electronic Structures and NMR Spectra of Ollgo(4-vinylpyridine)

    Institute of Scientific and Technical Information of China (English)

    ZHAO Hongjian; ZHOU Jia; HU Lingjing; TENG Qiwen

    2009-01-01

    Poly(4-vinylpyridine)was determined to possess conductivity in the experiment.In order to understand properties of the polymer,a series of 4-vinylpyridine oligomers were designed.The structures of these oligomers were optimized using density function theory(DFT)at B3LYP/6-31G(d)level.The energy gaps and thermal stabilities of the oligomers were decreased when the chain lengths were increased.These properties were also decreased owing to the protonation of the pyridine ring.The holes were easily injected into the oligomers in the presence of hydrochloride.The electrons were conducted in the side chain composed of the pytidine rings rather than the main chain owing to the saturation of the main chain.The 13C nuclear magnetic resonance(NMR)spectra and nucleus independent chemical shifts(NICS)of these compounds were calculated at B3LYP/6-31G(d)level.The chemical shifts of the carbon atoms connected with the nitrogen atoms in the protonated pyridines were moved upfield in comparison with those of the pyridines.The addition of hydrochioride on the pyridine ring in the oligomers led to the increase of the aromaficifies,namely the aromaticities of the oligomers were obviously improved when the pyridine rings were protonated.

  19. Atomic structure of icosahedral B4C boron carbide from a first principles analysis of NMR spectra.

    Science.gov (United States)

    Mauri, F; Vast, N; Pickard, C J

    2001-08-20

    Density functional theory is demonstrated to reproduce the 13C and 11B NMR chemical shifts of icosahedral boron carbides with sufficient accuracy to extract previously unresolved structural information from experimental NMR spectra. B4C can be viewed as an arrangement of 3-atom linear chains and 12-atom icosahedra. According to our results, all the chains have a CBC structure. Most of the icosahedra have a B11C structure with the C atom placed in a polar site, and a few percent have a B (12) structure or a B10C2 structure with the two C atoms placed in two antipodal polar sites.

  20. Nonclassical dynamics of the methyl group in 1,1,1-triphenylethane. Evidence from powder 1H NMR spectra

    KAUST Repository

    Osior, Agnieszka

    2017-03-14

    According to the damped quantum rotation (DQR) theory, hindered rotation of methyl groups, evidenced in nuclear magnetic resonance (NMR) line shapes, is a nonclassical process. It comprises a number of quantum-rate processes measured by two different quantum-rate constants. The classical jump model employing only one rate constant is reproduced if these quantum constants happen to be equal. The values of their ratio, or the nonclassicallity coefficient, determined hitherto from NMR spectra of single crystals and solutions range from about 1.20 to 1.30 in the latter case to above 5.0 in the former, with the value of 1 corresponding to the jump model. Presently, first systematic investigations of the DQR effects in wide-line NMR spectra of a powder sample are reported. For 1,1,1-triphenylethane deuterated in the aromatic positions, the relevant line-shape effects were monitored in the range 99–121 K. The values of the nonclassicality coefficient dropping from 2.7 to 1.7 were evaluated in line shape fits to the experimental powder spectra from the range 99–108 K. At these temperatures, the fits with the conventional line-shape model are visibly inferior to the DQR fits. Using a theoretical model reported earlier, a semiquantitative interpretation of the DQR parameters evaluated from the spectra is given. It is shown that the DQR effects as such can be detected in wide-line NMR spectra of powdered samples, which are relatively facile to measure. However, a fully quantitative picture of these effects can only be obtained from the much more demanding experiments on single crystals.

  1. MetaboHunter: an automatic approach for identification of metabolites from 1H-NMR spectra of complex mixtures

    Directory of Open Access Journals (Sweden)

    Culf Adrian

    2011-10-01

    Full Text Available Abstract Background One-dimensional 1H-NMR spectroscopy is widely used for high-throughput characterization of metabolites in complex biological mixtures. However, the accurate identification of individual compounds is still a challenging task, particularly in spectral regions with higher peak densities. The need for automatic tools to facilitate and further improve the accuracy of such tasks, while using increasingly larger reference spectral libraries becomes a priority of current metabolomics research. Results We introduce a web server application, called MetaboHunter, which can be used for automatic assignment of 1H-NMR spectra of metabolites. MetaboHunter provides methods for automatic metabolite identification based on spectra or peak lists with three different search methods and with possibility for peak drift in a user defined spectral range. The assignment is performed using as reference libraries manually curated data from two major publicly available databases of NMR metabolite standard measurements (HMDB and MMCD. Tests using a variety of synthetic and experimental spectra of single and multi metabolite mixtures show that MetaboHunter is able to identify, in average, more than 80% of detectable metabolites from spectra of synthetic mixtures and more than 50% from spectra corresponding to experimental mixtures. This work also suggests that better scoring functions improve by more than 30% the performance of MetaboHunter's metabolite identification methods. Conclusions MetaboHunter is a freely accessible, easy to use and user friendly 1H-NMR-based web server application that provides efficient data input and pre-processing, flexible parameter settings, fast and automatic metabolite fingerprinting and results visualization via intuitive plotting and compound peak hit maps. Compared to other published and freely accessible metabolomics tools, MetaboHunter implements three efficient methods to search for metabolites in manually curated

  2. All-atom Molecular Dynamic Simulations and NMR Spectra Study on Intermolecular Interactions of N,N-dimethylacetamide-Water System

    Institute of Scientific and Technical Information of China (English)

    Rong Zhang; Zai-you Tan; San-lai Luo

    2008-01-01

    N,N-dimethylacetamide (DMA) has been investigated extensively in studying models of peptide bonds. An all-atom MD simulation and the NMR spectra were performed to investigate the interactions in the DMA- water system. The radial distribution functions (RDFs) and the hydrogen-bonding network were used in MD simulations. There are strong hydrogen bonds and weak C-H…O contacts in the mixtures, as shown by the analysis of the RDFs. The insight structures in the DMA-water mixtures can be classified into different regions by the analysis of the hydrogen-bonding network. Chemical shifts of the hydrogen atom of water molecule with concentration and temperatures are adopted to study the interactions in the mixtures. The results of NMR spectra show good agreement with the statistical results of hydrogen bonds in MD simulations.

  3. Exploring Supernova Remnants with the SPIES Project

    Science.gov (United States)

    Frank, Kari A.; Burrows, David N.; Dwarkadas, Vikram

    2017-01-01

    X-ray observations provide a key window into supernova remnants, providing measurements of a plethora of physical properties that are critical for understanding SNRs, their environments, their progenitors, and the SNe that created them. However, characterizing the entire volume of shocked plasma in a SNR is difficult, due to their complicated three dimensional morphologies and spectra. The SPIES project aims to address this problem by applying a novel X-ray analysis method, Smoothed Particle Inference (SPI), to XMM observations of 12 SNRs. SPI is a Bayesian modeling process that fits a population of gas blobs ("smoothed particles") such that their superposed emission reproduces the observed spatial and spectral distribution of photons. Emission-weighted distributions and maps of plasma properties, such as abundances and temperatures, are then extracted from the properties of the individual blobs. Additionally, because the collection of blobs is a multi-dimensional representation of the shocked plasma, we can carry out a more detailed exploration of plasma properties by extracting any subset of the blobs (e.g. those with the highest temperatures) and investigating its properties (e.g. map the abundances). Here we present preliminary results from SPI analyses of the first 6 remnants in the SPIES project.

  4. Resonance Assignment of the NMR Spectra of Disordered Proteins Using a Multi-Objective Non-Dominated Sorting Genetic Algorithm

    Science.gov (United States)

    Yang, Yu; Fritzsching, Keith J.

    2014-01-01

    A multi-objective genetic algorithm is introduced to predict the assignment of protein solid-state NMR spectra with partial resonance overlap and missing peaks due to broad linewidths, molecular motion, and low sensitivity. This non-dominated sorting genetic algorithm II (NSGA-II) aims to identify all possible assignments that are consistent with the spectra and to compare the relative merit of these assignments. Our approach is modeled after the recently introduced Monte Carlo simulated annealing (MC/SA) protocol, with the key difference that NSGA-II simultaneously optimizes multiple assignment objectives instead of searching for possible assignments based on a single composite score. The multiple objectives include maximizing the number of consistently assigned peaks between multiple spectra (“good connections”), maximizing the number of used peaks, minimizing the number of inconsistently assigned peaks between spectra (“bad connections”), and minimizing the number of assigned peaks that have no matching peaks in the other spectra (“edges”). Using six solid-state NMR protein chemical shift datasets with varying levels of imperfection that was introduced by peak deletion, random chemical shift changes, and manual peak picking of spectra with moderately broad linewidths, we show that the NSGA-II algorithm produces a large number of valid and good assignments rapidly. For high-quality chemical shift peak lists, NSGA-II and MC/SA perform similarly well. However, when the peak lists contain many missing peaks that are uncorrelated between different spectra and have chemical shift deviations between spectra, the modified NSGA-II produces a larger number of valid solutions than MC/SA, and is more effective at distinguishing good from mediocre assignments by avoiding the hazard of suboptimal weighting factors for the various objectives. These two advantages, namely diversity and better evaluation, lead to a higher probability of predicting the correct

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

    Science.gov (United States)

    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.

  6. Quantitative Quantum Mechanical Spectral Analysis (qQMSA) of (1)H NMR spectra of complex mixtures and biofluids.

    Science.gov (United States)

    Tiainen, Mika; Soininen, Pasi; Laatikainen, Reino

    2014-05-01

    The quantitative interpretation of (1)H NMR spectra of mixtures like the biofluids is a demanding task due to spectral complexity and overlap. Complications may arise also from water suppression, T2-editing, protein interactions, relaxation differences of the species, experimental artifacts and, furthermore, the spectra may contain unknown components and macromolecular background which cannot be easily separated from baseline. In this work, tools and strategies for quantitative Quantum Mechanical Spectral Analysis (qQMSA) of (1)H NMR spectra from complex mixtures were developed and systematically assessed. In the present approach, the signals of well-defined, stoichiometric components are described by a QM model, while the background is described by a multiterm baseline function and the unknown signals using optimizable and adjustable lines, regular multiplets or any spectral structures which can be composed from spectral lines. Any prior knowledge available from the spectrum can also be added to the model. Fitting strategies for weak and strongly overlapping spectral systems were developed and assessed using two basic model systems, the metabolite mixtures without and with macromolecular (serum) background. The analyses show that if the spectra are measured in high-throughput manner, the consistent absolute quantification demands some calibration to compensate the different response factors of the protons and compounds. On the other hand, the results show that also the T2-edited spectra can be measured so that they obey well the QM rules. In general, qQMSA exploits and interprets the spectral information in maximal way taking full advantage from the QM properties of the spectra and, at the same time, offers chemical confidence which means that individual components can be identified with high confidence on the basis of their accurate spectral parameters.

  7. Quantification and identification of components in solution mixtures from 1D proton NMR spectra using singular value decomposition.

    Science.gov (United States)

    Xu, Qiuwei; Sachs, Jeffrey R; Wang, Ting-Chuan; Schaefer, William H

    2006-10-15

    One-dimensional proton NMR spectra of complex solutions provide rich molecular information, but limited chemical shift dispersion creates peak overlap that often leads to difficulty in peak identification and analyte quantification. Modern high-field NMR spectrometers provide high digital resolution with improved peak dispersion. We took advantage of these spectral qualities and developed a quantification method based on linear least-squares fitting using singular value decomposition (SVD). The linear least-squares fitting of a mixture spectrum was performed on the basis of reference spectra from individual small-molecule analytes. Each spectrum contained an internal quantitative reference (e.g., DSS-d6 or other suitable small molecules) by which the intensity of the spectrum was scaled. Normalization of the spectrum facilitated quantification based on peak intensity using linear least-squares fitting analysis. This methodology provided quantification of individual analytes as well as chemical identification. The analysis of small-molecule analytes over a wide concentration range indicated the accuracy and reproducibility of the SVD-based quantification. To account for the contribution from residual protein, lipid or polysaccharide in solution, a reference spectrum showing the macromolecules or aggregates was obtained using a diffusion-edited 1D proton NMR analysis. We demonstrated this approach with a mixture of small-molecule analytes in the presence of macromolecules (e.g., protein). The results suggested that this approach should be applicable to the quantification and identification of small-molecule analytes in complex biological samples.

  8. An inversion method of 2D NMR relaxation spectra in low fields based on LSQR and L-curve

    Science.gov (United States)

    Su, Guanqun; Zhou, Xiaolong; Wang, Lijia; Wang, Yuanjun; Nie, Shengdong

    2016-04-01

    The low-field nuclear magnetic resonance (NMR) inversion method based on traditional least-squares QR decomposition (LSQR) always produces some oscillating spectra. Moreover, the solution obtained by traditional LSQR algorithm often cannot reflect the true distribution of all the components. Hence, a good solution requires some manual intervention, for especially low signal-to-noise ratio (SNR) data. An approach based on the LSQR algorithm and L-curve is presented to solve this problem. The L-curve method is applied to obtain an improved initial optimal solution by balancing the residual and the complexity of the solutions instead of manually adjusting the smoothing parameters. First, the traditional LSQR algorithm is used on 2D NMR T1-T2 data to obtain its resultant spectra and corresponding residuals, whose norms are utilized to plot the L-curve. Second, the corner of the L-curve as the initial optimal solution for the non-negative constraint is located. Finally, a 2D map is corrected and calculated iteratively based on the initial optimal solution. The proposed approach is tested on both simulated and measured data. The results show that this algorithm is robust, accurate and promising for the NMR analysis.

  9. Resonance assignment of the NMR spectra of disordered proteins using a multi-objective non-dominated sorting genetic algorithm

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yu; Fritzsching, Keith J.; Hong, Mei, E-mail: mhong@iastate.edu [Iowa State University, Department of Chemistry (United States)

    2013-10-17

    A multi-objective genetic algorithm is introduced to predict the assignment of protein solid-state NMR (SSNMR) spectra with partial resonance overlap and missing peaks due to broad linewidths, molecular motion, and low sensitivity. This non-dominated sorting genetic algorithm II (NSGA-II) aims to identify all possible assignments that are consistent with the spectra and to compare the relative merit of these assignments. Our approach is modeled after the recently introduced Monte-Carlo simulated-annealing (MC/SA) protocol, with the key difference that NSGA-II simultaneously optimizes multiple assignment objectives instead of searching for possible assignments based on a single composite score. The multiple objectives include maximizing the number of consistently assigned peaks between multiple spectra (“good connections”), maximizing the number of used peaks, minimizing the number of inconsistently assigned peaks between spectra (“bad connections”), and minimizing the number of assigned peaks that have no matching peaks in the other spectra (“edges”). Using six SSNMR protein chemical shift datasets with varying levels of imperfection that was introduced by peak deletion, random chemical shift changes, and manual peak picking of spectra with moderately broad linewidths, we show that the NSGA-II algorithm produces a large number of valid and good assignments rapidly. For high-quality chemical shift peak lists, NSGA-II and MC/SA perform similarly well. However, when the peak lists contain many missing peaks that are uncorrelated between different spectra and have chemical shift deviations between spectra, the modified NSGA-II produces a larger number of valid solutions than MC/SA, and is more effective at distinguishing good from mediocre assignments by avoiding the hazard of suboptimal weighting factors for the various objectives. These two advantages, namely diversity and better evaluation, lead to a higher probability of predicting the correct

  10. Resonance assignment of the NMR spectra of disordered proteins using a multi-objective non-dominated sorting genetic algorithm.

    Science.gov (United States)

    Yang, Yu; Fritzsching, Keith J; Hong, Mei

    2013-11-01

    A multi-objective genetic algorithm is introduced to predict the assignment of protein solid-state NMR (SSNMR) spectra with partial resonance overlap and missing peaks due to broad linewidths, molecular motion, and low sensitivity. This non-dominated sorting genetic algorithm II (NSGA-II) aims to identify all possible assignments that are consistent with the spectra and to compare the relative merit of these assignments. Our approach is modeled after the recently introduced Monte-Carlo simulated-annealing (MC/SA) protocol, with the key difference that NSGA-II simultaneously optimizes multiple assignment objectives instead of searching for possible assignments based on a single composite score. The multiple objectives include maximizing the number of consistently assigned peaks between multiple spectra ("good connections"), maximizing the number of used peaks, minimizing the number of inconsistently assigned peaks between spectra ("bad connections"), and minimizing the number of assigned peaks that have no matching peaks in the other spectra ("edges"). Using six SSNMR protein chemical shift datasets with varying levels of imperfection that was introduced by peak deletion, random chemical shift changes, and manual peak picking of spectra with moderately broad linewidths, we show that the NSGA-II algorithm produces a large number of valid and good assignments rapidly. For high-quality chemical shift peak lists, NSGA-II and MC/SA perform similarly well. However, when the peak lists contain many missing peaks that are uncorrelated between different spectra and have chemical shift deviations between spectra, the modified NSGA-II produces a larger number of valid solutions than MC/SA, and is more effective at distinguishing good from mediocre assignments by avoiding the hazard of suboptimal weighting factors for the various objectives. These two advantages, namely diversity and better evaluation, lead to a higher probability of predicting the correct assignment for a

  11. Spectral fitting of NMR spectra using an alternating optimization method with a priori knowledge.

    Science.gov (United States)

    Bi, Z; Bruner, A P; Li, J; Scott, K N; Liu, Z S; Stopka, C B; Kim, H W; Wilson, D C

    1999-09-01

    As alternatives to the fast Fourier transform, advanced parametric methods based on the damped sinusoidal data model have been devised to better quantify the nuclear magnetic resonance (NMR) spectroscopy time-domain data. Previously, linear prediction (LP) fitting methods using Householder triangularization and singular value decomposition (SVD) techniques have been applied to the NMR spectroscopy data analysis. In this paper, we propose an alternating optimization method to quantify the time-domain NMR spectroscopy data. The proposed algorithm uses the a priori knowledge of the possible frequency intervals of the damped sinusoids to obtain more accurate parameter estimates when the NMR spectroscopy data are obtained under low signal-to-noise ratio conditions and the peaks are close together. None of the LP and SVD type of methods can use such approximate a priori knowledge. We have shown with measured NMR spectroscopy data that the proposed algorithm can be used to obtain accurate parameter estimates of frequencies, amplitudes, and damping ratios of the damped sinusoids and therefore the ultimate fit of the spectrum by using the a priori knowledge about the possible frequency intervals of the damped sinusoids. Copyright 1999 Academic Press.

  12. Structural Determination of Bis-histidinopeptide Zinc Complexes by 15N NMR (HMBC) Spectra

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Cheng-He; Juan F.Miravet; M.Isabel Burguete; Santiago V.Luis; BAI,Xue; YUAN,Yong

    2004-01-01

    @@ Polynitrogen receptors such as bis-histidine peptides possess strong ability to bind metals, which play much important roles in medicinal, bioinorganic, bioorganic, biomimetic and supramolecular chemistry. In order to investigate the interaction of these hosts with a variety of neutral, cationic and anionic guests, several techniques, for example, NMR,potentiometric tirations and monocrystal X-ray diffraction have been employed. Among them NMR is a powerful technique for unraveling the structure of polynitrogen receptors as long as they are in solution where the rapid tumbling of molecules averages out the anisotropies such as chemical shift and dipole-dipole interactions. General 1H NMR approach has been widely used for the study of host-guest interaction, but it is difficult for the accurate measurement in complexes structures, particularly metal complexes structures in which how the polynitrogen receptors bind metal, and which nitrogen binds metal and so on.

  13. Correlation analysis of the /sup 13/C NMR spectra of some para-substituted benzaldehyde oximes and their anions

    Energy Technology Data Exchange (ETDEWEB)

    Rutkovskii, G.V.; Zmeikov, V.P.

    1987-06-20

    For the case of the /sup 13/C NMR spectra of a series of para-substituted benzaldehyde oximes and their anions it was shown that to describe the chemical shifts of all the carbon atoms of the benzene ring and the exocyclic CH group it is necessary to use three-parameter equations with the parameters F and R (which characterize the inductive and resonance effects respectively of the substituents), and Q (which corresponds to the paramagnetic interaction between the substituents and the carbon atoms).

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

    Science.gov (United States)

    O'Dell, Luke A; Schurko, Robert W

    2009-05-20

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

  15. Periodic ab initio calculation of nuclear quadrupole parameters as an assignment tool in solid-state NMR spectroscopy: applications to 23Na NMR spectra of crystalline materials.

    Science.gov (United States)

    Johnson, Clive; Moore, Elaine A; Mortimer, Michael

    2005-05-01

    Periodic ab initio HF calculations using the CRYSTAL code have been used to calculate (23)Na NMR quadrupole parameters for a wide range of crystalline sodium compounds including Na(3)OCl. An approach is developed that can be used routinely as an alternative to point-charge modelling schemes for the assignment of distinct lines in (23)Na NMR spectra to specific crystallographic sodium sites. The calculations are based on standard 3-21 G and 6-21 G molecular basis sets and in each case the same modified basis set for sodium is used for all compounds. The general approach is extendable to other quadrupolar nuclei. For the 3-21 G calculations a 1:1 linear correlation between experimental and calculated values of C(Q)((23)Na) is obtained. The 6-21 G calculations, including the addition of d-polarisation functions, give better accuracy in the calculation of eta((23)Na). The sensitivity of eta((23)Na) to hydrogen atom location is shown to be useful in testing the reported hydrogen-bonded structure of Na(2)HPO(4).

  16. "I Spy" Engaged Learners.

    Science.gov (United States)

    Sassano, Lisa

    2003-01-01

    Encourages student awareness of the connections between their classroom experiences and real life. Develops an idea to motivate and keep track of students' findings, the "I Spy Vocab Words" contest. Describes how the author implemented the contest. Notes how the program has students keep a log of vocabulary words they find in their everyday lives.…

  17. HiFSA Fingerprinting Applied to Isomers with Near-Identical NMR Spectra: The Silybin/Isosilybin Case

    Science.gov (United States)

    Napolitano, José G.; Lankin, David C.; Graf, Tyler N.; Friesen, J. Brent; Chen, Shao-Nong; McAlpine, James B.; Oberlies, Nicholas H.; Pauli, Guido F.

    2013-01-01

    This study demonstrates how regio- and diastereo-isomers with near-identical NMR spectra can be distinguished and unambiguously assigned using quantum mechanical driven, 1H iterative Full Spin Analysis (HiFSA). The method is illustrated with four natural products, the flavonolignans silybin A, silybin B, isosilybin A, and isosilybin B, which exhibit extremely similar coupling patterns and chemical shift differences well below the commonly reported level of accuracy of 0.01 ppm. The HiFSA approach generated highly reproducible 1H NMR fingerprints that enable distinction of all four isomers at 1H frequencies from 300 to 900 MHz. Furthermore, it is demonstrated that the underlying numeric 1H NMR profiles, combined with iterative computational analysis, allow parallel quantification of all four isomers, even in difficult to characterize reference materials and mixtures. The results shed new light on the historical challenges to the qualitative and quantitative analysis of these therapeutically relevant flavonolignans and open new opportunities to explore hidden diversity in the chemical space of organic molecules. PMID:23461697

  18. A Global Approach to Accurate and Automatic Quantitative Analysis of NMR Spectra by Complex Least-Squares Curve Fitting

    Science.gov (United States)

    Martin, Y. L.

    The performance of quantitative analysis of 1D NMR spectra depends greatly on the choice of the NMR signal model. Complex least-squares analysis is well suited for optimizing the quantitative determination of spectra containing a limited number of signals (20). From a general point of view it is concluded, on the basis of mathematical considerations and numerical simulations, that, in the absence of truncation of the free-induction decay, complex least-squares curve fitting either in the time or in the frequency domain and linear-prediction methods are in fact nearly equivalent and give identical results. However, in the situation considered, complex least-squares analysis in the frequency domain is more flexible since it enables the quality of convergence to be appraised at every resonance position. An efficient data-processing strategy has been developed which makes use of an approximate conjugate-gradient algorithm. All spectral parameters (frequency, damping factors, amplitudes, phases, initial delay associated with intensity, and phase parameters of a baseline correction) are simultaneously managed in an integrated approach which is fully automatable. The behavior of the error as a function of the signal-to-noise ratio is theoretically estimated, and the influence of apodization is discussed. The least-squares curve fitting is theoretically proved to be the most accurate approach for quantitative analysis of 1D NMR data acquired with reasonable signal-to-noise ratio. The method enables complex spectral residuals to be sorted out. These residuals, which can be cumulated thanks to the possibility of correcting for frequency shifts and phase errors, extract systematic components, such as isotopic satellite lines, and characterize the shape and the intensity of the spectral distortion with respect to the Lorentzian model. This distortion is shown to be nearly independent of the chemical species, of the nature of the molecular site, and of the type of nucleus, but

  19. Site-resolved 2H relaxation experiments in solid materials by global line-shape analysis of MAS NMR spectra

    Science.gov (United States)

    Lindh, E. L.; Stilbs, P.; Furó, I.

    2016-07-01

    We investigate a way one can achieve good spectral resolution in 2H MAS NMR experiments. The goal is to be able to distinguish between and study sites in various deuterated materials with small chemical shift dispersion. We show that the 2H MAS NMR spectra recorded during a spin-relaxation experiment are amenable to spectral decomposition because of the different evolution of spectral components during the relaxation delay. We verify that the results are robust by global least-square fitting of the spectral series both under the assumption of specific line shapes and without such assumptions (COmponent-REsolved spectroscopy, CORE). In addition, we investigate the reliability of the developed protocol by analyzing spectra simulated with different combinations of spectral parameters. The performance is demonstrated in a model material of deuterated poly(methacrylic acid) that contains two 2H spin populations with similar chemical shifts but different quadrupole splittings. In 2H-exchanged cellulose containing two 2H spin populations with very similar chemical shifts and quadrupole splittings, the method provides new site-selective information about the molecular dynamics.

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

    Science.gov (United States)

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

    2015-10-29

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

  1. QUEST-QUadrupolar Exact SofTware: a fast graphical program for the exact simulation of NMR and NQR spectra for quadrupolar nuclei.

    Science.gov (United States)

    Perras, Frédéric A; Widdifield, Cory M; Bryce, David L

    2012-01-01

    We present a new program for the exact simulation of solid-state NMR spectra of quadrupolar nuclei in stationary powdered samples which employs diagonalization of the combined Zeeman-quadrupolar Hamiltonian. The program, which we call QUEST (QUadrupolar Exact SofTware), can simulate NMR spectra over the full regime of Larmor and quadrupolar frequency ratios, which encompasses scenarios ranging from high-field NMR to nuclear quadrupole resonance (NQR, where the Larmor frequency is zero) and does not make use of approximations when treating the quadrupolar interaction. With the use of the fast powder averaging scheme of Alderman, Solum, and Grant, exact NMR spectral simulations are only marginally slower than the second-order perturbation theory counterpart. The program, which uses a graphical user interface, also incorporates chemical shift anisotropy and non-coincident chemical shift and quadrupolar tensor frames. The program is validated against newly-acquired experimental data through several examples including: the low-field (79/81)Br NMR spectra of CaBr(2), the (14)N overtone NMR spectrum of glycine, the (187)Re NQR spectra of Re(2)(CO)(10), and lastly the (127)I overtone NQR spectrum of SrI(2), which, to the best of our knowledge, represents the first direct acquisition of an overtone NQR spectrum for a powdered sample.

  2. Metabonomics classifies pathways affected by bioactive compounds. Artificial neural network classification of NMR spectra of plant extracts.

    Science.gov (United States)

    Ott, Karl-Heinz; Araníbar, Nelly; Singh, Bijay; Stockton, Gerald W

    2003-03-01

    The biochemical mode-of-action (MOA) for herbicides and other bioactive compounds can be rapidly and simultaneously classified by automated pattern recognition of the metabonome that is embodied in the 1H NMR spectrum of a crude plant extract. The ca. 300 herbicides that are used in agriculture today affect less than 30 different biochemical pathways. In this report, 19 of the most interesting MOAs were automatically classified. Corn (Zea mays) plants were treated with various herbicides such as imazethapyr, glyphosate, sethoxydim, and diuron, which represent various biochemical modes-of-action such as inhibition of specific enzymes (acetohydroxy acid synthase [AHAS], protoporphyrin IX oxidase [PROTOX], 5-enolpyruvylshikimate-3-phosphate synthase [EPSPS], acetyl CoA carboxylase [ACC-ase], etc.), or protein complexes (photosystems I and II), or major biological process such as oxidative phosphorylation, auxin transport, microtubule growth, and mitosis. Crude isolates from the treated plants were subjected to 1H NMR spectroscopy, and the spectra were classified by artificial neural network analysis to discriminate the herbicide modes-of-action. We demonstrate the use and refinement of the method, and present cross-validated assignments for the metabolite NMR profiles of over 400 plant isolates. The MOA screen also recognizes when a new mode-of-action is present, which is considered extremely important for the herbicide discovery process, and can be used to study deviations in the metabolism of compounds from a chemical synthesis program. The combination of NMR metabolite profiling and neural network classification is expected to be similarly relevant to other metabonomic profiling applications, such as in drug discovery.

  3. Magnetism, optical absorbance, and 19F NMR spectra of nafion films with self-assembling paramagnetic networks

    Energy Technology Data Exchange (ETDEWEB)

    Levin, E. M.; Chen, Q.; Bud' ko, S. L.

    2012-01-15

    Magnetization, optical absorbance, and {sup 19}F NMR spectra of Nafion transparent films as received and doped with Mn{sup 2+}, Co{sup 2+}, Fe{sup 2+}, and Fe{sup 3+} ions with and without treatment in 1H-1,2,4-triazole (trz) have been studied. Doping of Nafion with Fe{sup 2+} and Co{sup 2+} and their bridging to nitrogen of triazole yields a hybrid self-assembling paramagnetic system that exhibits interesting magnetic and optical properties. These include spin crossover phenomena between high-spin (HS) and low-spin (LS) states in Nafion-Fe{sup 2+}-trz and Nafion-Co{sup 2+}-trz accompanied by thermochromic effects in the visible range induced by temperature. A large shift of the magnetization curve induced by a magnetic field in the vicinity of the HS {leftrightarrow} LS, {approx}220 K, observed for Nafion-Fe{sup 2+}-trz has a rate of {approx}6 K/kOe, which is about three orders of magnitude larger than that in bulk spin crossover Fe{sup 2+} materials. Selective response of {sup 19}F NMR signals on doping with paramagnetic ions demonstrates that NMR can be used as spatially resolved method to study Nafion film with paramagnetic network. Both chemical shift and width of {sup 19}F NMR signals show that SO groups of Nafion, Fe or Co ions, and nitrogen of triazole are bonded whereas they form a spin crossover system. Based on a model of nanosize cylinders proposed for Nafion [K. Schmidt-Rohr and Q. Chen, Nat Mater (2008), 75], we suggest that paramagnetic ions are located inside these cylinders, forming self-assembling magnetically and optically active nanoscale networks.

  4. Substituent Effects in the 13C-NMR Spectra of Six-Membered Nitrogen Heteroaromatic Compounds

    Directory of Open Access Journals (Sweden)

    Janusz Oszczapowicz

    2005-01-01

    Full Text Available Abstract: It is shown that the 13C-NMR chemical shifts of carbon atoms in substituted sixmembered heteroaromatic compounds correlate with the correponding "additivity parameters" for substituted benzene derivatives. Thus, for precalculation of chemical shifts in such compounds, just one set of parameters can be used. The differences between experimental chemical shifts and those calculated from correlation with the common set may provide insights into intramolecular interactions not reported in the literature.

  5. Automatic Assignment of Methyl-NMR Spectra of Supramolecular Machines Using Graph Theory.

    Science.gov (United States)

    Pritišanac, Iva; Degiacomi, Matteo T; Alderson, T Reid; Carneiro, Marta G; Ab, Eiso; Siegal, Gregg; Baldwin, Andrew J

    2017-07-19

    Methyl groups are powerful probes for the analysis of structure, dynamics and function of supramolecular assemblies, using both solution- and solid-state NMR. Widespread application of the methodology has been limited due to the challenges associated with assigning spectral resonances to specific locations within a biomolecule. Here, we present Methyl Assignment by Graph Matching (MAGMA), for the automatic assignment of methyl resonances. A graph matching protocol examines all possibilities for each resonance in order to determine an exact assignment that includes a complete description of any ambiguity. MAGMA gives 100% accuracy in confident assignments when tested against both synthetic data, and 9 cross-validated examples using both solution- and solid-state NMR data. We show that this remarkable accuracy enables a user to distinguish between alternative protein structures. In a drug discovery application on HSP90, we show the method can rapidly and efficiently distinguish between possible ligand binding modes. By providing an exact and robust solution to methyl resonance assignment, MAGMA can facilitate significantly accelerated studies of supramolecular machines using methyl-based NMR spectroscopy.

  6. A novel tridentate Schiff base dioxo-molybdenum(VI) complex: synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, ¹H NMR and ¹³C NMR spectra.

    Science.gov (United States)

    Saheb, Vahid; Sheikhshoaie, Iran; Stoeckli-Evans, Helen

    2012-09-01

    A new dioxo-molybdenum(VI) complex [MoO(2)(L)(H(2)O)] has been synthesized, using 5-methoxy 2-[(2-hydroxypropylimino)methyl]phenol as tridentate ONO donor Schiff base ligand (H(2)L) and MoO(2)(acac)(2). The yellow crystals of the compound are used for single-crystal X-ray analysis and measuring Fourier Transform Infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the UV-visible, FTIR, (1)H NMR and (13)C NMR spectra of the compound. Vibrational assignments and analysis of the fundamental modes of the compound are performed. Time-dependent density functional theory (TDDFT) method is used to calculate the electronic transitions of the complex. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR shielding tensors computed at the B3LYP/DGDZVP level of theory is in agreement with experimental (1)H NMR spectra. However, the (13)C NMR shielding tensors computed at the B3LYP level, employing a combined basis set of DGDZVP for Mo and 6-31+G(2df,p) for other atoms, are in better agreement with experimental (13)C NMR spectra. The electronic transitions calculated at the B3LYP/DGDZVP level by using TD-DFT method is in accordance with the observed UV-visible spectrum of the compound. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. A new Schiff base compound N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone): synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, 1H NMR and 13C NMR spectra.

    Science.gov (United States)

    Saheb, Vahid; Sheikhshoaie, Iran

    2011-10-15

    The Schiff base compound, N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone) (NDHA) is synthesized through the condensation of 2-hydroxylacetophenone and 2,2-dimethyl 1,3-amino propane in methanol at ambient temperature. The yellow crystalline precipitate is used for X-ray single-crystal determination and measuring Fourier transform infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP, PBEPBE and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the FTIR, (1)H NMR and (13)C NMR spectra of the compound. Time-dependent density functional theory (TDDFT) method is used to calculate the UV-visible spectrum of NDHA. Vibrational frequencies are determined experimentally and compared with those obtained theoretically. Vibrational assignments and analysis of the fundamental modes of the compound are also performed. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR and (13)C NMR chemical shifts calculated by all DFT methods are consistent with the experimental data. However, the NMR shielding tensors computed at the B3LYP/6-31+G(d,p) level of theory are in better agreement with experimental (1)H NMR and (13)C NMR spectra. The electronic absorption spectrum calculated at the B3LYP/6-31+G(d,p) level by using TD-DFT method is in accordance with the observed UV-visible spectrum of NDHA. In addition, some quantum descriptors of the molecule are calculated and conformational analysis is performed and the results were compared with the crystallographic data. Copyright © 2011 Elsevier B.V. All rights reserved.

  8. The INTEGRAL scatterometer SPI

    Science.gov (United States)

    Mandrou, P.; Vedrenne, G.; Jean, P.; Kandel, B.; vonBallmoos, P.; Albernhe, F.; Lichti, G.; Schoenfelder, V.; Diehl, R.; Georgii, R.; hide

    1997-01-01

    The INTErnational Gamma Ray Astrophysics Laboratory (INTEGRAL) mission's onboard spectrometer, the INTEGRAL spectrometer (SPI), is described. The SPI constitutes one of the four main mission instruments. It is optimized for detailed measurements of gamma ray lines and for the mapping of diffuse sources. It combines a coded aperture mask with an array of large volume, high purity germanium detectors. The detectors make precise measurements of the gamma ray energies over the 20 keV to 8 MeV range. The instrument's characteristics are described and the Monte Carlo simulation of its performance is outlined. It will be possible to study gamma ray emission from compact objects or line profiles with a high energy resolution and a high angular resolution.

  9. Optical detection of NMR J-spectra at zero magnetic field.

    Science.gov (United States)

    Ledbetter, M P; Crawford, C W; Pines, A; Wemmer, D E; Knappe, S; Kitching, J; Budker, D

    2009-07-01

    Scalar couplings of the form JI(1) x I(2) between nuclei impart valuable information about molecular structure to nuclear magnetic-resonance spectra. Here we demonstrate direct detection of J-spectra due to both heteronuclear and homonuclear J-coupling in a zero-field environment where the Zeeman interaction is completely absent. We show that characteristic functional groups exhibit distinct spectra with straightforward interpretation for chemical identification. Detection is performed with a microfabricated optical atomic magnetometer, providing high sensitivity to samples of microliter volumes. We obtain 0.1 Hz linewidths and measure scalar-coupling parameters with 4-mHz statistical uncertainty. We anticipate that the technique described here will provide a new modality for high-precision "J spectroscopy" using small samples on microchip devices for multiplexed screening, assaying, and sample identification in chemistry and biomedicine.

  10. Optical detection of NMR J-spectra at zero magnetic field

    CERN Document Server

    Ledbetter, M P; Pines, A; Wemmer, D E; Knappe, S; Kitching, J; Budker, D

    2009-01-01

    Scalar couplings of the form J I_1 \\cdot I_2 between nuclei impart valuable information about molecular structure to nuclear magnetic-resonance spectra. Here we demonstrate direct detection of J-spectra due to both heteronuclear and homonuclear J-coupling in a zero-field environment where the Zeeman interaction is completely absent. We show that characteristic functional groups exhibit distinct spectra with straightforward interpretation for chemical identification. Detection is performed with a microfabricated optical atomic magnetometer, providing high sensitivity to samples of microliter volumes. We obtain 0.1 Hz linewidths and measure scalar-coupling parameters with 4-mHz statistical uncertainty. We anticipate that the technique described here will provide a new modality for high-precision "J spectroscopy" using small samples on microchip devices for multiplexed screening, assaying, and sample identification in chemistry and biomedicine.

  11. Crystal structures and 77Se NMR spectra of molybdenum(IV) areneselenolates having intramolecular NH...Se hydrogen bonds.

    Science.gov (United States)

    Okamura, Taka-Aki; Taniuchi, Kaku; Lee, Keonil; Yamamoto, Hitoshi; Ueyama, Norikazu; Nakamura, Akira

    2006-11-13

    Salts of the monooxomolybdenum(IV,V) areneselenolates having intramolecular NH...Se hydrogen bonds, [Mo(IV)O(Se-2-RCONHC6H4)4]2- (R = t-Bu, CH3, CF3) and [Mo(V)O(Se-2-t-BuCONHC6H4)4]-, were synthesized and characterized by 1H nuclear magnetic resonance (NMR), 77Se NMR, electron spin resonance (ESR), UV-visible spectra, X-ray analysis, and electrochemical measurements. 77Se-1H correlated spectroscopy (COSY) indicated a significant correlation between amide 1H and selenolate 77Se atoms through an NH...Se hydrogen bond with 1J(77Se-1H) = 5.4 Hz coupling. The hydrogen bonds contribute to the positive shift in the Mo(V)/Mo(IV) redox potential. In the crystal structure of (PPh4)2[Mo(IV)O(Se-2-CH3CONHC6H4)4], an NH...O=Mo hydrogen bond was found. Ab inito calculations support the presence of intramolecular NH...O=Mo and NH...Se hydrogen bonds.

  12. New insight into hydration and aging mechanisms of paper by the line shape analysis of proton NMR spectra

    Science.gov (United States)

    Mallamace, D.; Vasi, S.; Missori, M.; Corsaro, C.

    2016-05-01

    The action of water within biological systems is strictly linked either with their physical chemical properties and with their functions. Cellulose is one of the most studied biopolymers due to its biological importance and its wide use in manufactured products. Among them, paper is mainly constituted by an almost equimolar ratio of cellulose and water. Therefore the study of the behavior of water within pristine and aged paper samples can help to shed light on the degradation mechanisms that irremediably act over time and spoil paper. In this work we present Nuclear Magnetic Resonance (NMR) experiments on modern paper samples made of pure cellulose not aged and artificially aged as well as on ancient paper samples made in 1413 in Perpignan (France). The line shape parameters of the proton NMR spectra were studied as a function of the hydration content. Results indicate that water in aged samples is progressively involved in the hydration of the byproducts of cellulose degradation. This enhances the degradation process itself through the progressive consumption of the cellulose amorphous regions.

  13. Structure of dimethylphenyl betaine hydrochloride studied by X-ray diffraction, DFT calculation, NMR and FTIR spectra

    Science.gov (United States)

    Szafran, M.; Katrusiak, A.; Dega-Szafran, Z.; Kowalczyk, I.

    2013-01-01

    The structure of dimethylphenyl betaine hydrochloride (1) has been studied by X-ray diffraction, DFT calculations, NMR and FTIR spectra. The crystals are monoclinic, space group P21/c. In the crystal, the Cl- anion is connected with protonated betaine through the O-H⋯Cl- hydrogen bond of 2.943(2) Å. The structures in the gas phase (2) and water solution (3) have been optimized by the B3LYP/6-311++G(d,p) approach and the geometrical results have been compared with the X-ray data of 1. The FTIR spectrum of the solid compound is consistent with the X-ray results. The probable assignments of the anharmonic experimental vibrational frequencies of the investigated chloride (1) based on the calculated harmonic frequencies in water solution (3) are proposed. The correlations between the experimental 1H and 13C NMR chemical shifts (δexp) of 1 in D2O and the magnetic isotropic shielding constants (σcalc) calculated by the GIAO/B3LYP/6-311G++(d,p) approach, using the screening solvation model (COSMO), δexp = a + b σcalc, for optimized molecule 3 in water solution are linear and correctly reproduce the experimental chemical shifts.

  14. A systematic approach to obtain validated partial least square models for predicting lipoprotein subclasses from serum NMR spectra.

    Science.gov (United States)

    Mihaleva, Velitchka V; van Schalkwijk, Daniël B; de Graaf, Albert A; van Duynhoven, John; van Dorsten, Ferdinand A; Vervoort, Jacques; Smilde, Age; Westerhuis, Johan A; Jacobs, Doris M

    2014-01-07

    A systematic approach is described for building validated PLS models that predict cholesterol and triglyceride concentrations in lipoprotein subclasses in fasting serum from a normolipidemic, healthy population. The PLS models were built on diffusion-edited (1)H NMR spectra and calibrated on HPLC-derived lipoprotein subclasses. The PLS models were validated using an independent test set. In addition to total VLDL, LDL, and HDL lipoproteins, statistically significant PLS models were obtained for 13 subclasses, including 5 VLDLs (particle size 64-31.3 nm), 4 LDLs (particle size 28.6-20.7 nm) and 4 HDLs (particle size 13.5-9.8 nm). The best models were obtained for triglycerides in VLDL (0.82 < Q(2) <0.92) and HDL (0.69 < Q(2) <0.79) subclasses and for cholesterol in HDL subclasses (0.68 < Q(2) <0.96). Larger variations in the model performance were observed for triglycerides in LDL subclasses and cholesterol in VLDL and LDL subclasses. The potential of the NMR-PLS model was assessed by comparing the LPD of 52 subjects before and after a 4-week treatment with dietary supplements that were hypothesized to change blood lipids. The supplements induced significant (p < 0.001) changes on multiple subclasses, all of which clearly exceeded the prediction errors.

  15. Effects of anoxia on 31P NMR spectra of Phycomyces blakesleeanus during development

    Directory of Open Access Journals (Sweden)

    Stanić Marina

    2009-01-01

    Full Text Available The method of 31P NMR spectroscopy was used to investigate the effects of anoxia on Phycomyces blakesleea­nus mycelium during development. The greatest changes were recorded in the PPc, NADH, and α-ATP signals. Decrease of PPc signal intensity is due to chain length reduction and reduction in number of PPn molecules. Smaller decrease of β-ATP compared to α-ATP signal intensity can be attributed to maintenance of ATP concentration at the expense of PPn hydrolysis. Sensitivity to anoxia varies with the growth stage. It is greatest in 32-h and 44-h mycelium, in which PPn is used as an additional energy source, while the smallest effect was noted for 36-h fungi.

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

    Science.gov (United States)

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

    1991-01-01

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

  17. 1H MAS NMR spectra of hy- droxyl species on diatomite surface

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    High spinning speed 1H magic-angle spinning nuclear magnetic resonance (1H MAS NMR) was used to detect surface hydroxyl groups of diatomite, which include isolated hydroxyl groups and hydrogen-bonded hydroxyl groups, and water adsorbed on diatomite surface that include pore water and hydrogen-bonded water. The corresponding proton chemical shifts of above species are ca. 2.0, 6.0-7.1, 4.9 and 3.0 respectively. Accompanied by thermal treatment temperature ascending, the pore water and hydrogen-bonded water are desorbed successively. As a result, the relative intensities of the peaks assigned to protons of isolat-ed hydroxyl groups and hydrogen-bonded hydroxyl groups increase gradually and reach their maxima at 1000℃. After 1100℃ calcination, the hydroxyl groups that classified to strongly hydrogen-bonded ones and the isolated hydroxyl groups condense basically. But some weakly hydrogen-bonded hydroxyl groups may still persist in the micropores.

  18. Evaluation of standard and advanced preprocessing methods for the univariate analysis of blood serum 1H-NMR spectra.

    Science.gov (United States)

    De Meyer, Tim; Sinnaeve, Davy; Van Gasse, Bjorn; Rietzschel, Ernst-R; De Buyzere, Marc L; Langlois, Michel R; Bekaert, Sofie; Martins, José C; Van Criekinge, Wim

    2010-10-01

    Proton nuclear magnetic resonance ((1)H-NMR)-based metabolomics enables the high-resolution and high-throughput assessment of a broad spectrum of metabolites in biofluids. Despite the straightforward character of the experimental methodology, the analysis of spectral profiles is rather complex, particularly due to the requirement of numerous data preprocessing steps. Here, we evaluate how several of the most common preprocessing procedures affect the subsequent univariate analyses of blood serum spectra, with a particular focus on how the standard methods perform compared to more advanced examples. Carr-Purcell-Meiboom-Gill 1D (1)H spectra were obtained for 240 serum samples from healthy subjects of the Asklepios study. We studied the impact of different preprocessing steps--integral (standard method) and probabilistic quotient normalization; no, equidistant (standard), and adaptive-intelligent binning; mean (standard) and maximum bin intensity data summation--on the resonance intensities of three different types of metabolites: triglycerides, glucose, and creatinine. The effects were evaluated by correlating the differently preprocessed NMR data with the independently measured metabolite concentrations. The analyses revealed that the standard methods performed inferiorly and that a combination of probabilistic quotient normalization after adaptive-intelligent binning and maximum intensity variable definition yielded the best overall results (triglycerides, R = 0.98; glucose, R = 0.76; creatinine, R = 0.70). Therefore, at least in the case of serum metabolomics, these or equivalent methods should be preferred above the standard preprocessing methods, particularly for univariate analyses. Additional optimization of the normalization procedure might further improve the analyses.

  19. Sensitivity gains, linearity, and spectral reproducibility in nonuniformly sampled multidimensional MAS NMR spectra of high dynamic range

    Science.gov (United States)

    Suiter, Christopher L.; Paramasivam, Sivakumar; Hou, Guangjin; Sun, Shangjin; Rice, David; Hoch, Jeffrey C.; Rovnyak, David

    2014-01-01

    Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear 13C–13C correlation spectra. We demonstrate on model compounds and on 1–73-(U-13C, 15N)/74–108-(U-15N) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7–2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear 13C–13C MAS correlation experiments that yield high-quality artifact-free datasets. PMID:24752819

  20. Sensitivity Gains, Linearity, and Spectral Reproducibility in Nonuniformly Sampled Multidimensional MAS NMR Spectra of High Dynamic Range.

    Energy Technology Data Exchange (ETDEWEB)

    Suiter, Christopher L.; Paramasivam, Sivakumar; Hou, Guangjin; Sun, Shangjin; Rice, David M.; Hoch, Jeffrey C.; Rovnyak, David S.; Polenova, Tatyana E.

    2014-04-22

    Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear 13C–13C correlation spectra. We demonstrate on model compounds and on 1–73-(U-13C,15N)/74–108-(U-15N) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7–2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear 13C–13C MAS correlation experiments that yield high quality artifact-free datasets.

  1. ;Click; analytics for ;click; chemistry - A simple method for calibration-free evaluation of online NMR spectra

    Science.gov (United States)

    Michalik-Onichimowska, Aleksandra; Kern, Simon; Riedel, Jens; Panne, Ulrich; King, Rudibert; Maiwald, Michael

    2017-04-01

    Driven mostly by the search for chemical syntheses under biocompatible conditions, so called ;click; chemistry rapidly became a growing field of research. The resulting simple one-pot reactions are so far only scarcely accompanied by an adequate optimization via comparably straightforward and robust analysis techniques possessing short set-up times. Here, we report on a fast and reliable calibration-free online NMR monitoring approach for technical mixtures. It combines a versatile fluidic system, continuous-flow measurement of 1H spectra with a time interval of 20 s per spectrum, and a robust, fully automated algorithm to interpret the obtained data. As a proof-of-concept, the thiol-ene coupling between N-boc cysteine methyl ester and allyl alcohol was conducted in a variety of non-deuterated solvents while its time-resolved behaviour was characterized with step tracer experiments. Overlapping signals in online spectra during thiol-ene coupling could be deconvoluted with a spectral model using indirect hard modeling and were subsequently converted to either molar ratios (using a calibration-free approach) or absolute concentrations (using 1-point calibration). For various solvents the kinetic constant k for pseudo-first order reaction was estimated to be 3.9 h-1 at 25 °C. The obtained results were compared with direct integration of non-overlapping signals and showed good agreement with the implemented mass balance.

  2. A specialized database manager for interpretation of NMR spectra of synthetic glucides: JPD

    Science.gov (United States)

    Czaplicki, J.; Ponthus, C.

    1998-02-01

    The current communication presents a program, written specifically to create and handle a specialized database, containing NMR spectral patterns of various monosaccharidic units. The program's database format is compatible with that of the Aurelia/Amix Bruker software package. The software facilitates the search for J patterns included in the database and their comparison with an experimental spectrum, in order to identify the components of the studied system, including the contaminants. Nous présentons ici un logiciel écrit spécifiquement pour créer et gérer une base de données spécialisées, contenant les motifs du couplage J des unités monosaccharidiques différentes. Le format de la base de données est compatible avec le format utilisé par le logiciel Aurelia/Amix de Bruker. Le logiciel facilite la recherche des motifs J inclus dans la base de données de leurs comparaisons avec un spectre expérimental, afin d'identifier les constituants de l'échantillon étudié, et ses éventuelles impuretés.

  3. 1MAS NMR spectra of kao linite/formamide intercalation compound

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The high spinning speed 1H magic angle spinning nuclear magnetic resonance (1H MAS NMR) technique was employed to distinguish the two groups of surface hydroxyls of kaolinite and investigate the intercalation mechanism of kaolinite/formamide compound. The proton chemical shifts of the inner hydroxyl and inner surface hydroxyl of kaolinte are in the range of δ-1.3-0.9 and δ 2.4-3.0 respectively. After formamide intercalation three proton peaks were detected. The proton peak of the inner surface hydroxyls of the intercalation compound shifts to high-field with δ 2.3-2.7, which is assigned to the formation of the hydrogen bond between the inner surface hydroxyl and formamide carbonyl group. Whereas, the proton peak of the inner hydroxyl shifts to δ-0.3 toward low-field, that is attributed to van der Waal's effect between the inner hydroxyl proton and the amino group proton of the formamide which may be keyed into the ditrigonal hole of the kaolinite. The third peak, additional proton peak, is in the range of δ5.4-5.6, that is ascribed to the hydrogen bond formation between the amino group proton of formimide and SiO4 tetrahedral oxygen of the kaolinite.

  4. Relativistic force field: parametric computations of proton-proton coupling constants in (1)H NMR spectra.

    Science.gov (United States)

    Kutateladze, Andrei G; Mukhina, Olga A

    2014-09-05

    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. Study of Structural Stability of Cyclophilin A by NMR and Circular Dichroism Spectra

    Institute of Scientific and Technical Information of China (English)

    SHI, Yan-Hong; LIN, Dong-Hai; HUANG, Jian-Ying; SHEN, Xu

    2006-01-01

    The structural stability of cyclophilin A (CypA) was investigated using H/D exchange and temperature coefficients of chemical shifts of amide protons, monitored by 2D heteronuclear NMR spectroscopy. Amide proton exchange rates were measured by H/D exchange experiments for slow-exchange protons and measured by SEA (Solvent Exposed Amides)-HSQC experiments for fast-exchange protons. Temperature coefficients of chemical shifts and hydrogen exchange rates of amide protons show reasonably good correlation with the protein structure. Totally,44 out of 153 non-proline assigned residues still exist in 86 d of hydrogen-deuterium exchange at 4 ℃, suggesting that CypA structure should be highly stable. Residues in secondary structures of α2, β1, β2, β5,β6 and β7 might constitute the hydrophobic core of the protein. The change in free energy of unfolding ( AGuH2O ) of CypA was estimated to be (21.99± 1.53) kJ·mol-1 by circular dichroism (CD). The large free energy change is also an indicator of the high structural stability.

  6. RF Based Spy

    Directory of Open Access Journals (Sweden)

    Robot Prerna Jain

    2014-04-01

    Full Text Available The intention of this paper is to reduce human victims in terrorist attack such as 26/11. So this problem can be overcome by designing the RF based spy robot which involves wireless camera. so that from this we can examine rivals when it required. This robot can quietly enter into enemy area and sends us the information via wireless camera. On the other hand one more feature is added in this robot that is colour sensor. Colour sensor senses the colour of surface and according to that robot will change its colour. Because of this feature this robot can’t easily detected by enemies. The movement of this robot is wirelessly controlled by a hand held RF transmitter to send commands to the RF receiver mounted on the moving robot. Since human life is always Valueable, these robots are the substitution of soldiers in war areas. This spy robot can also be used in star hotels, shopping malls, jewelry show rooms, etc where there can be threat from intruders or terrorists.

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

    Science.gov (United States)

    Pelter, Michael W.; Walker, Natalie M.

    2012-01-01

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

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

    Science.gov (United States)

    Pelter, Michael W.; Walker, Natalie M.

    2012-01-01

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

  9. Infrared and NMR spectra, tautomerism, vibrational assignment, normal coordinate analysis, and quantum mechanical calculations of 4-amino-5-pyrimidinecarbonitrile.

    Science.gov (United States)

    Afifi, Mahmoud S; Farag, Rabei S; Shaaban, Ibrahim A; Wilson, Lee D; Zoghaib, Wajdi M; Mohamed, Tarek A

    2013-07-01

    The infrared (4000-200 cm(-1)) spectrum for 4-amino-5-pyrimidinecarbonitrile (APC, C5H4N4) was acquired in the solid phase. In addition, the (1)H and (13)C NMR spectra of APC were obtained in DMSO-d6 along with its mass spectrum. Initially, six isomers were hypothesized and then investigated by means of DFT/B3LYP and MP2(full) quantum mechanical calculations using a 6-31G(d) basis set. Moreover, the (1)H and (13)C NMR chemical shifts were predicted using a GIAO approximation at the 6-311+G(d,p) basis set and the B3LYP method with (and without) solvent effects using PCM method. The correlation coefficients showed good agreement between the experimental/theoretical chemical shift values of amino tautomers (1 and 2) rather than the eliminated imino tautomers (3-6), in agreement with the current quantum mechanical calculations. Structures 3-6 are less stable than the amino tautomers (1 and 2) by about 5206-8673 cm(-1) (62.3-103.7 kJ/mol). The MP2(full)/6-31G(d) computational results favor the amino structure 1 with a pyramidal NH2 moiety and calculated real vibrational frequencies, however; structure 2 is considered a transition state owing to the calculated imaginary frequency. It is worth mentioning that, the calculated structural parameters suggest a strong conjugation between the amino nitrogen and pyrimidine ring. Aided by frequency calculations, normal coordinate analysis, force constants and potential energy distributions (PEDs), a complete vibrational assignment for the observed bands is proposed herein. Finally, NH2 internal rotation barriers for the stable non-planar isomer (1) were carried out using MP2(full)/6-31G(d) optimized structural parameters. Our results are discussed herein and compared to structural parameters for similar molecules whenever appropriate.

  10. Preparation of platinum(IV) complexes with dipeptide and diimine. X-ray crystal structure and 195Pt NMR spectra.

    Science.gov (United States)

    Watabe, Masatoshi; Fukuda, Hiroto; Kitsukawa, Koichiro; Nakajima, Hiroshi; Yukawa, Yasuhiko; Igarashi, Satoshi; Fujii, Yuki; Takayama, Toshio

    2006-10-01

    We prepared platinum(IV) complexes containing dipeptide and diimine or diamine, the [PtCl(dipeptide-N,N,O)(diimine or diamine)]Cl complex, where -N,N,O means dipeptide coordinated as a tridentate chelate, dipeptide=glycylglycine (NH(2)CH(2)CON(-)CH(2)COO(-), digly, where two protons of dipeptide are detached when the dipeptide coordinates to metal ion as a tridentate chelate), glycyl-L-alanine (NH(2)CH(2)CON(-)CHCH(3)COO(-), gly-L-ala), L-alanylglycine (NH(2)CH CH(3)CON(-)CH(2)COO(-), L-alagly), or L-alanyl-L-alanine (NH(2)CHCH(3)CON(-)CHCH(3)COO(-), dil-ala), and diimine or diamine=bipyridine (bpy), ethylenediamine (en), N-methylethylenediamine (N-Me-en), or N,N'-dimethylethylenediamine (N,N'-diMe-en). In the complexes containing gly-L-ala or dil-ala, two separate peaks of the (195)Pt NMR spectra of the [PtCl(dipeptide-N,N,O)(diimine or diamine)]Cl complexes appeared in, but in the complexes containing digly or L-alagly, one peak which contained two overlapped signals appeared. One of the two complexes containing gly-L-ala and bpy, [PtCl(gly-L-ala-N,N,O)(bpy)]NO(3), crystallized and was analyzed. This complex has the monoclinic space group P2(1)2(1)2(1) with unit cell dimensions of a=9.7906(3)A, b=11.1847(2)A, c=16.6796(2)A, Z=4. The crystal data revealed that this [PtCl(gly-L-ala-N,N,O)(bpy)]NO(3) complex has the near- (Cl, CH(3)) configuration of two possible isomers. Based on elemental analysis, the other complex must have the near- (Cl, CH(3))-[PtCl(gly-L-ala-N,N,O)(bpy)]NO(3) configuration. The (195)Pt NMR chemical shifts of the near- (Cl, CH(3))-[PtCl(gly-L-ala-N,N,O)(bpy)]NO(3) complex and the far- (Cl, CH(3))-[PtCl(gly-L-ala-N,N,O)(bpy)]NO(3) complex are 0 ppm and -19 ppm, respectively (0 ppm for the Na(2)[PtCl(6)] signal). The additive property of the (195)Pt NMR chemical shift is discussed. The (195)Pt NMR chemical shifts of [PtCl(dipeptide-N,N,O)(bpy)]Cl appeared at a higher field when the H attached to the dipeptide carbon atom was replaced with a

  11. sup 29 Si magic angle spinning NMR spectra of alkali metal, alkaline earth metal, and rare earth metal ion exchanged Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Chao, Kueijung; Chern, Jeryoung (Tsinghua Univ., Taiwan (China))

    1989-02-23

    The variation of the extraframework cation location in groups IA and IIA metals and rare earth metal (RE) Y zeolites as a function of the dehydration and the rehydration is monitored by {sup 29}Si MAS NMR. Unheated hydrated zeolites give similar {sup 29}Si spectra as they present the similar cation distributions. Upon dehydration a high-field shift is observed which correlates with the distortion of bond angles in silicon-oxygen tetrahedra. The line shapes of {sup 29}Si spectra depend on the nature and the location of the exchangeable cations and the occupancy of the different sites in dehydrated and rehydrated states. The correlation between the line shape of {sup 29}Si spectra and the migration of cations from the supercages to the sodalite cages after heating treatment was studied. The results of {sup 29}Si NMR agree with the known structure data.

  12. Indirect two-dimensional heteronuclear NMR spectroscopy. (/sup 31/P, /sup 57/Fe) spectra of organoiron complexes

    Energy Technology Data Exchange (ETDEWEB)

    Benn, R.; Brenneke, H.; Frings, A.; Lehmkuhl, H.; Mehler, G.; Rufinska, A.; Wildt, T.

    1988-08-17

    The indirect heteronuclear two-dimensional (2D) triple-resonance (S,I)-(/sup 1/H) NMR spectroscopy is introduced for measuring the chemical shift and scalar spin-spin coupling constants of an insensitive nucleus I via its scalar coupling J(S,I) by detection of the nucleus S of higher sensitivity. The versatility of this approach is demonstrated by extracting delta(/sup 57/Fe) and J(Fe,X) from (/sup 31/P,/sup 57/Fe)-(/sup 1/H) spectra of various dissolved ((/eta//sup 5/-Cp)(L/sub 2/(R)))Fe, ((/eta//sup 3/-allyl)(/eta//sup 5/-Cp)(L))Fe, and ((/eta//sup 1/,/eta//sup 2/-alkenyl)(/eta//sup 5/-Cp)(L))Fe complexes (R = alkyl, hydride; L = PR/sub 3/). In practice the sensitivity of 2D (/sup 31/P,/sup 57/Fe) spectra was found to be higher than that of the direct observation scheme by at least a factor (..gamma../sub P//..gamma../sub Fe/)/sup 5/2/. Due to the intrinsically higher resolving power of a two-dimensional experiment, small scalar couplings like /sup 2J/(Fe,F) and /sup 1/J(Fe,H) were readily obtained from indirect two-dimensional spectra. Combinations of (/sup 1/H,/sup 57/Fe) and (/sup 31/P,/sup 57/Fe) spectra yielded the relative signs of the J(Fe,X) couplings: /sup 1/J(Fe,P) is positive and increases with increasing ..pi..-acceptor power of the phosphorus ligand L from 55 (L = PMe/sub 3/, R = H) to 149 Hz (L = PF/sub 3/). /sup 1/J(Fe,H) is around +9 Hz (R = H), whereas /sup 2/J(P,H) in these complexes was found to be negative. In all of the allyl complexes investigated, /sup 2J/(Fe,F) (L = PF/sub 3/) is positive and around 3 Hz. In the quasi-tetragonal and -trigonal iron complexes, delta(/sup 57/Fe) varies by about 4000 ppM. This can be rationalized qualitatively by the electronegativity of the atoms directly bonded to iron and the higher oxidation potential in the presence of more basic ligands L via the paramagnetic shielding term. 52 references, 5 figures, 5 tables.

  13. 1D 13C-NMR Data as Molecular Descriptors in Spectra — Structure Relationship Analysis of Oligosaccharides

    Directory of Open Access Journals (Sweden)

    Florbela Pereira

    2012-03-01

    Full Text Available Spectra-structure relationships were investigated for estimating the anomeric configuration, residues and type of linkages of linear and branched trisaccharides using 13C-NMR chemical shifts. For this study, 119 pyranosyl trisaccharides were used that are trimers of the α or β anomers of D-glucose, D-galactose, D-mannose, L-fucose or L-rhamnose residues bonded through a or b glycosidic linkages of types 1→2, 1→3, 1→4, or 1→6, as well as methoxylated and/or N-acetylated amino trisaccharides. Machine learning experiments were performed for: (1 classification of the anomeric configuration of the first unit, second unit and reducing end; (2 classification of the type of first and second linkages; (3 classification of the three residues: reducing end, middle and first residue; and (4 classification of the chain type. Our previously model for predicting the structure of disaccharides was incorporated in this new model with an improvement of the predictive power. The best results were achieved using Random Forests with 204 di- and trisaccharides for the training set—it could correctly classify 83%, 90%, 88%, 85%, 85%, 75%, 79%, 68% and 94% of the test set (69 compounds for the nine tasks, respectively, on the basis of unassigned chemical shifts.

  14. Study of molecular structure, vibrational, electronic and NMR spectra of oncocalyxone A using DFT and quantum chemical calculations

    Science.gov (United States)

    Joshi, Bhawani Datt; Srivastava, Anubha; Honorato, Sara Braga; Tandon, Poonam; Pessoa, Otília Deusdênia Loiola; Fechine, Pierre Basílio Almeida; Ayala, Alejandro Pedro

    2013-09-01

    Oncocalyxone A (C17H18O5) is the major secondary metabolite isolated from ethanol extract from the heartwood of Auxemma oncocalyx Taub popularly known as “pau branco”. Oncocalyxone A (Onco A) has many pharmaceutical uses such as: antitumor, analgesic, antioxidant and causative of inhibition of platelet activation. We have performed the optimized geometry, total energy, conformational study, molecular electrostatic potential mapping, frontier orbital energy gap and vibrational frequencies of Onco A employing ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) method with 6-311++G(d, p) basis set. Stability of the molecule arising from hyperconjugative interactions and/or charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-vis spectrum of the compound was recorded in DMSO and MeOH solvent. The TD-DFT calculations have been performed to explore the influence of electronic absorption spectra in the gas phase, as well as in solution environment using IEF-PCM and 6-31G basis set. The 13C NMR chemical shifts have been calculated with the B3LYP/6-311++G(d, p) basis set and compared with the experimental values. These methods have been used as tools for structural characterization of Onco A.

  15. Study of molecular structure, vibrational, electronic and NMR spectra of oncocalyxone A using DFT and quantum chemical calculations.

    Science.gov (United States)

    Joshi, Bhawani Datt; Srivastava, Anubha; Honorato, Sara Braga; Tandon, Poonam; Pessoa, Otília Deusdênia Loiola; Fechine, Pierre Basílio Almeida; Ayala, Alejandro Pedro

    2013-09-01

    Oncocalyxone A (C17H18O5) is the major secondary metabolite isolated from ethanol extract from the heartwood of Auxemma oncocalyx Taub popularly known as "pau branco". Oncocalyxone A (Onco A) has many pharmaceutical uses such as: antitumor, analgesic, antioxidant and causative of inhibition of platelet activation. We have performed the optimized geometry, total energy, conformational study, molecular electrostatic potential mapping, frontier orbital energy gap and vibrational frequencies of Onco A employing ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) method with 6-311++G(d,p) basis set. Stability of the molecule arising from hyperconjugative interactions and/or charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-vis spectrum of the compound was recorded in DMSO and MeOH solvent. The TD-DFT calculations have been performed to explore the influence of electronic absorption spectra in the gas phase, as well as in solution environment using IEF-PCM and 6-31G basis set. The (13)C NMR chemical shifts have been calculated with the B3LYP/6-311++G(d,p) basis set and compared with the experimental values. These methods have been used as tools for structural characterization of Onco A.

  16. The Simple Publishing Interface (SPI)

    NARCIS (Netherlands)

    Ternier, Stefaan; Massart, David; Totschnig, Michael; Klerkx, Joris; Duval, Erik

    2010-01-01

    Ternier, S., Massart, D., Totschnig, M., Klerkx, J., & Duval, E. (2010). The Simple Publishing Interface (SPI). D-Lib Magazine, September/October 2010, Volume 16 Number 9/10, doi:10.1045/september2010-ternier

  17. The Simple Publishing Interface (SPI)

    NARCIS (Netherlands)

    Ternier, Stefaan; Massart, David; Totschnig, Michael; Klerkx, Joris; Duval, Erik

    2010-01-01

    Ternier, S., Massart, D., Totschnig, M., Klerkx, J., & Duval, E. (2010). The Simple Publishing Interface (SPI). D-Lib Magazine, September/October 2010, Volume 16 Number 9/10, doi:10.1045/september2010-ternier

  18. Evaluation of the reliability of the maximum entropy method for reconstructing 3D and 4D NOESY-type NMR spectra of proteins.

    Science.gov (United States)

    Shigemitsu, Yoshiki; Ikeya, Teppei; Yamamoto, Akihiro; Tsuchie, Yuusuke; Mishima, Masaki; Smith, Brian O; Güntert, Peter; Ito, Yutaka

    2015-02-06

    Despite their advantages in analysis, 4D NMR experiments are still infrequently used as a routine tool in protein NMR projects due to the long duration of the measurement and limited digital resolution. Recently, new acquisition techniques for speeding up multidimensional NMR experiments, such as nonlinear sampling, in combination with non-Fourier transform data processing methods have been proposed to be beneficial for 4D NMR experiments. Maximum entropy (MaxEnt) methods have been utilised for reconstructing nonlinearly sampled multi-dimensional NMR data. However, the artefacts arising from MaxEnt processing, particularly, in NOESY spectra have not yet been clearly assessed in comparison with other methods, such as quantitative maximum entropy, multidimensional decomposition, and compressed sensing. We compared MaxEnt with other methods in reconstructing 3D NOESY data acquired with variously reduced sparse sampling schedules and found that MaxEnt is robust, quick and competitive with other methods. Next, nonlinear sampling and MaxEnt processing were applied to 4D NOESY experiments, and the effect of the artefacts of MaxEnt was evaluated by calculating 3D structures from the NOE-derived distance restraints. Our results demonstrated that sufficiently converged and accurate structures (RMSD of 0.91Å to the mean and 1.36Å to the reference structures) were obtained even with NOESY spectra reconstructed from 1.6% randomly selected sampling points for indirect dimensions. This suggests that 3D MaxEnt processing in combination with nonlinear sampling schedules is still a useful and advantageous option for rapid acquisition of high-resolution 4D NOESY spectra of proteins.

  19. Revolutionaries and spies: Spy-good and spy-bad graphs

    CERN Document Server

    Butterfield, Jane V; Puleo, Gregory J; West, Douglas B; Zamani, Reza

    2012-01-01

    We study a game played on a graph $G$ by a team of $r$ {\\it revolutionaries} and a team of $s$ {\\it spies}. Initially, revolutionaries and then spies take positions at vertices. In each subsequent round, each revolutionary may move to an adjacent vertex or not move, and then each spy has the same option. The revolutionaries win by holding a meeting of $m$ revolutionaries at some vertex having no spy at the end of a round; the spies win if they can prevent this forever. Let $\\sigma(G,m,r)$ denote the minimum number of spies needed to win. Trivially, $\\min\\{\\floor{r/m},|V(G)|\\}\\le \\sigma(G,m,r)\\le r-m+1$. We prove that $\\sigma(G,m,r)$ equals the lower bound whenever $G$ has a rooted spanning tree $T$ such that every edge of $G$ not in $T$ joins two vertices having the same parent in $T$. Such graphs include graphs that have a dominating vertex. In general, $\\sigma(G,m,r)\\le\\gamma(G)\\floor{r/m}$, where $\\gamma(G)$ is the domination number, and this bound is nearly sharp when $\\gamma(G)\\le m$. For fixed $r$ and $...

  20. Fast MinMax energy-based phase correction method for NMR spectra with linear phase distortion

    Science.gov (United States)

    Zieliński, Tomasz P.; Duda, Krzysztof; Ostrowska, Katarzyna

    2017-08-01

    This paper addresses the problem of phase correction of dense NMR spectra on the example of the etoxy derivative of the fused heterocyclic system 5,6,10b-triazaacephenanthrylene (TAAP-OEt). A new estimation method for the linear phase correction coefficients is proposed that successfully extends the min-max (minimization of maximum errors) approach of Siegel (1981). Distinctive to the Siegel method, the smallest values of the real part of the discrete Fourier transform (DFT) spectrum are maximized, not for the whole spectrum but only for DFT bins near the peaks selected by a new energy-based criterion. Additionally, the method makes use of two one-parameter optimizations for finding the phase correction line coefficients and not the single two-parameter search. The new method is demonstrated to be precise, fast and robust against additive noise. The method's properties are verified in comparison with the state-of-the-art algorithms of Chen et al. (2002) and Bao et al. (2013) for laboratory recorded TAAP-OEt FID data and for simulated TAAP-OEt signal consisting of the sum of more than 100 complex damped exponentials. Extensive simulations were also conducted on the set of test signals derived from the TAAP-OEt signal by deterministic and pseudorandom manipulation of its content. The components of the signal model were identified by the Bertocco-Yoshida Interpolated DFT (IpDFT) algorithm with a spectral leakage correction. Simulated signals were embedded in the additive Gaussian noise, and the noise-robustness of all of the algorithms was evaluated. The obtained results demonstrate that the proposed method outperforms the Chen and the Bao algorithms, being more than 100 times faster than the Bao method (for a signal having 216 samples).

  1. A Simple Approach for Obtaining High Resolution, High Sensitivity ¹H NMR Metabolite Spectra of Biofluids with Limited Mass Supply

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Jian Zhi; Rommereim, Donald N.; Wind, Robert A.; Minard, Kevin R.; Sears, Jesse A.

    2006-11-01

    A simple approach is reported that yields high resolution, high sensitivity ¹H NMR spectra of biofluids with limited mass supply. This is achieved by spinning a capillary sample tube containing a biofluid at the magic angle at a frequency of about 80Hz. A 2D pulse sequence called ¹H PASS is then used to produce a high-resolution ¹H NMR spectrum that is free from magnetic susceptibility induced line broadening. With this new approach a high resolution ¹H NMR spectrum of biofluids with a volume less than 1.0 µl can be easily achieved at a magnetic field strength as low as 7.05T. Furthermore, the methodology facilitates easy sample handling, i.e., the samples can be directly collected into inexpensive and disposable capillary tubes at the site of collection and subsequently used for NMR measurements. In addition, slow magic angle spinning improves magnetic field shimming and is especially suitable for high throughput investigations. In this paper first results are shown obtained in a magnetic field of 7.05T on urine samples collected from mice using a modified commercial NMR probe.

  2. Synthesis and NMR Spectral Analysis of Amine Heterocycles: The Effect of Asymmetry on the [superscript 1]H and [superscript 13]C NMR Spectra of N,O-Acetals

    Science.gov (United States)

    Saba, Shahrokh; Ciaccio, James A.; Espinal, Jennifer; Aman, Courtney E.

    2007-01-01

    The stereochemical investigation is conducted to give students the combined experience of chemical synthesis of amines and N-heterocycles and structural stereochemical analysis using NMR spectroscopy. Students are introduced to the concept of topicity-stereochemical relationships between ligands within a molecule by synthesizing N,O-acetals.

  3. MetIDB: A Publicly Accessible Database of Predicted and Experimental 1H NMR Spectra of Flavonoids

    NARCIS (Netherlands)

    Mihaleva, V.V.; Beek, te T.A.; Zimmeren, van F.; Moco, S.I.A.; Laatikainen, R.; Niemitz, M.; Korhonen, S.P.; Driel, van M.A.; Vervoort, J.

    2013-01-01

    Identification of natural compounds, especially secondary metabolites, has been hampered by the lack of easy to use and accessible reference databases. Nuclear magnetic resonance (NMR) spectroscopy is the most selective technique for identification of unknown metabolites. High quality 1H NMR (proton

  4. Noninvasive Recognition and Biomarkers of Early Allergic Asthma in Cats Using Multivariate Statistical Analysis of NMR Spectra of Exhaled Breath Condensate

    Science.gov (United States)

    Fulcher, Yan G.; Fotso, Martial; Chang, Chee-Hoon; Rindt, Hans; Reinero, Carol R.

    2016-01-01

    Asthma is prevalent in children and cats, and needs means of noninvasive diagnosis. We sought to distinguish noninvasively the differences in 53 cats before and soon after induction of allergic asthma, using NMR spectra of exhaled breath condensate (EBC). Statistical pattern recognition was improved considerably by preprocessing the spectra with probabilistic quotient normalization and glog transformation. Classification of the 106 preprocessed spectra by principal component analysis and partial least squares with discriminant analysis (PLS-DA) appears to be impaired by variances unrelated to eosinophilic asthma. By filtering out confounding variances, orthogonal signal correction (OSC) PLS-DA greatly improved the separation of the healthy and early asthmatic states, attaining 94% specificity and 94% sensitivity in predictions. OSC enhancement of multi-level PLS-DA boosted the specificity of the prediction to 100%. OSC-PLS-DA of the normalized spectra suggest the most promising biomarkers of allergic asthma in cats to include increased acetone, metabolite(s) with overlapped NMR peaks near 5.8 ppm, and a hydroxyphenyl-containing metabolite, as well as decreased phthalate. Acetone is elevated in the EBC of 74% of the cats with early asthma. The noninvasive detection of early experimental asthma, biomarkers in EBC, and metabolic perturbation invite further investigation of the diagnostic potential in humans. PMID:27764146

  5. Conformational studies of 3-[(2,2-dimethylhydrazinyl)methylene]-pentane-2,4-dione using vibrational and NMR spectra, X-ray analysis and ab initio calculations

    Science.gov (United States)

    Gatial, Anton; Herich, Peter; Tarabová, Denisa; Milata, Viktor; Prónayová, Nadežda

    2017-07-01

    The conformers of push-pull 3-[(2,2-dimethylhydrazinyl)methylene]-pentane-2,4-dione (CH3)2Nsbnd NHsbnd CHdbnd C(COCH3)2 (DMHMP) have been studied experimentally by NMR and vibrational spectroscopy and theoretically by ab initio calculations at MP2 and DFT B3LYP levels in various basis sets. The NMR spectra were obtained in chloroform and dimethylsulfoxide and the IR and Raman spectra of DMHMP as a solid and as a solute in various less and more polar solvents at room temperature have been recorded. DMHMP was prepared as a pure solid and the data from X-ray analysis revealed that DMHMP exists in solid state as EZa conformer with an intramolecular hydrogen bond. The geometries and relative energies of possible conformers of DMHMP were evaluated at the both levels of theory in several basis sets and compared with the data from X-ray analysis. According to the NMR spectra the studied compound exists as a single entity. On the other hand vibrational spectra revealed that in less polar DMHMP solutions the presence of the second less polar ZZa conformer is possible, whereas in more polar solvent only one EZa conformer is observed. The influence of the environment polarity on this conformational equilibrium is discussed with respect to the SCRF solvent effect calculations using IEFPCM model. The observed IR and Raman bands were compared with calculated MP2/cc-pVTZ harmonic vibrational frequencies and assigned on the basis of potential energy distribution.

  6. Identification of Lignin and Polysaccharide Modifications in Populus Wood by Chemometric Analysis of 2D NMR Spectra from Dissolved Cell Walls

    Institute of Scientific and Technical Information of China (English)

    Mattias Hedenstrom; Susanne Wiklund-Lindstrom; Tommy (O)man; Fachuang Lu; Lorenz Gerber; Paul Schatz; Bj(o)rn Sundberg; John Ralph

    2009-01-01

    2D ~(13)C-~1H HSQC NMR spectroscopy of acetylated cell walls in solution gives a detailed fingerprint that can be used to assess the chemical composition of the complete wall without extensive degradation. We demonstrate how multivariate analysis of such spectra can be used to visualize cell wall changes between sample types as high-resolution 2D NMR loading spectra. Changes in composition and structure for both lignin and polysaccharides can subsequently be interpreted on a molecular level. The multivariate approach alleviates problems associated with peak picking of overlap-ping peaks, and it allows the deduction of the relative importance of each peak for sample discrimination. As a first proof of concept, we compare Populus tension wood to normal wood. All well established differences in cellulose, hemicellulose, and lignin compositions between these wood types were readily detected, confirming the reliability of the multivariate approach. In a second example, wood from transgenic Populus modified in their degree of pectin methylesterification was compared to that of wild-type trees. We show that differences in both lignin and polysaccharide composition that are difficult to detect with traditional spectral analysis and that could not be a priori predicted were revealed by the multi-variate approach. 2D NMR of dissolved cell wall samples combined with multivariate analysis constitutes a novel approach in cell wall analysis and provides a new tool that will benefit cell wall research.

  7. A NMR reverse diffusion filter for the simplification of spectra of complex mixtures and the study of drug receptor interactions.

    Science.gov (United States)

    Vega-Vázquez, M; Cobas, J C; Oliveira de Sousa, F F; Martin-Pastor, M

    2011-08-01

    A reverse diffusion filter NMR experiment (Drev) is proposed for the study of small molecules in binding with macromolecules. The filtering efficiency of Drev to eliminate the signals of the macromolecule is shown to be superior to conventional transverse relaxation filters at least for macromolecules containing a significant fraction of flexible residues. The Drev filter was also a useful complement for ligand-based NMR screening in combination with saturation transfer difference experiments.

  8. Separation of small metabolites and lipids in spectra from biopsies by diffusion-weighted HR-MAS NMR: a feasibility study.

    Science.gov (United States)

    Diserens, G; Vermathen, M; Precht, C; Broskey, N T; Boesch, C; Amati, F; Dufour, J-F; Vermathen, P

    2015-01-07

    High Resolution Magic Angle Spinning (HR-MAS) NMR allows metabolic characterization of biopsies. HR-MAS spectra from tissues of most organs show strong lipid contributions that are overlapping metabolite regions, which hamper metabolite estimation. Metabolite quantification and analysis would benefit from a separation of lipids and small metabolites. Generally, a relaxation filter is used to reduce lipid contributions. However, the strong relaxation filter required to eliminate most of the lipids also reduces the signals for small metabolites. The aim of our study was therefore to investigate different diffusion editing techniques in order to employ diffusion differences for separating lipid and small metabolite contributions in the spectra from different organs for unbiased metabonomic analysis. Thus, 1D and 2D diffusion measurements were performed, and pure lipid spectra that were obtained at strong diffusion weighting (DW) were subtracted from those obtained at low DW, which include both small metabolites and lipids. This subtraction yielded almost lipid free small metabolite spectra from muscle tissue. Further improved separation was obtained by combining a 1D diffusion sequence with a T2-filter, with the subtraction method eliminating residual lipids from the spectra. Similar results obtained for biopsies of different organs suggest that this method is applicable in various tissue types. The elimination of lipids from HR-MAS spectra and the resulting less biased assessment of small metabolites have potential to remove ambiguities in the interpretation of metabonomic results. This is demonstrated in a reproducibility study on biopsies from human muscle.

  9. Controlling Macromolecular Topology with Genetically Encoded SpyTag-SpyCatcher Chemistry

    OpenAIRE

    Zhang, Wen-Bin; Sun, Fei; Tirrell, David A.; Arnold, Frances H.

    2013-01-01

    Control of molecular topology constitutes a fundamental challenge in macromolecular chemistry. Here we describe the synthesis and characterization of artificial elastin-like proteins (ELPs) with unconventional nonlinear topologies including circular, tadpole, star, and H-shaped proteins using genetically encoded SpyTag–SpyCatcher chemistry. SpyTag is a short polypeptide that binds its protein partner SpyCatcher and forms isopeptide bonds under physiological conditions. Sequences encoding SpyT...

  10. H/D isotope effect of {sup 1}H MAS NMR spectra and {sup 79}Br NQR frequencies of piperidinium p-bromobenzoate and pyrrolidinium p-bromobenzoate

    Energy Technology Data Exchange (ETDEWEB)

    Honda, Hisashi, E-mail: hhonda@yokohama-cu.ac.jp [Yokohama City University, Graduate School of Nanobioscience (Japan); Kyo, Shinshin [Yokohama City University, Faculty of Sciences (Japan); Akaho, Yousuke [Yokohama City University, Faculty of International College of Arts and Sciences (Japan); Takamizawa, Satoshi [Yokohama City University, Graduate School of Nanobioscience (Japan); Terao, Hiromitsu [Tokushima University, Faculty of Integrated Arts and Sciences (Japan)

    2010-04-15

    H/D isotope effects onto {sup 79}Br NQR frequencies of piperidinium p-bromobenzoate were studied by deuterium substitution of hydrogen atoms which form two kinds of N-H Midline-Horizontal-Ellipsis O type hydrogen bonds, and the isotope shift of ca. 100 kHz were detected for a whole observed temperature range. In addition, {sup 1}H MAS NMR spectra measurements of piperidinium and pyrrolidinium p-bromobenzoate were carried out and little isotope changes of NMR line shape were detected. In order to reveal effects of molecular arrangements into the obtained isotope shift of NQR frequencies, single-crystal X-ray measurement of piperidinium p-bromobenzoate-d2 and density-functional-theory calculation were carried out. Our estimation showed the dihedral-angle change between piperidine and benzene ring contributes to isotope shift rather than those of N-H lengths by deuterium substitution.

  11. N-15 NMR spectra of naturally abundant nitrogen in soil and aquatic natural organic matter samples of the International Humic Substances Society

    Science.gov (United States)

    Thorn, K.A.; Cox, L.G.

    2009-01-01

    The naturally abundant nitrogen in soil and aquatic NOM samples from the International Humic Substances Society has been characterized by solid state CP/MAS 15N NMR. Soil samples include humic and fulvic acids from the Elliot soil, Minnesota Waskish peat and Florida Pahokee peat, as well as the Summit Hill soil humic acid and the Leonardite humic acid. Aquatic samples include Suwannee River humic, fulvic and reverse osmosis isolates, Nordic humic and fulvic acids and Pony Lake fulvic acid. Additionally, Nordic and Suwannee River XAD-4 acids and Suwannee River hydrophobic neutral fractions were analyzed. Similar to literature reports, amide/aminoquinone nitrogens comprised the major peaks in the solid state spectra of the soil humic and fulvic acids, along with heterocyclic and amino sugar/terminal amino acid nitrogens. Spectra of aquatic samples, including the XAD-4 acids, contain resolved heterocyclic nitrogen peaks in addition to the amide nitrogens. The spectrum of the nitrogen enriched, microbially derived Pony Lake, Antarctica fulvic acid, appeared to contain resonances in the region of pyrazine, imine and/or pyridine nitrogens, which have not been observed previously in soil or aquatic humic substances by 15N NMR. Liquid state 15N NMR experiments were also recorded on the Elliot soil humic acid and Pony Lake fulvic acid, both to examine the feasibility of the techniques, and to determine whether improvements in resolution over the solid state could be realized. For both samples, polarization transfer (DEPT) and indirect detection (1H-15N gHSQC) spectra revealed greater resolution among nitrogens directly bonded to protons. The amide/aminoquinone nitrogens could also be observed by direct detection experiments.

  12. N-15 NMR spectra of naturally abundant nitrogen in soil and aquatic natural organic matter samples of the International Humic Substances Society

    Energy Technology Data Exchange (ETDEWEB)

    Thorn, Kevin A.; Cox, Larry G.

    2009-02-28

    The naturally abundant nitrogen in soil and aquatic NOM samples from the International Humic Substances Society has been characterized by solid state CP/MAS ¹⁵N NMR. Soil samples include humic and fulvic acids from the Elliot soil, Minnesota Waskish peat and Florida Pahokee peat, as well as the Summit Hill soil humic acid and the Leonardite humic acid. Aquatic samples include Suwannee River humic, fulvic and reverse osmosis isolates, Nordic humic and fulvic acids and Pony Lake fulvic acid. Additionally, Nordic and Suwannee River XAD-4 acids and Suwannee River hydrophobic neutral fractions were analyzed. Similar to literature reports, amide/aminoquinone nitrogens comprised the major peaks in the solid state spectra of the soil humic and fulvic acids, along with heterocyclic and amino sugar/terminal amino acid nitrogens. Spectra of aquatic samples, including the XAD-4 acids, contain resolved heterocyclic nitrogen peaks in addition to the amide nitrogens. The spectrum of the nitrogen enriched, microbially derived Pony Lake, Antarctica fulvic acid, appeared to contain resonances in the region of pyrazine, imine and/or pyridine nitrogens, which have not been observed previously in soil or aquatic humic substances by ¹⁵N NMR. Liquid state ¹⁵N NMR experiments were also recorded on the Elliot soil humic acid and Pony Lake fulvic acid, both to examine the feasibility of the techniques, and to determine whether improvements in resolution over the solid state could be realized. For both samples, polarization transfer (DEPT) and indirect detection (¹H–¹⁵N gHSQC) spectra revealed greater resolution among nitrogens directly bonded to protons. The amide/aminoquinone nitrogens could also be observed by direct detection experiments.

  13. Ultrafast Magic-Angle Spinning: Benefits for the Acquisition of Ultrawide-Line NMR Spectra of Heavy Spin-1/2 Nuclei.

    Science.gov (United States)

    Pöppler, Ann-Christin; Demers, Jean-Philippe; Malon, Michal; Singh, Amit Pratap; Roesky, Herbert W; Nishiyama, Yusuke; Lange, Adam

    2016-03-16

    The benefits of the ultrafast magic-angle spinning (MAS) approach for the acquisition of ultrawide-line NMR spectra-spectral simplification, increased mass sensitivity allowing the fast study of small amounts of material, efficient excitation, and application to multiple heavy nuclei-are demonstrated for tin(II) oxide (SnO) and the tin complex [(LB)Sn(II) Cl](+) [Sn(II) Cl3 ](-) [LB=2,6-diacetylpyridinebis(2,6-diisopropylanil)] containing two distinct tin environments. The ultrafast MAS experiments provide optimal conditions for the extraction of the chemical-shift anisotropy tensor parameters, anisotropy, and asymmetry for heavy spin-1/2 nuclei.

  14. /sup 13/C NMR spectra of cyclic nitrones. 1. 2-substituted 4-methyl- and 4-phenyl-1-hydroxy-5,5-dimethyl-3-imidazoline 3-oxides

    Energy Technology Data Exchange (ETDEWEB)

    Grigor' ev, I.A.; Martin, V.V.; Shchukin, G.I.; Mamatyuk, V.I.; Volodarskii, L.B.

    1985-08-01

    The introduction of an N-oxide oxygen atom into azomethines leads to an upfield shift of the signals for the carbon atom of the C=N group in the /sup 13/C NMR spectra by 30-33 ppm. This is consistent with the increase in the electron density on this atom. The signal of the nitrone carbon atom is observed in the region of 140-147 ppm, depending on the nature of the substituent at the C/sub (2)/ atom of the 3-imidazoline 3-oxide ring.

  15. Secrets of a covalent interaction for biomaterials and biotechnology: SpyTag and SpyCatcher.

    Science.gov (United States)

    Reddington, Samuel C; Howarth, Mark

    2015-12-01

    SpyTag is a short peptide that forms an isopeptide bond upon encountering its protein partner SpyCatcher. This covalent peptide interaction is a simple and powerful tool for bioconjugation and extending what protein architectures are accessible. Here we review the origin and mechanism of SpyTag/SpyCatcher, focusing on recent innovative applications. Ligation of targeting-antibody with antigen provided a simple route to vaccine generation. SpyRings, from head-to-tail cyclisation, gave major enhancements in enzyme resilience. Linking multiple SpyCatchers gave dendrimers for T-cell activation or Spy networks forming hydrogels for stem cell culture. Synthetic biology applications include integrating amyloid biomaterials with living bacteria, for irreversible derivatisation of biofilms with enzymes or nanoparticles. We also discuss further opportunities to apply and enhance SpyTag/SpyCatcher technology.

  16. Using a Problem Solving-Cooperative Learning Approach to Improve Students' Skills for Interpreting [Superscript 1]H NMR Spectra of Unknown Compounds in an Organic Spectroscopy Course

    Science.gov (United States)

    Angawi, Rihab F.

    2014-01-01

    To address third- and fourth-year chemistry students' difficulties with the challenge of interpreting [superscript 1]H NMR spectra, a problem solving-cooperative learning technique was incorporated in a Spectra of Organic Compounds course. Using this approach helped students deepen their understanding of the basics of [superscript 1]H NMR…

  17. Follow-up Observations of SPY White Dwarf + M-Dwarf Binaries

    NARCIS (Netherlands)

    Maxted, P.F.L.; Napiwotzki, R.; Marsh, T.R.; Burleigh, M.R.; Dobbie, P.D.; Hogan, E.; Nelemans, G.A.

    2007-01-01

    We present the results of follow-up observations of white-dwarf + M-dwarf binaries identified using spectra obtained as part of the SPY survey. Spectra of the Halpha region were obtained with the SPIRAL spectrograph on the AAT telescope. Of the eleven stars observed, seven are binaries with periods

  18. Anomalous resonances in 29Si and 27Al NMR spectra of pyrope ([Mg,Fe]3Al2Si3O12) garnets: effects of paramagnetic cations.

    Science.gov (United States)

    Stebbins, Jonathan F; Kelsey, Kimberly E

    2009-08-28

    In oxide and silicate materials, particularly naturally-occurring minerals with contents of iron oxides greater than a few percent, paramagnetic impurities are well-known to broaden MAS NMR peaks, decrease relaxation times, and even cause overall loss of signal intensity. However, detection of resolved, discrete peaks that are shifted in frequency by nearby unpaired electron spins is rare in such systems. We report here high-resolution (27)Al and (29)Si spectra for synthetic and natural samples of pyrope garnet ([Mg,Fe](3)Al(2)Si(3)O(12)), the latter containing up to 3.5 wt% FeO. For both nuclides, spectra contain anomalous NMR peaks at frequencies that are 25 to 200 ppm from normal ranges, possibly through pseudocontact shifts induced by paramagnetic cations. Quantitation of peak areas suggests that signals from nuclides with such cations in their first shell may be broadened enough to be unobservable, while those with paramagnetics in their second cation shells may be substantially shifted. Overall spin-lattice relaxation rates are greatly enhanced by such impurities, and shifted resonances relax much faster than the unshifted main peaks. A high symmetry crystal structure (in this case cubic), which limits the number of different cation-cation distances in each shell, combined with a relatively low (non-cubic) symmetry for the sites hosting the magnetic cations, may be needed to readily detect such features.

  19. Influence of the computerized {sup 31}P NMR spectra processing on the tissues pH determination precision; Wplyw obrobki cyfrowej widm {sup 31}P MRJ na dokladnosc pomiaru pH tkanek

    Energy Technology Data Exchange (ETDEWEB)

    Kupka, T. [Inst. Chemii, Univ. Slaski, Katowice (Poland)]|[Zaklad Ciala Stalego, Polska Akademia Nauk, Zabrze (Poland); Religa, Z.; Zembala, M.; Nozynski, J.; Wojtek, P. [Slaska Akademia Medyczna, Zabrze (Poland); Pasterna, G. [Inst. Fizyki, Univ. Slaski, Katowice (Poland); Makhyanov, N. [Nizhnekamskneftekhym, Nizhnekamsk, Tatarstan (Russian Federation)

    1995-12-31

    The {sup 31}P NMR spectra of different tissues have been measured. To improve the spectra resolution two method of Fourier transformation have been used and namely the CDRE (Convulsion Difference Resolution Enhancement) and LGM (Lorentz-to-Gaussian Multiplication). It was shown that these procedures allow one to improve the quality of measured spectra what results in better precision of the tissues pH determination. 5 refs, 2 figs.

  20. Anomalous peaks in NMR spectra of iron-containing silicate minerals: pseudo-contact shifts and the potential for mapping the distributions of transition metal ions

    Science.gov (United States)

    Stebbins, J. F.; Kelsey, K. E.

    2009-04-01

    High-resolution nuclear magnetic resonance (NMR) spectroscopy has now been applied to problems of mineral structure for more than 25 years. Early attempts to collect MAS spectra on natural minerals rich in iron (or other cations with unpaired electron spins, e.g. more than a few % FeO) showed serious peak broadening, loss of signal, and thus loss of structural information. Spectroscopists have thus largely avoided such materials and have worked either with low-Fe natural minerals (e.g. zeolites) or with Fe-free synthetic compositions. While this problem remains, it has recently become apparent that in silicates with minor contents of such elements (100's to 1000's of ppm), or, in special cases, with much higher contents (at least 4% FeO), NMR spectra of nuclides such as Si-29 and Al-27 may indeed provide interesting and useful structural information that may eventually reveal new details of cation distribution, ordering, clustering, etc. Here we report on the early stages of this new application. In a recent report (Stebbins, Panero, Smyth and Frost, Am. Min. in press) we noted the presence of a variety of tiny "extra" peaks in Si-29 spectra of forsterite and wadsleyite, both containing 10's to 1000's of ppm of transition metal impurities. Some of these have chemical shifts well outside the known range for diamagnetic silicates, and were hypothesized to result from "pseudo-contact" interactions with unpaired electrons, which depend strongly on local structure. Peak shifts of this type have long been known in Sn-119 and Y-89 spectra for oxides such as rare-earth stannates (Grey et al.), but have apparently not been previously reported for silicates. New data on Si-29 and Al-27 NMR of synthetic pyrope (0.6 % CoO) and natural pyropes from the Dora Maira massif (1.5 to 3.5 wt % FeO) also show "anomalous" resonances, some of which again fall well outside the range of normal chemical shifts (e.g. +140 ppm in a Si-29 spectrum, 70 and 35 ppm in the Al-27 spectrum of a

  1. SPI/INTEGRAL observation of the Cygnus region

    Science.gov (United States)

    Bouchet, L.; Jourdain, E.; Roques, J. P.; Mandrou, P.; von Ballmoos, P.; Boggs, S.; Caraveo, P.; Cassé, M.; Cordier, B.; Diehl, R.; Durouchoux, P.; von Kienlin, A.; Knodlseder, J.; Jean, P.; Leleux, P.; Lichti, G. G.; Matteson, J.; Sanchez, F.; Schanne, S.; Schoenfelder, V.; Skinner, G.; Strong, A.; Teegarden, B.; Vedrenne, G.; Wunderer, C.

    2003-11-01

    We present the analysis of the first observations of the Cygnus region by the SPI spectrometer onboard the Integral Gamma Ray Observatory, encompassing ~600 ks of data. Three sources namely Cyg X-1, Cyg X-3 and EXO 2030+375 were clearly detected. Our data illustrate the temporal variability of Cyg X-1 in the energy range from 20 keV to 300 keV. The spectral analysis shows a remarkable stability of the Cyg X-1 spectra when averaged over one day timescale. The other goal of these observations is SPI inflight calibration and performance verification. The latest objective has been achieved as demonstrated by the results presented in this paper.

  2. {sup 13}C-{sup 13}C NOESY spectra of a 480 kDa protein: solution NMR of ferritin

    Energy Technology Data Exchange (ETDEWEB)

    Matzapetakis, Manolis; Turano, Paola [University of Florence, Department of Chemistry, CERM (Italy); Theil, Elizabeth C. [Children' s Hospital Oakland Research Institute, CeBIC (Council for BioIron at CHORI) (United States); Bertini, Ivano [University of Florence, Department of Chemistry, CERM (Italy)], E-mail: ivanobertini@cerm.unifi.it

    2007-07-15

    Molecular size has limited solution NMR analyses of proteins. We report {sup 13}C-{sup 13}C NOESY experiments on a 480 kDa protein, the multi-subunit ferritin nanocage with gated pores. By exploiting {sup 13}C-resonance-specific chemical shifts and spin diffusion effects, we identified 75% of the amino acids, with intraresidue C-C connectivities between nuclei separated by 1-4 bonds. These results show the potential of {sup 13}C-{sup 13}C NOESY for solution studies of molecular assemblies >100 kDa.

  3. Binding modes of phosphonic acid derivatives adsorbed on TiO2 surfaces: Assignments of experimental IR and NMR spectra based on DFT/PBC calculations

    Science.gov (United States)

    Geldof, D.; Tassi, M.; Carleer, R.; Adriaensens, P.; Roevens, A.; Meynen, V.; Blockhuys, F.

    2017-01-01

    A DFT study on the adsorption of a series of phosphonic acids (PAs) on the TiO2 anatase (101) and (001) surfaces was performed. The adsorption energies and geometries of the most stable binding modes were compared to literature data and the effect of the inclusion of dispersion forces in the energy calculations was gauged. As the (101) surface is the most exposed surface of TiO2 anatase, the calculated chemical shifts and vibrational frequencies of PAs adsorbed on this surface were compared to experimental 31P and 17O NMR and IR data in order to assign the two possible binding modes (mono- and bidentate) to peaks and bands in these spectra; due to the corrugated nature of anatase (101) tridentate binding is not possible on this surface. Analysis of the calculated and experimental 31P chemical shifts indicates that both monodentate and bidentate binding modes are present. For the reactive (001) surface, the results of the calculations indicate that both bi- and tridentate binding modes result in stable systems. Due to the particular sensitivity of 17O chemical shifts to hydrogen bonding and solvent effects, the model used is insufficient to assign these spectra at present. Comparison of calculated and experimental IR spectra leads to the conclusion that IR spectroscopy is not suitable for the characterization of the different binding modes of the adsorption complexes.

  4. Absolute nutrient concentration measurements in cell culture media: 1H q-NMR spectra and data to compare the efficiency of pH-controlled protein precipitation versus CPMG or post-processing filtering approaches

    Directory of Open Access Journals (Sweden)

    Luca Goldoni

    2016-09-01

    Full Text Available The NMR spectra and data reported in this article refer to the research article titled “A simple and accurate protocol for absolute polar metabolite quantification in cell cultures using q-NMR” [1]. We provide the 1H q-NMR spectra of cell culture media (DMEM after removal of serum proteins, which show the different efficiency of various precipitating solvents, the solvent/DMEM ratios, and pH of the solution. We compare the data of the absolute nutrient concentrations, measured by PULCON external standard method, before and after precipitation of serum proteins and those obtained using CPMG (Carr-Purcell-Meiboom-Gill sequence or applying post-processing filtering algorithms to remove, from the 1H q-NMR spectra, the proteins signal contribution. For each of these approaches, the percent error in the absolute value of every measurement for all the nutrients is also plotted as accuracy assessment.

  5. Android/GUI Controlled Bluetooth Spy Robot (SPY-BOT

    Directory of Open Access Journals (Sweden)

    Nirmal K Thomas

    2017-05-01

    Full Text Available The robotic vehicle can be controlled by a PC or an android device. The GUI interface used to control the robot is developed in MATLAB, and the android app is developed using MIT appinventor 2. The robotic vehicle is equipped with an IP web camera for GUI interface and another wireless camera having night vision capability for remote monitoring/spying purposes. This system can be used in sensitive areas where humans cannot enter directly. The commands provided by android application/GUI interface are used to move the robot in front, back and left right directions. The vehicle consists of a Bluetooth receiver interfaced to a PIC microcontroller. On receiving command from the receiver, the PIC microcontroller operates on the movement of motor through a driver IC. The android device or laptop can operate the vehicle at a good Bluetooth communication range. The night vision camera mounted on robot allows for efficient spying even in darkest areas using infrared lighting.

  6. Molecular dynamics and information on possible sites of interaction of intramyocellular metabolites in vivo from resolved dipolar couplings in localized 1H NMR spectra

    Science.gov (United States)

    Schröder, Leif; Schmitz, Christian; Bachert, Peter

    2004-12-01

    Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl- L-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct 1H- 1H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized 1H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD0 ( S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 ( δ = 8 ppm) and H4 ( δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD0 from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution 1H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D0 (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 - 3) × 10 -4 indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 - 137) × 10 -4. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, 1H NMR experiments on aqueous model

  7. Metabolic trajectories based on 1H NMR spectra of urines from sheep exposed to nutritional challenges during prenatal and early postnatal life

    DEFF Research Database (Denmark)

    Nyberg, Nils; Nielsen, Mette Benedicte Olaf; Jaroszewski, Jerzy W.

    2010-01-01

    1H NMR metabolic profiles of urine from sheep exposed to prenatal nutritional restriction (n = 19) and a control group with normal prenatal nutritional requirements (n = 19), followed by either conventional (n = 10 + 10) or high carbohydrate high fat postnatal diet (n = 9 + 9), were studied. Urine...... was sampled from 2, 6, 19 and 24-month-old animals receiving differential dietary treatments during the first 6 months and the same normal diet later. Principal component analysis of 1H NMR spectra (n = 164) showed a V-shaped metabolic trajectory as a function of age and diet, starting with urines with a high...... amount of glucose, indicative of monogastric-like metabolism, and exhibiting concomitant increase of metabolites related to rumen microflora (mainly glycine conjugates of benzoic and phenylacetic acid) as the ruminal metabolism developed. Urines from young (2-month-old) animals exposed to prenatal...

  8. Anisotropy effect of three-membered rings in (1)H NMR spectra: quantification by TSNMRS and assignment of the stereochemistry.

    Science.gov (United States)

    Kleinpeter, Erich; Krüger, Stefanie; Koch, Andreas

    2015-05-07

    The spatial magnetic properties (through space NMR shieldings, TSNMRSs) of cyclopropane; of the heteroanalogous oxirane, thiirane, and aziridine; and of various substituted mono-, dis-, and tris-cyclic analogues have been computed by the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSSs) of various size and direction. The TSNMRS values, thus obtained, can be employed to visualize the anisotropy (ring current) effect of the cyclopropane ring moiety. This approach has been employed to qualify and quantify substituent influences and contributions of appropriate ring heteroatoms O, NH, and S on the anisotropy (ring current) effect of three-membered ring moieties, and to assign the stereochemistry of mono-, bis-, and tris-cyclic structures containing cyclopropane as a structural element. Characteristic examples are included.

  9. Peculiarities in the director reorientation and evolution of NMR spectra under the influence of crossed electric and magnetic fields

    Science.gov (United States)

    Zakharov, A. V.

    2016-12-01

    Theoretical description is proposed for new modes of reorientation of the director field widehat n and the evolution of the NMR spectrum I(ν) of a nematic liquid crystal (LC) formed by molecules of deuterated 4-n-pentyl-4'-cyanobiphenyl encapsulated in a rectangular LC cell under the action of crossed electric, E, and magnetic, B, fields directed at an angle of α to one another. Numerical calculations in the framework of the nonlinear generalization of the classical Ericksen-Leslie theory show that, under certain relations between the forces and moments acting upon a unit volume of the LC phase upon the reorientation of widehat n, transient periodic structures can arise if the corresponding distortion mode is characterized by the fastest response and thus suppresses all other modes, including uniform ones. It is shown that the rise of these periodic structures leads to a reduction in the time for the reorientation of the director field.

  10. FT-IR, FT-Raman, NMR and UV-Vis spectra and DFT calculations of 5-bromo-2-ethoxyphenylboronic acid (monomer and dimer structures).

    Science.gov (United States)

    Sas, E B; Kose, E; Kurt, M; Karabacak, M

    2015-02-25

    In this study, the Fourier Transform Infrared (FT-IR) and Fourier Transform Raman (FT-Raman) spectra of 5-bromo-2-ethoxyphenylboronic acid (5Br2EPBA) are recorded in the solid phase in the region 4000-400 cm(-1) and 3500-10 cm(-1), respectively. The (1)H, (13)C and DEPT nuclear magnetic resonance (NMR) spectra are recorded in DMSO solution. The UV-Vis absorption spectrum of 5Br2EPBA is saved in the range of 200-400 nm in ethanol and water. The following theoretical calculations for monomeric and dimeric structures are supported by experimental results. The molecular geometry and vibrational frequencies in the ground state are calculated by using DFT methods with 6-31G(d,p) and 6-311G(d,p) basis sets. There are four conformers for the present molecule. The computational results diagnose the most stable conformer of 5Br2EPBA as Trans-Cis (TC) form. The complete assignments are performed on the basis of the total energy distribution (TED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method in parallel quantum solutions (PQS) program. The (1)H and (13)C NMR chemical shifts of 5Br2EPBA molecule are calculated by using the Gauge Invariant Atomic Orbital (GIAO) method in DMSO and gas phase for monomer and dimer structures of the most stable conformer. Moreover, electronic properties, such as the HOMO and LUMO energies (by TD-DFT and CIS methods) and molecular electrostatic potential surface (MEPs) are investigated. Stability of the molecule arising from hyper-conjugative interactions, charge delocalization is analyzed using natural bond orbital (NBO) analysis. Nonlinear optical (NLO) properties and thermodynamic features are presented. All calculated results are compared with the experimental data of the title molecule. The correlation of theoretical and experimental results provides a detailed description of the structural and physicochemical properties of the title molecule.

  11. Scoping out the International Spy Museum

    Science.gov (United States)

    Radosh, Ronald

    2010-01-01

    The International Spy Museum in Washington, D.C.--a private museum that opened in July 2002 at the cost of $40 million--is rated as one of the most visited and popular tourist destinations in the nation's capital, despite stiff competition from the various public museums that are part of the Smithsonian. The popularity of the Spy Museum has a…

  12. Experimental FTIR, FT-IR (gas phase), FT-Raman and NMR spectra, hyperpolarizability studies and DFT calculations of 3,5-dimethylpyrazole.

    Science.gov (United States)

    Sundaraganesan, N; Kavitha, E; Sebastian, S; Cornard, J P; Martel, M

    2009-10-15

    In the present study, structural properties of 3,5-dimethylpyrazole (3,5-DMP) have been studied extensively utilizing density functional theory (DFT) employing B3LYP exchange correlation. The Fourier transform infrared (solid phase and gas phase) and Fourier transform Raman spectra of 3,5-DMP were recorded. The Vibrational frequencies of 3,5-DMP in the ground state have been calculated by using density functional method (B3LYP) with 6-31G(d,p), 6-311G(d,p) and 6-311++G(d,p) as basis sets. Comparison of the observed fundamental vibrational frequencies of 3,5-DMP with calculated results show that 6-311++G(d,p) superior to other basis sets for molecular vibrational problems. Non linear optical NLO behavior of the examined molecule was investigated by the determination of the electric dipole moment mu, the polarizability alpha and the hyperpolarizability beta using the B3LYP/cc-pvdz method. The isotropic chemical shifts computed by (13)C and (1)H NMR analysis also show good agreement with experimental observations. The theoretically predicted FTIR and FT-Raman spectra of the title molecule have been constructed.

  13. NMR of 133Cs+ in stretched hydrogels: One-dimensional, z- and NOESY spectra, and probing the ion's environment in erythrocytes

    Science.gov (United States)

    Kuchel, Philip W.; Shishmarev, Dmitry; Puckeridge, Max; Levitt, Malcolm H.; Naumann, Christoph; Chapman, Bogdan E.

    2015-12-01

    133Cs nuclear magnetic resonance (NMR) spectroscopy was conducted on 133Cs+ in gelatin hydrogels that were either relaxed or stretched. Stretching generated a septet from this spin-7/2 nucleus, and its nuclear magnetic relaxation was studied via z-spectra, and two-dimensional nuclear Overhauser (NOESY) spectroscopy. Various spectral features were well simulated by using Mathematica and the software package SpinDynamica. Spectra of CsCl in suspensions of human erythrocytes embedded in gelatin gel showed separation of the resonances from the cation inside and outside the cells. Upon stretching the sample, the extracellular 133Cs+ signal split into a septet, while the intracellular peak was unchanged, revealing different alignment/ordering properties of the environment inside and around the cells. Differential interference contrast light microscopy confirmed that the cells were stretched when the overall sample was elongated. Analysis of the various spectral features of 133Cs+ reported here opens up applications of this K+ congener for studies of cation-handling by metabolically-active cells and tissues in aligned states.

  14. NMR spectra and potentiometry studies of aluminum(III) binding with coenzyme NAD+ in acidic aqueous solutions.

    Science.gov (United States)

    Yang, Xiaodi; Bi, Shuping; Yang, Xiaoliang; Yang, Li; Hu, Jun; Liu, Jian; Yang, Zhengbiao

    2003-06-01

    Complexation and conformational studies of coenzyme NAD+ with aluminum were conducted in acidic aqueous solutions (pH 2-5) by means of potentiometry as well as multinuclear (1H, 13C, 31P, 27Al) and two-dimensional (1H, 1H-NOESY) NMR spectroscopy. These led to the following results: (1) Al could coordinate with NAD+ through the following binding sites: N7' of adenine and pyrophosphate free oxygen (O(A)1, O(N)1,O(A)2) to form various mononuclear 1:1 (AlLH23+, AlLH2+) and 2:1 (AlL2-) species, and dinuclear 2:2 (Al2L22+) species. (2) The conformations of NAD+ and Al-NAD+ depended on the solvents and different species in the complexes. The results suggest the occurrence of an Al-linked complexation, which causes structural changes at the primary recognition sites and secondary conformational alterations for coenzymes. This finding will help us to understand role of Al in biological enzyme reaction systems.

  15. Using Bulk Magnetic Susceptibility to Resolve Internal and External Signals in the NMR Spectra of Plant Tissues

    Science.gov (United States)

    Shachar-Hill, Yair; Befroy, Douglas E.; Pfeffer, Philip E.; Ratcliffe, R. George

    1997-07-01

    Internal and external NMR signals from a variety of plant cells and plant tissues can be resolved by changing the bulk magnetic susceptibility (BMS) of the perfusing medium with [Gd (EDTA)]-or Dy(DTPA-BMA). This separation is observed in samples consisting of cylindrical cells oriented along theB0field, and is consistent with established theoretical predictions about BMS effects. Evidence is presented that the shifted signals represent material outside the tissue as well as some contribution from intercellular spaces and cell walls, while intracellular signals are unshifted. The paramagnetic complexes used to separate the signals are shown to be nontoxic and to have no effect on a number of transport processes. The method has been applied to roots, shoots, and giant algal cells, facilitating the interpretation of thein vivospectra from a range of biologically important magnetic isotopes. The potential of the method for studies of transport is illustrated with experiments showing: (i)14N/15N isotopic exchange of nitrate in roots; (ii) the influx of HDO into root and shoot segments; and (iii) the use of saturation transfer to follow water movement into and out of plant cells.

  16. Polymeric Structure and Solid NMR Spectra of Cadmuim ( Ⅱ)Dialkyldithiophosphates(Alkyl=Propyl,Butyl,Isopropyl and Isobutyl)

    Institute of Scientific and Technical Information of China (English)

    尹业高; WILLIS; ,Forsling; 等

    2003-01-01

    By dropwise adding thio ligands to concentrated aqueous solutions of Cd(ClO4)2·6H2O ,polymeric complexes,Cd(Ⅱ)O,O′-dipropyldithiophosphate(1),O,O′-dibutyl-dithiophosphate(2),O,O′-diisopropyl-dithiophosphate(3) and O,O′-diisobutyl-dithiophos phate(4) were obtained.The structure of 4 was determined by Xray diffraction analysis,showing that the metal ion sits in distorted tetrahedral sulphur coordination sphere and that the eight-memberd bimetallic rings take the twist chair and boat conformations, alternately.Based on facts that the S(1)-Cd Bond length [0.25099(12)nm] is shorter than the other S-Cd bond length [0.25399(12)-0.25701(18)nm] and that the S(1)-involving angles [113.45(4)°-118.43(5)°] are systematically large than the normal angles of a tetrahedron,the ligands are hypothesized to be erratically functionalized to Cd(Ⅱ).To certify the steric nonequivalence of ligands,the compounds were investigated by solid 13C,31P and 113Cd NMR spectroscopy.

  17. SPI/INTEGRAL observation of the Cygnus region

    OpenAIRE

    Bouchet, L.; Jourdain, E; Roques, JP; Mandrou, P.; von Ballmoos, P.; Boggs, S; Caraveo, P.; Casse, M.; Cordier, B.; Diehl, R.; Durouchoux, P.; von Kienlin, A.; Knodlseder, J.; Jean, P.; Leleux, Pierre

    2003-01-01

    We present the analysis of the first observations of the Cygnus region by the SPI spectrometer onboard the Integral Gamma Ray Observatory, encompassing similar to600 ks of data. Three sources namely Cyg X-1, Cyg X-3 and EXO 2030+375 were clearly detected. Our data illustrate the temporal variability of Cyg X-1 in the energy range from 20 keV to 300 keV. The spectral analysis shows a remarkable stability of the Cyg X-1 spectra when averaged over one day timescale. The other goal of these obser...

  18. Infrared, Raman and NMR spectra, conformational stability, normal coordinate analysis and B3LYP calculations of 5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde

    Science.gov (United States)

    Bahgat, Khaled; EL-Emary, Talaat

    2013-02-01

    FT Raman and IR spectra of the crystallized biologically active molecule, 5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (5-APHC, C11H11N3O) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies of 5-APHC have been investigated with the help of B3LYP density functional theory (DFT) method with 6-31G(d) and 6-311+G(d,p) as basis set. The calculated molecular geometry has been compared with the experimental data. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field (SQM) technique. The optimized geometry shows the co-planarity of the aldehyde group with pyrazole ring. Potential energy surface (PES) scan studies has also been carried out by ab initio calculations with B3LYP/6-311+G(d,p) basis set. The red shifting of NH2 stretching wavenumber indicates the formation of N-H⋯O hydrogen bonding. 1H and 13C NMR spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-Vis spectrum of the compound was recorded in the region 200-400 nm and the electronic properties HOMO and LUMO energies were calculated by time-dependent TD-DFT approach. Mulliken charges of the 5-APHC molecule was also calculated and interpreted.

  19. The crystal structure Escherichia coli Spy.

    Science.gov (United States)

    Kwon, Eunju; Kim, Dong Young; Gross, Carol A; Gross, John D; Kim, Kyeong Kyu

    2010-11-01

    Escherichia coli spheroplast protein y (EcSpy) is a small periplasmic protein that is homologous with CpxP, an inhibitor of the extracytoplasmic stress response. Stress conditions such as spheroplast formation induce the expression of Spy via the Cpx or the Bae two-component systems in E. coli, though the function of Spy is unknown. Here, we report the crystal structure of EcSpy, which reveals a long kinked hairpin-like structure of four α-helices that form an antiparallel dimer. The dimer contains a curved oval shape with a highly positively charged concave surface that may function as a ligand binding site. Sequence analysis reveals that Spy is highly conserved over the Enterobacteriaceae family. Notably, three conserved regions that contain identical residues and two LTxxQ motifs are placed at the horizontal end of the dimer structure, stabilizing the overall fold. CpxP also contains the conserved sequence motifs and has a predicted secondary structure similar to Spy, suggesting that Spy and CpxP likely share the same fold.

  20. Compact NMR

    Energy Technology Data Exchange (ETDEWEB)

    Bluemich, Bernhard; Haber-Pohlmeier, Sabina; Zia, Wasif [RWTH Aachen Univ. (Germany). Inst. fuer Technische und Makromolekulare Chemie (ITMC)

    2014-06-01

    Nuclear Magnetic Resonance (NMR) spectroscopy is the most popular method for chemists to analyze molecular structures, while Magnetic Resonance Imaging (MRI) is a non-invasive diagnostic tool for medical doctors that provides high-contrast images of biological tissue. In both applications, the sample (or patient) is positioned inside a large, superconducting magnet to magnetize the atomic nuclei. Interrogating radio-frequency pulses result in frequency spectra that provide the chemist with molecular information, the medical doctor with anatomic images, and materials scientist with NMR relaxation parameters. Recent advances in magnet technology have led to a variety of small permanent magnets to allow compact and low-cost instruments. The goal of this book is to provide an introduction to the practical use of compact NMR at a level nearly as basic as the operation of a smart phone.

  1. Analysis list: Spi1 [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Spi1 Blood,Embryonic fibroblast,Neural,Pluripotent stem cell + mm9 http://dbarchive....biosciencedbc.jp/kyushu-u/mm9/target/Spi1.1.tsv http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/target/Spi1....5.tsv http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/target/Spi1.10.tsv http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/colo/Spi...1.Blood.tsv,http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/colo/Spi...1.Embryonic_fibroblast.tsv,http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/colo/Spi1.Neural.tsv,http://d

  2. Genetic diversity of Salmonella pathogenicity islands SPI-5 and SPI-6 in Salmonella Newport.

    Science.gov (United States)

    Cao, Guojie; Allard, Marc; Strain, Errol; Stones, Robert; Zhao, Shaohua; Brown, Eric; Meng, Jianghong

    2014-10-01

    Salmonella enterica subspecies enterica serotype Newport is one of the common serotypes causing foodborne salmonellosis outbreaks in the United States. Salmonella Newport consists of three lineages exhibiting extensive genetic diversity. Due to the importance of Salmonella pathogenicity islands 5 and 6 (SPI-5 and SPI-6) in virulence of pathogenic Salmonella, the genetic diversity of these two SPIs may relate to different potentials of Salmonella Newport pathogenicity. Most Salmonella Newport strains from North America belong to Salmonella Newport lineages II and III. A total 28 Salmonella Newport strains of lineages II and III from diverse sources and geographic locations were analyzed, and 11 additional Salmonella genomes were used as outgroup in phylogenetic analyses. SPI-5 was identified in all Salmonella Newport strains and 146 single nucleotide polymorphisms (SNPs) were detected. Thirty-nine lineage-defining SNPs were identified, including 18 nonsynonymous SNPs. Two 40-kb genomic islands (SPI5-GI1 and SPI5-GI2) encoding bacteriophage genes were found between tRNA-ser and pipA. SPI5-GI1 was only present in Salmonella Newport multidrug-resistant strains of lineage II. SPI-6 was found in all strains but three Asian strains in Salmonella Newport lineage II, whereas the three Asian strains carried genomic island SPI6-GI1 at the same locus as SPI-6 in other Salmonella. SPI-6 exhibited 937 SNPs, and phylogenetic analysis demonstrated that clustering of Salmonella Newport isolates was a reflection of their geographic origins. The sequence diversity within SPI-5 and SPI-6 suggests possible recombination events and different virulence potentials of Salmonella Newport. The SNPs could be used as biomarkers during epidemiological investigations.

  3. Correcting human heart 31P NMR spectra for partial saturation. Evidence that saturation factors for PCr/ATP are homogeneous in normal and disease states

    Science.gov (United States)

    Bottomley, Paul A.; Hardy, Christopher J.; Weiss, Robert G.

    Heart PCr/ATP ratios measured from spatially localized 31P NMR spectra can be corrected for partial saturation effects using saturation factors derived from unlocalized chest surface-coil spectra acquired at the heart rate and approximate Ernst angle for phosphor creatine (PCr) and again under fully relaxed conditions during each 31P exam. To validate this approach in studies of normal and disease states where the possibility of heterogeneity in metabolite T1 values between both chest muscle and heart and normal and disease states exists, the properties of saturation factors for metabolite ratios were investigated theoretically under conditions applicable in typical cardiac spectroscopy exams and empirically using data from 82 cardiac 31P exams in six study groups comprising normal controls ( n = 19) and patients with dilated ( n = 20) and hypertrophic ( n = 5) cardiomyopathy, coronary artery disease ( n = 16), heart transplants ( n = 19), and valvular heart disease ( n = 3). When TR ≪ T1,(PCr), with T1(PCr) ⩾ T1(ATP), the saturation factor for PCr/ATP lies in the range 1.5 ± 0.5, regardless of the T1 values. The precise value depends on the ratio of metabolite T1 values rather than their absolute values and is insensitive to modest changes in TR. Published data suggest that the metabolite T1 ratio is the same in heart and muscle. Our empirical data reveal that the saturation factors do not vary significantly with disease state, nor with the relative fractions of muscle and heart contributing to the chest surface-coil spectra. Also, the corrected myocardial PCr/ATP ratios in each normal or disease state bear no correlation with the corresponding saturation factors nor the fraction of muscle in the unlocalized chest spectra. However, application of the saturation correction (mean value, 1.36 ± 0.03 SE) significantly reduced scatter in myocardial PCr/ATP data by 14 ± 11% (SD) ( p ⩽ 0.05). The findings suggest that the relative T1 values of PCr and ATP are

  4. Infrared, Raman and NMR spectra, conformational stability, normal coordinate analysis and B3LYP calculations of 5-amino-4-cyano-3-(methylthio)-1H-pyrazole-1-carbothioamide

    Science.gov (United States)

    Mohamed, Tarek A.; Hassan, Ali M.; Soliman, Usama A.; Zoghaib, Wajdi M.; Husband, John; Abdelall, Mahmoud M.

    2011-01-01

    The Raman and infrared spectra of solid 5-amino-4-cyano-3-(methylthio)-1H-pyrazole-1-carbothioamide (AMPC, C 6H 7N 5S 2) were measured in the spectral range of 3700-100 cm -1 and 4000-200 cm -1 with a resolution of 4 and 0.5 cm -1, respectively. Aided by normal coordinate analysis and potential energy distributions, a confident vibrational assignment of all fundamentals is proposed herein. As a result of internal rotation around C sbnd N and/or C sbnd S bonds, 32 rotational isomers are suggested for AMPC (C s symmetry). RHF and DFT/B3LYP quantum mechanical calculations including polarization and diffusion functions up to 6-311++G(d,p) basis sets, predict that after complete relaxation of the 32 possible isomers, four structures lie within 1500 cm -1 of the lowest energy conformer. However, vibrational analysis reveals the lowest energy conformer to be the only structure giving all real frequencies. Thus, the only stable conformer of AMPC is shown to have a fully planar skeleton with the NH 2 groups trans to one another. The recorded IR and Raman spectral measurements favor the calculated structural parameters which are further supported by spectral simulation. Additional support is given by 1H and 13C NMR spectra recorded with the sample dissolved in DMSO-d 6 and by predicted chemical shifts at the B3LYP/6-311+G(2d,p) level obtained using the Gauge-Invariant Atomic Orbitals (GIAO) method with and without inclusion of solvent using the Polarizable Continuum Model (PCM). Finally, CH 3, CH 3S, and NH 2 torsional barriers to internal rotation have been investigated using the optimized structural parameters from the B3LYP method with the 6-31G(d) basis set. The results are discussed herein and compared with similar molecules whenever appropriate.

  5. Synthesis and conformational study of some r(2), c(4)-bis(isopropoxycarbonyl)- t(3)-aryl- c(5)-hydroxy- t(5)-methylcyclohexanones using NMR spectra

    Science.gov (United States)

    Pandiarajan, K.; Mohan, R. T. Sabapathy; Murugavel, K.; Hema, R.

    2008-03-01

    Seven r(2), c(4)-bis(isopropoxycarbonyl)- t(3)-aryl- c(5)-hydroxy- t(5)-methylcyclohexanones 7- 13 (aryl = C 6H 5, p-ClC 6H 4, p-FC 6H 4, p-OMeC 6H 4, p-Me 2NC 6H 4, m-O 2NC 6H 4 and m-C 6H 5OC 6H 4) have been synthesized by condensing isopropyl acetoacetate with aromatic aldehydes in the presence of methylamine. For all these compounds 1H and 13C NMR spectra have been recorded. For 7, HOMOCOSY, NOESY, HSQC and HMBC spectra also have been recorded. The spectral data suggest that compounds 7- 13 exist in chair conformation with axial orientation of the hydroxy group and equatorial orientations of all the other substituents. Long range coupling is observed between OH proton and H(6a) in all cases suggesting that OH group is anti to C(5) sbnd C(6) bond. In all cases four distinct doublets are observed for the methyl protons of the two isopropyl groups. In 7 and 13 four separate, closely spaced signals are observed for the methyl carbons of the two isopropyl groups. All signals could be assigned unambiguously in the case of 7. The protons of one methyl group of the isopropoxycarbonyl group at C-4 seems to be highly shielded. This suggests that these protons lie above the plane of the aryl group at C(3). This conclusion is in accordance with the structure of 7, determined by X-ray crystallography. MOPAC calculations on 7 suggest that the chair conformation with OH group anti to C(5) sbnd C(6) bond is more stable than the chair conformation with OH bond anti to C(5) sbnd CH 3 bond by 1.5 kcal mol -1.

  6. Regio-selective detection of dynamic structure of transmembrane alpha-helices as revealed from (13)C NMR spectra of [3-13C]Ala-labeled bacteriorhodopsin in the presence of Mn2+ ion.

    Science.gov (United States)

    Tuzi, S; Hasegawa, J; Kawaminami, R; Naito, A; Saitô, H

    2001-07-01

    13C Nuclear magnetic resonance (NMR) spectra of [3-(13)C]Ala-labeled bacteriorhodopsin (bR) were edited to give rise to regio-selective signals from hydrophobic transmembrane alpha-helices by using NMR relaxation reagent, Mn(2+) ion. As a result of selective suppression of (13)C NMR signals from the surfaces in the presence of Mn(2+) ions, several (13)C NMR signals of Ala residues in the transmembrane alpha-helices were identified on the basis of site-directed mutagenesis without overlaps from (13)C NMR signals of residues located near the bilayer surfaces. The upper bound of the interatomic distances between (13)C nucleus in bR and Mn(2+) ions bound to the hydrophilic surface to cause suppressed peaks by the presence of Mn(2+) ion was estimated as 8.7 A to result in the signal broadening to 100 Hz and consistent with the data based on experimental finding. The Ala C(beta) (13)C NMR peaks corresponding to Ala-51, Ala-53, Ala-81, Ala-84, and Ala-215 located around the extracellular half of the proton channel and Ala-184 located at the kink in the helix F were successfully identified on the basis of (13)C NMR spectra of bR in the presence of Mn(2+) ion and site-directed replacement of Ala by Gly or Val. Utilizing these peaks as probes to observe local structure in the transmembrane alpha-helices, dynamic conformation of the extracellular half of bR at ambient temperature was examined, and the local structures of Ala-215 and 184 were compared with those elucidated at low temperature. Conformational changes in the transmembrane alpha-helices induced in D85N and E204Q and its long-range transmission from the proton release site to the site around the Schiff base in E204Q were also examined.

  7. NMR (1H,13C) AND VIBRATIONAL SPECTRA OF SODIUM o-,m-,AND p- CHLOROBENZOATES%邻、间、对-氯苯甲酸钠的NMR(1H,13C)和振动光谱

    Institute of Scientific and Technical Information of China (English)

    P. Koczon; H. Baranska; W. Lewandowski

    1996-01-01

    Sodium o-, m-, and p-chlorobenzoates were under study. The vibrational and NMR spectra of compounds were recorded and studied. We have carried out single point calculations with energy optimized molecules. To establish influence of chlorine and sodium on the electronic charge distribution in the molecule, we have compared experimental data for ortho, m-, and p- chlorobenzoates with those for sodium benzoate, and o-, m-, and p-chlorobenzoic acids, respectively. Conclusions drawn from various methods are the same and indicate that chlorine and sodium perturbate the aromatic system of benzoic acid. The character of chlorine and sodium influence depends on position of chlorine in the ring. Correlation between calculated formal charge on carbon atoms and their chemical shifts were suggested.%研究了邻、间、对-氯苯甲酸钠并记录了这些化合物的NMR和振动光谱.用能量合适的分子做了单点计算,确立了氯和钠对分子中电荷分布的影响,并对邻、间、对氯苯甲酸钠分别与苯甲酸钠以及邻、间、对氯苯甲酸做了比较.从各种不同的方法中得出的结论是相同的,且表明氯和钠影响了苯甲酸的芳香体系,氯和钠的影响特征取决于氯在环上的位置,并在碳原子上计算的形式电荷和它的化学位移之间提出相关性.

  8. HOMO-LUMO, UV, NLO, NMR and vibrational analysis of 3-methyl-1-phenylpyrazole using FT-IR, FT-RAMAN FT-NMR spectra and HF-DFT computational methods

    Science.gov (United States)

    Carthigayan, K.; Xavier, S.; Periandy, S.

    2015-05-01

    In this paper, the spectral analysis of 3-methyl-1-phenylpyrazole is carried out using the FT-IR, FT Raman, FT NMR and UV-Vis spectra with the help of quantum mechanical computations using HF and density functional theories. The different conformers of the compound and their minimum energies are studied using B3LYP functional with 6-311+G (d, p) basis set and the most stable conformer with minimum energy was identified and the same conformer was used for further computations. The computed wave numbers from different methods are scaled so as to agree with the experimental values and the scaling factors are reported. All the modes of vibrations are assigned and the structure the molecule is analyzed in terms of parameters like bond length, bond angle and dihedral angle predicted by both HF and B3LYP methods with 6-311+G (d, p) and 6-311++G (d, p) basis sets. The values of dipole moment (μ), polarizability (α) and hyperpolarizability (β) of the molecule are reported, using which the non-linear property of the molecule is discussed. The HOMO-LUMO mappings are reported which reveals the different charge transfer possibilities within the molecule. The isotropic chemical shifts predicted for 1H and 13C atoms using gauge invariant atomic orbital (GIAO) theory show good agreement with experimental shifts. NBO analysis is carried out to picture the charge transfer between the localized bonds and lone pairs. The thermodynamic properties (heat capacity, entropy and enthalpy) at different temperatures are also calculated.

  9. Effect of organic matter application on CP-MAS-13C-NMR spectra of humic acids from a brown soil

    Science.gov (United States)

    Dou, S.

    2009-04-01

    -MAS-13C-NMR spectrum of HA. The CP-MAS- 13C-NMR spectra of the HA were quite similar to each other. These spectra exhibited signals for alkyl (0~50 ppm), O-alkyl (50~110 ppm), aromatic (110~160 ppm) and carbonyl (160~200 ppm) regions. The signals in carbonyl C region concentrated between 172 ppm and 173 ppm, and with a small signal occurred in the region of 190~200 ppm, indicating that there was carbonyl C of carboxylic acid, ester and amide, but a little amount carbonyl C of ketonic compounds. In the region of aromatic C, the most obvious peaks were the absorption at 131~133 ppm and 114~117 ppm. The former was mainly the aromatic C substituted by -COOH or -COOMe and the unsubstituted aromatic meta to carbons bearing an oxygen or nitrogen atom; the latter was mainly the unsubstituted aromatic C ortho and para to carbons bearing an oxygen and nitrogen atom. There was a small peak at 152-154ppm, which was the signal of phenolic OH. The signal at 55~56 ppm was methoxyl C. The signals at 71~73 ppm were due to the -CH(OH)- in carbohydrate. The peak at 102~103 ppm was generally assigned to double oxygen-C in polysaccharide (possibly acetal). The maximum absorption at 30 ppm was the contribution of the polymethylene chain -(CH2)n- in saturated hydrocarbons (Wilson, 1981). After OM application, the contents of alkyl C and O-alkyl C increased and the contents of aromatic C and carbonxyl C except to 1986 decreased. Compared with 1986, the contents of O-alkyl C increased and the contents of alkyl C decreased for the same treatment CKbr and O2. Aromaticity decreased significantly in OM treatments, indicating that the OM decreased the content of aromatic C and was simplified the molecular structure. The relative content of O-alkyl C increased indicating that OM application increased the content of methoxyl C and -CH(OH)- in carbohydrate. Alkyl C was probably derived from compounds of plants with high resistance to degradation, such as cutin and suberin (Baldock et al., 1992; Preston

  10. Lubiprostone: RU 0211, SPI 0211.

    Science.gov (United States)

    2005-01-01

    Lubiprostone [RU 0211, SPI 0211] is a bicyclic fatty acid that acts as a chloride channel opener, increasing intestinal water secretion. Lubiprostone, an orally-administered formulation, is one of a series of functional fatty acid compounds discovered by Dr Ryuji Ueno, and is currently undergoing development for the treatment of constipation, constipation-predominant irritable bowel syndrome (IBS-C) and postoperative ileus with Sucampo Pharmaceutical's. Lubiprostone activates a specific chloride channel (CLC2) on cells lining the gut, thereby naturally increasing intestinal fluid secretion. The increased fluid level softens the stool, promotes spontaneous bowel movements, and reduces abdominal discomfort/pain and bloating. The chloride channel is a protein that controls cell membrane transport of chloride ion. Lubiprostone acts on the ClC-2 chloride channel, which is located in the apical intestinal membrane. In November 2004, Takeda Pharmaceuticals entered into a collaboration and licensing agreement for Lubiprostone with Sucampo Pharmaceuticals for the treatment of chronic constipation and constipation-predominant Irritable Bowel Syndrome (c-IBS). Under the terms of the agreement, Takeda received the right to market the product in the US and Canada, while Sucampo reserved the co-promotion rights for these countries. Takeda's wholly-owned US subsidiary, Takeda Pharmaceuticals North America Inc., will sell lubiprostone once the product is approved by the US FDA. Takeda will also receive an option for marketing rights in other territories, including Japan and Europe. Takeda and Sucampo agreed on the exclusive manufacturing and supply of Lubiprostone by R-Tech Ueno, Ltd, a member of the Sucampo Group. Sucampo has the potential to receive up to dollar US 210 million in initial and milestone payments, some of which are contingent upon the successful achievement of several milestones. Takeda will fund a major part of development costs not only for chronic constipation

  11. Comparison of different theory models and basis sets in the calculations of structures and 13C NMR spectra of [Pt(en)(CBDCA-O, O')], an analogue of the antitumor drug carboplatin.

    Science.gov (United States)

    Gao, Hongwei; Wei, Xiujuan; Liu, Xuting; Yan, Tingxia

    2010-03-25

    Comparisons of various density functional theory (DFT) methods at different basis sets in predicting the molecular structures and (13)C NMR spectra for [Pt(en)(CBDCA-O, O')], an analogue of the antitumor drug carboplatin, are reported. DFT methods including B3LYP, B3PW91, mPW1PW91, PBE1PBE, BPV86, PBEPBE, and LSDA are examined. Different basis sets including LANL2DZ, SDD, LANL2MB, CEP-4G, CEP-31G, and CEP-121G are also considered. It is remarkable that the LSDA/SDD level is clearly superior to all of the remaining density functional methods in predicting the structure of [Pt(en)(CBDCA-O, O')]. The results also indicate that the B3LYP/SDD level is the best to predict (13)C NMR spectra for [Pt(en)(CBDCA-O, O')] among all DFT methods.

  12. 1H NMR spectra. Part 30(+): 1H chemical shifts in amides and the magnetic anisotropy, electric field and steric effects of the amide group.

    Science.gov (United States)

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

    2013-03-01

    The (1)H spectra of 37 amides in CDCl(3) solvent were analysed and the chemical shifts obtained. The molecular geometries and conformational analysis of these amides were considered in detail. The NMR spectral assignments are of interest, e.g. the assignments of the formamide NH(2) protons reverse in going from CDCl(3) to more polar solvents. The substituent chemical shifts of the amide group in both aliphatic and aromatic amides were analysed using an approach based on neural network data for near (≤3 bonds removed) protons and the electric field, magnetic anisotropy, steric and for aromatic systems π effects of the amide group for more distant protons. The electric field is calculated from the partial atomic charges on the N.C═O atoms of the amide group. The magnetic anisotropy of the carbonyl group was reproduced with the asymmetric magnetic anisotropy acting at the midpoint of the carbonyl bond. The values of the anisotropies Δχ(parl) and Δχ(perp) were for the aliphatic amides 10.53 and -23.67 (×10(-6) Å(3)/molecule) and for the aromatic amides 2.12 and -10.43 (×10(-6) Å(3)/molecule). The nitrogen anisotropy was 7.62 (×10(-6) Å(3)/molecule). These values are compared with previous literature values. The (1)H chemical shifts were calculated from the semi-empirical approach and also by gauge-independent atomic orbital calculations with the density functional theory method and B3LYP/6-31G(++) (d,p) basis set. The semi-empirical approach gave good agreement with root mean square error of 0.081 ppm for the data set of 280 entries. The gauge-independent atomic orbital approach was generally acceptable, but significant errors (ca. 1 ppm) were found for the NH and CHO protons and also for some other protons.

  13. Involvement of SPI-2-encoded SpiC in flagellum synthesis in Salmonella enterica serovar Typhimurium

    Directory of Open Access Journals (Sweden)

    Sugita Asami

    2009-08-01

    Full Text Available Abstract Background SpiC encoded within Salmonella pathogenicity island 2 on the Salmonella enterica serovar Typhimurium chromosome is required for survival within macrophages and systemic infection in mice. Additionally, SpiC contributes to Salmonella-induced activation of the signal transduction pathways in macrophages by affecting the expression of FliC, a component of flagella filaments. Here, we show the contribution of SpiC in flagellum synthesis. Results Quantitative RT-PCR shows that the expression levels of the class 3 fliD and motA genes that encode for the flagella cap and motor torque proteins, respectively, were lower for a spiC mutant strain than for the wild-type Salmonella. Further, this mutant had lower expression levels of the class 2 genes including the fliA gene encoding the flagellar-specific alternative sigma factor. We also found differences in flagella assembly between the wild-type strain and the spiC mutant. Many flagella filaments were observed on the bacterial surface of the wild-type strain, whereas the spiC mutant had only few flagella. The absence of spiC led to reduced expression of the FlhD protein, which functions as the master regulator in flagella gene expression, although no significant difference at the transcription level of the flhDC operon was observed between the wild-type strain and the spiC mutant. Conclusion The data show that SpiC is involved in flagella assembly by affecting the post-transcription expression of flhDC.

  14. Scientific expectations from the INTEGRAL spectrometer SPI

    Science.gov (United States)

    Schoenfelder, Volker

    2003-03-01

    The spectrometer SPI - one of the two main instruments aboard ESA's INTEGRAL - is dedicated to high resolution gamma-ray line spectroscopy with modest imaging. SPI will mainly concentrate on the study of lines from radioactive isotopes. A wealth of new information is expected from interstellar line emission with narrow line profiles. But existing results are also expected from profile measurements of individual line emitting objects such as supernovae, supernova remnants, novae or stellar black hole systems. In addition, sensitive measurements of continuum emission from compact sources and from interstellar space are expected, especially in the sub-MeV region.

  15. The Spy in Early America: The Emergence of a Genre

    Science.gov (United States)

    2007-11-02

    that the modern spy story represents the modern version of the epic ; it satisfies 74 similar reader needs as epic poetry : familiar plots and clearly...with spies who engage in espionage for personal enrichment, the American literary spy rarely does (only the villains do). Wit rather than avarice...deal of spy literary material produced in this country prior to 1900. After the Civil War, greater literacy, advances in publishing, and the personal

  16. Spy Works: A Collaborative Creative Writing Model.

    Science.gov (United States)

    Bruce, Charlotte

    2001-01-01

    Students in a creative writing class at McLean High School (Virginia) were asked to write an original piece of spy fiction. A four-way collaboration model, which utilized the strengths and expertise of a teacher, library media specialist, business partner (the technology division of the CIA), and vendor, provided students with unusual learning…

  17. The Spy Story as Modern Tragedy

    Science.gov (United States)

    Snyder, John R.

    1977-01-01

    Supplements the idea of the realistic spy story as reflector of modern problems with a theory of its meaning or a "metaphysics" of the genre. Available from: Thomas L. Erskine, Co-Editor; Literature/Film Quarterly, Salisbury State College, Salisbury, Maryland 21801, Subscription Rates: individuals, $6.00; students, $5.00; single copies, $2.00. (MH)

  18. Coherence transfer between spy nuclei and nitrogen-14 in solids.

    Science.gov (United States)

    Cavadini, Simone; Abraham, Anuji; Bodenhausen, Geoffrey

    2008-01-01

    Coherence transfer from 'spy nuclei' such as (1)H or (13)C (S=1/2) was used to excite single- or double-quantum coherences of (14)N nuclei (I=1) while the S spins were aligned along the static field, in the manner of heteronuclear single-quantum correlation (HSQC) spectroscopy. For samples spinning at the magic angle, coherence transfer can be achieved through a combination of scalar couplings J(I,S) and second-order quadrupole-dipole cross-terms, also known as residual dipolar splittings (RDS). The second-order quadrupolar powder patterns in the two-dimensional spectra allow one to determine the quadrupolar parameters of (14)N in amino acids.

  19. Increase resolution of {sup 13}C NMR spectra of humic acids in solution by previous treatment with 0,03 mol L{sup -1} KCl; Aumento da resolucao de espectros de RMN {sup 13}C de acidos humicos em solucao atraves do tratamento previo com KCl 0,03 mol L{sup -1}

    Energy Technology Data Exchange (ETDEWEB)

    Canellas, Luciano Pasqualoto; Guridi, Fernando; Santos, Gabriel de A. [Universidade Federal Rural do Rio de Janeiro, RJ (Brazil). Dept. de Solos; Rumjanek, Victor Marcos [Universidade Federal, Rio de Janeiro, RJ (Brazil). Dept. de Quimica; Braz-Filho, Raimundo [Universidade Estadual do Norte Fluminense, Campos, RJ (Brazil). Setor de Quimica dos Produtos Naturais

    2001-02-01

    High levels of Fe and Mn present in some soils and compost organic matter decrease the resolution of {sup 13} C NMR spectra of humic substances. Addition of K Cl up to a concentration of 0,03 mol L{sub -}{sup 1} to humic substances extracts followed by centrifugation is an efficient method of eliminating clays and minerals containing high levels of paramagnetic metals such as Fe and Mn thus increasing the resolution of {sup 13} C NMR spectra. (author)

  20. The hard X-ray continuum of Cen A observed with INTEGRAL SPI

    CERN Document Server

    Burke, Mark J; Roques, Jean-Pierre; Evans, Daniel A

    2014-01-01

    We revisit the average hard X-ray spectrum from the AGN of Centaurus A (Cen A) using ten years worth of observations with INTEGRAL SPI. This source has the highest flux observed from any AGN in the SPI bandpass (23 keV--8 MeV). The 10 year lightcurve of Cen A is presented, and hardness ratios confirm that the spectral shape changes very little despite the luminosity varying by a factor of a few. Primarily, we establish the presence of a reflection component in the average spectrum by demonstrating an excess between 20-60 keV, from extending the spectral shape observed at low energy to the SPI regime. The excess in Chandra HETGS and INTEGRAL SPI data is well described by reflection of the dominant power law spectrum from a neutral, optically-thick atmosphere. We find that the reprocessed emission contributes 20-25% of the 23-100 keV flux. The existence of a cut-off at tens to hundreds of keV remains controversial. Using simulated spectra, we demonstrate that a high energy cut off reproduces the observed spectr...

  1. PIC microcontroller based external fast analog to digital converter to acquire wide-lined solid NMR spectra by BRUKER DRX and Avance-I spectrometers.

    Science.gov (United States)

    Koczor, Bálint; Rohonczy, János

    2015-01-01

    Concerning many former liquid or hybrid liquid/solid NMR consoles, the built in Analog-to-Digital Converters (ADCs) are incapable of digitizing the fids at sampling rates in the MHz range. Regarding both strong anisotropic interactions in the solid state and wide chemical shift dispersion nuclei in solution phase such as (195)Pt, (119)Sn, (207)Pb etc., the spectrum range of interest might be in the MHz range. As determining the informative tensor components of anisotropic NMR interactions requires nonlinear fitting over the whole spectrum including the asymptotic baseline, it is prohibited by low sampling rates of the ADCs. Wide spectrum width is also useful in solution NMR, since windowing of wide chemical shift ranges is avoidable. We built an external analog to digital converter with 10 MHz maximal sampling rate, which can work simultaneously with the built in ADC of the spectrometer. The ADC was tested on both Bruker DRX and Avance-I NMR consoles. In addition to the analog channels it only requires three external digital lines of the NMR console. The ADC sends data to PC via USB. The whole process is controlled by software written in JAVA which is implemented under TopSpin. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Human- and computer-accessible 2D correlation data for a more reliable structure determination of organic compounds. Future roles of researchers, software developers, spectrometer managers, journal editors, reviewers, publisher and database managers toward artificial-intelligence analysis of NMR spectra.

    Science.gov (United States)

    Jeannerat, Damien

    2017-01-01

    The introduction of a universal data format to report the correlation data of 2D NMR spectra such as COSY, HSQC and HMBC spectra will have a large impact on the reliability of structure determination of small organic molecules. These lists of assigned cross peaks will bridge signals found in NMR 1D and 2D spectra and the assigned chemical structure. The record could be very compact, human and computer readable so that it can be included in the supplementary material of publications and easily transferred into databases of scientific literature and chemical compounds. The records will allow authors, reviewers and future users to test the consistency and, in favorable situations, the uniqueness of the assignment of the correlation data to the associated chemical structures. Ideally, the data format of the correlation data should include direct links to the NMR spectra to make it possible to validate their reliability and allow direct comparison of spectra. In order to take the full benefits of their potential, the correlation data and the NMR spectra should therefore follow any manuscript in the review process and be stored in open-access database after publication. Keeping all NMR spectra, correlation data and assigned structures together at all time will allow the future development of validation tools increasing the reliability of past and future NMR data. This will facilitate the development of artificial intelligence analysis of NMR spectra by providing a source of data than can be used efficiently because they have been validated or can be validated by future users. Copyright © 2016 John Wiley & Sons, Ltd.

  3. InSpiRe - Intelligent Spine Rehabilitation

    DEFF Research Database (Denmark)

    Bøg, Kasper Hafstrøm; Helms, Niels Henrik; Kjær, Per;

    InSpiRe er et projekt, der har haft omdrejningspunkt i etableringen af et nyt netværk indenfor intelligent genoptræning med særligt fokus på rygsmerter. Projektet er gennemført i perioden 1/3 2011 2011-1/3 2012, med støtte fra Syddansk Vækstforum, og er blevet drevet af projektparterne Knowledge...

  4. Learning and Organizational Change in SPI Initiatives

    Science.gov (United States)

    Heikkilä, Marikka

    Explaining how organizations chance has been a central and enduring quest of management scholars and many other disciplines. In order to be successful change requires not only a new process or technology but also the engagement and participation of the people involved. In this vein the change process results in new behavior and is routinized in practical daily business life of the company. Change management provides a framework for managing the human side of these changes. In this article we present a literature review on the change management in the context of Software Process Improvement. The traditional view of learning, as a “lessons learned” or post-mortem reporting activity is often apparent in SPI literature. However, learning can also be viewed as a continuous change process where specific learning cycle starts with creative conflict and ends up in formal norms and systems. Since this perspective has almost no visibility in SPI literature of past it could show a new direction to the future development of change management in SPI.

  5. Vibrational (FT-IR and FT-Raman), electronic (UV-Vis), NMR (1H and 13C) spectra and reactivity analyses of 4,5-dimethyl-o-phenylenediamine.

    Science.gov (United States)

    Atac, Ahmet; Karaca, Caglar; Gunnaz, Salih; Karabacak, Mehmet

    2014-09-15

    The structure of 4,5-dimethyl-o-phenylenediamine (C8H12N2, DMPDA) was investigated on the basis of spectroscopic data and theoretical calculations. The sterochemical structure was determined by FT-IR, FT-Raman, UV, 1H and 13C NMR spectra. An experimental study and a theoretical analysis were associated by using the B3LYP method with Gaussian09 package program. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm(-1) and 4000-10 cm(-1), respectively. The vibrational spectra were calculated by DFT method and the fundamental vibrations were assigned on the basis of the total energy distribution (TED), calculated with scaled quantum mechanics (SQM) method with Parallel Quantum Solutions (PQS) program. The UV absorption spectrum of the compound that dissolved in ethanol solution were recorded in the range of 190-400 nm. Total density of state (TDOS) and partial density of state (PDOS) of the DMPDA in terms of HOMOs and LUMOs were calculated and analyzed. Chemical shifts were reported in ppm relative to tetramethylsilane (TMS) for 1H and 13C NMR spectra. The compound was dissolved in dimethyl sulfoxide (DMSO). Also, 1H and 13C chemical shifts calculated using the gauge independent atomic orbital (GIAO) method. Mullikan atomic charges and other thermo-dynamical parameters were investigated with the help of B3LYP (DFT) method using 6-311++G** basis set. On the basis of the thermodynamic properties of the title compound at different temperatures have been carried out, revealing the correlations between heat capacity (C), entropy (S), enthalpy changes (H) and temperatures. The optimized bond lengths, bond angles, chemical shifts and vibrational wavenumbers showed the best agreement with the experimental results. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Salmonella pathogenicity island 1(SPI-1) at work.

    Science.gov (United States)

    Que, Fengxia; Wu, Shuyan; Huang, Rui

    2013-06-01

    As an indispensable virulence determinant, Salmonella pathogenicity island 1(SPI-1) has gained much attention in host-pathogen interactions. More and more studies on SPI-1 have demonstrated that it is far more complex than the one we used to expect. It not only affects sophisticated activities during infection, including invasion, replication, and host responses, but also extends to other fields like biofilm formation. In addition, mutants in SPI-1 effectors have been explored as vaccines, the effective ways to prevent salmonellosis. The activity of SPI-1 is influenced by many factors which have been widely reported. Investigations on these factors may provide new insights into prevention and treatment of salmonellosis. Therefore, SPI-1 is a tempting issue worthy of further exploration. In this review, we will probe into SPI-1 systematically.

  7. Analysis of theoretical NMR spectra generated by exact solutions of the Bloch-McConnell and the Bloch-Torrey equations for a two-compartment radial diffusive exchange model

    CERN Document Server

    Gherase, Mihai R

    2012-01-01

    Diffusive spin exchange is one of the most important relaxation mechanisms in the Nuclear Magnetic Resonance (NMR) applications to medicine and biology. Two models based on the Bloch-McConnell (B-M) and the Bloch-Torrey (B-T) equations are commonly used for modelling the physical processes which determine the NMR lineshapes. Qualitative arguments for each of the two methods can be found in various studies in the literature. However, there is a lack of systematic quantitative investigations of the diffusive exchange spectra calculated with the two methods for the same physical system or model. In this work exact frequency-domain transverse magnetization solutions of the B-M and the B-T equations with boundary conditions for a two-compartment radial diffusive exchange model are presented. Theoretical spectra and the two corresponding metrics were computed by varying three different parameters: diffusive permeability of the separating membrane between the two compartments (P), the radius of the inner spherical c...

  8. FT-IR, UV-vis, 1H and 13C NMR spectra and the equilibrium structure of organic dye molecule disperse red 1 acrylate: a combined experimental and theoretical analysis.

    Science.gov (United States)

    Cinar, Mehmet; Coruh, Ali; Karabacak, Mehmet

    2011-12-01

    This study reports the characterization of disperse red 1 acrylate compound by spectral techniques and quantum chemical calculations. The spectroscopic properties were analyzed by FT-IR, UV-vis, (1)H NMR and (13)C NMR techniques. FT-IR spectrum in solid state was recorded in the region 4000-400 cm(-1). The UV-vis absorption spectrum of the compound that dissolved in methanol was recorded in the range of 200-800 nm. The (1)H and (13)C NMR spectra were recorded in CDCl(3) solution. The structural and spectroscopic data of the molecule in the ground state were calculated using density functional theory (DFT) employing B3LYP exchange correlation and the 6-311++G(d,p) basis set. The vibrational wavenumbers were calculated and scaled values were compared with experimental FT-IR spectrum. A satisfactory consistency between the experimental and theoretical spectra was obtained and it shows that the hybrid DFT method is very useful in predicting accurate vibrational structure, especially for high-frequency region. The complete assignments were performed on the basis of the experimental results and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Isotropic chemical shifts were calculated using the gauge-invariant atomic orbital (GIAO) method. A study on the electronic properties were performed by timedependent DFT (TD-DFT) and CIS(D) approach. To investigate non linear optical properties, the electric dipole moment μ, polarizability α, anisotropy of polarizability Δα and molecular first hyperpolarizability β were computed. The linear polarizabilities and first hyperpolarizabilities of the studied molecule indicate that the compound can be a good candidate of nonlinear optical materials.

  9. 1H NMR spectra of N-methyl-4-tolyl-1-(4-bromonaphthylamine and N-phenyl-1-(4-bromonaphthylamine: a combined experimental and theoretical study

    Directory of Open Access Journals (Sweden)

    Sergiy I. Okovytyy

    2014-03-01

    Full Text Available Theoretical investigations of the conformational properties and 1H NMR chemical shifts for N-methyl-4-tolyl-1-(4-bromonaphthylamine and N-phenyl-1-(4-bromonaphthylamine are reported. The calculations were performed at the DFT level (PBE1PBE functional using magnetically consistent 6-31G## and STO##-3Gmag basis sets. Conformational properties of the amines were studied using potential energy surface scanning. Chemical shifts were calculated using the GIAO and CSGT methods and averaged in proportion to the population of the corresponding conformations. Solvent effects (CDCl3 were accounted via PCM method. The obtained results allowed to assign the 1H NMR signals for the naphthalene moiety, which could not be done based on the experimental data alone.

  10. The Hard X-Ray Continuum of Cen A Observed With INTEGRAL SPI

    Science.gov (United States)

    Burke, Mark J.; Jourdain, Elisabeth; Roques, Jean-Pierre; Evans, Daniel A.

    2014-05-01

    We revisit the average hard X-ray spectrum from the active galactic nucleus (AGN) of Centaurus A (Cen A) using 10 yr worth of observations with INTEGRAL SPI. This source has the highest flux observed from any AGNs in the SPI bandpass (23 keV-8 MeV). The 10 year light curve of Cen A is presented, and hardness ratios confirm that the spectral shape changes very little despite the luminosity varying by a factor of a few. Primarily, we establish the presence of a reflection component in the average spectrum by demonstrating an excess between 20 and 60 keV, from extending the spectral shape observed at low energy to the SPI regime. The excess in Chandra HETGS and INTEGRAL SPI data is well described by reflection of the dominant power-law spectrum from a neutral, optically thick atmosphere. We find that the reprocessed emission contributes 20%-25% of the 23-100 keV flux. The existence of a cutoff at tens to hundreds of kiloelectron volts remains controversial. Using simulated spectra, we demonstrate that a high energy cutoff reproduces the observed spectral properties of Cen A more readily than a simple power law. However, we also show that such a cutoff is probably underestimated when neglecting (even modest) reflection, and for Cen A would be at energies >700 keV, with a confidence of >95%. This is atypically high for thermal Comptonizing plasmas observed in AGNs, and we propose that we are in fact modeling the more gradual change in spectral shape expected of synchrotron self-Compton spectra.

  11. Formation of Gel-like Nanodomains in Cholesterol-Containing Sphingomyelin or Phosphatidylcholine Binary Membrane As Examined by Fluorescence Lifetimes and (2)H NMR Spectra.

    Science.gov (United States)

    Yasuda, Tomokazu; Matsumori, Nobuaki; Tsuchikawa, Hiroshi; Lönnfors, Max; Nyholm, Thomas K M; Slotte, J Peter; Murata, Michio

    2015-12-29

    In this study, we measured the time-resolved fluorescence of trans-parinaric acid (tPA), steady-state fluorescence anisotropy of diphenylhexatriene (DPH), and (2)H NMR of 10,10-d2-stearoyl lipids in stearoyl sphingomyelin with cholesterol (SSM/Chol) and l-palmitoyl-2-stearoyl-sn-glycero-3-phosphocholine with Chol (PSPC/Chol) binary membranes. The results suggest that the membrane order obtained from the fluorescence experiments shows a similar temperature dependency as those of the (2)H NMR data. More importantly, the time-resolved fluorescence data implied the presence of at least two types of domains, cholesterol-poor gel-like domains (CPGLD) and cholesterol-enriched liquid-ordered (Lo) domains. These domains appear on a nano-to-micro second time scale for both SSM-Chol and PSPC-Chol membranes. The relative size of the gel-like domain was also estimated from the temperature-dependent lifetime measurements and (2)H NMR spectral changes. The results imply that the size of the gel-like domains is very small, probably on the nanometer scale, and smaller in SSM-Chol membrane than those in PSPC-Chol bilayers, which could account for the higher thermal stability of SM-Chol membranes. The present study demonstrates that gel-like nanodomains occur in SM-Chol binary membrane even with Chol content of over 33 mol %, which has been thought to consist exclusively of Lo phase, implying that not only Lo domains but also gel-like nanodomains are important for formation of lipid-ordered phase in SM-Chol and PC-Chol membranes.

  12. Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation

    Directory of Open Access Journals (Sweden)

    Yoshinori Kadoma

    2012-05-01

    Full Text Available The NMR chemical shift, i.e., the π-electron density of the double bond, of acrylates and methacrylates is related to the reactivity of their monomers. We investigated quantitative structure-property relationships (QSPRs between the base-catalyzed hydrolysis rate constants (k1 or the rate constant with glutathione (GSH (log kGSH for acrylates and methacrylates and the 13C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δCα and δCβ or heat of formation (Hf calculated by the semi-empirical MO method. Reported data for the independent variables were employed. A significant linear relationship between k1 and δCβ, but not δCα, was obtained for methacrylates (r2 = 0.93, but not for acrylates. Also, a significant relationship between k1 and Hf was obtained for both acrylates and methacrylates (r2 = 0.89. By contrast, log kGSH for acrylates and methacrylates was linearly related to their δCβ (r2 = 0.99, but not to Hf. These findings indicate that the 13C NMR chemical shifts and calculated Hf values for acrylates and methacrylates could be valuable for estimating the hydrolysis rate constants and GSH reactivity of these compounds. Also, these data for monomers may be an important tool for examining mechanisms of reactivity.

  13. Precursors of Short GRBs Registered by SPI-ACS/INTEGRAL

    Science.gov (United States)

    Minaev, P.; Pozanenko, A.

    2016-10-01

    We have searched for precursors in light curves of short gamma-ray bursts registered by SPI-ACS/INTEGRAL in 2002-2014. The portion of short bursts with precursor activity will be less than 0.4% from all short bursts registered by SPI-ACS.

  14. The Spy VI child : A newly discovered Neandertal infant

    NARCIS (Netherlands)

    Crevecoeur, Isabelle; Bayle, Priscilla; Rougier, Helene; Maureille, Bruno; Higham, Thomas; van der Plicht, Johannes; De Clerck, Nora; Semal, Patrick

    2010-01-01

    Spy cave (Jemeppe-sur-Sambre Belgium) is reputed for the two adult Neandertal individuals discovered in situ in 1886 Recent reassessment of the Spy collections has allowed direct radiocarbon dating of these individuals The sorting of all of the faunal collections has also led to the discovery of the

  15. A BRUTUS Logic for a Spi-Calculus Dialect

    NARCIS (Netherlands)

    Gnesi, S.; Latella, D.; Lenzini, G.

    2000-01-01

    In the field of process algebras, the spi-calculus, a modified version of the π-calculus with encryption primitives, is indicated as an expressive specification language for cryptographic protocols. In spi-calculus basic security properties, such as secrecy and integrity can be formalized as may-tes

  16. A BRUTUS Logic for a Spi-Calculus Dialect

    NARCIS (Netherlands)

    Gnesi, S.; Latella, D.; Lenzini, Gabriele

    2000-01-01

    In the field of process algebras, the spi-calculus, a modified version of the π-calculus with encryption primitives, is indicated as an expressive specification language for cryptographic protocols. In spi-calculus basic security properties, such as secrecy and integrity can be formalized as

  17. How Do Artifact Models Help Direct SPI Projects?

    DEFF Research Database (Denmark)

    Kuhrmann, Marco; Richardson, Ita

    2015-01-01

    To overcome shortcomings associated with software process improvement (SPI), we previously recommended that process engineers focus on the artifacts to be developed in SPI projects. These artifacts should define desired outcomes, rather than specific methods. During this prior research, we...... developed a model for Artifact-based Software Process Improvement & Management (ArSPI). We are now carrying out studies to confirm our claims that ArSPI will provide benefits such as quality assurance. In this paper, we report on an experimental setting in which we developed and analyzed a strategy to use...... artifact models to direct process model improvement. We analyzed a process specification, the realized model, and the generated electronic process guide. We used ArSPI v0.9 as our process model and the Capability Maturity Model Integration (CMMI) as an external reference to provide a set of overall...

  18. Plug-and-playable fluorescent cell imaging modular toolkits using the bacterial superglue, SpyTag/SpyCatcher.

    Science.gov (United States)

    Moon, Hyojin; Bae, Yoonji; Kim, Hansol; Kang, Sebyung

    2016-11-29

    Simple plug-and-playable fluorescent cell imaging modular toolkits are established using the bacterial superglue SpyTag/SpyCatcher protein ligation system. A variety of affibody-fluorescent protein conjugates (AFPCs) are post-translationally generated via the isopeptide bond formation, and each AFPC effectively recognizes and binds to its targeting cells, visualizing them with selective colors on demand.

  19. Elucidation of the CCR1- and CCR5-binding modes of MIP-1α by application of an NMR spectra reconstruction method to the transferred cross-saturation experiments

    Energy Technology Data Exchange (ETDEWEB)

    Yoshiura, Chie; Ueda, Takumi; Kofuku, Yutaka; Matsumoto, Masahiko; Okude, Junya; Kondo, Keita; Shiraishi, Yutaro; Shimada, Ichio, E-mail: shimada@iw-nmr.f.u-tokyo.ac.jp [The University of Tokyo, Graduate School of Pharmaceutical Sciences (Japan)

    2015-12-15

    C–C chemokine receptor 1 (CCR1) and CCR5 are involved in various inflammation and immune responses, and regulate the progression of the autoimmune diseases differently. However, the number of residues identified at the binding interface was not sufficient to clarify the differences in the CCR1- and CCR5-binding modes to MIP-1α, because the NMR measurement time for CCR1 and CCR5 samples was limited to 24 h, due to their low stability. Here we applied a recently developed NMR spectra reconstruction method, Conservation of experimental data in ANAlysis of FOuRier, to the amide-directed transferred cross-saturation experiments of chemokine receptors, CCR1 and CCR5, embedded in lipid bilayers of the reconstituted high density lipoprotein, and MIP-1α. Our experiments revealed that the residues on the N-loop and β-sheets of MIP-1α are close to both CCR1 and CCR5, and those in the C-terminal helix region are close to CCR5. These results suggest that the genetic influence of the single nucleotide polymorphisms of MIP-1α that accompany substitution of residues in the C-terminal helix region, E57 and V63, would provide clues toward elucidating how the CCR5–MIP-1α interaction affects the progress of autoimmune diseases.

  20. Elucidation of the CCR1- and CCR5-binding modes of MIP-1α by application of an NMR spectra reconstruction method to the transferred cross-saturation experiments.

    Science.gov (United States)

    Yoshiura, Chie; Ueda, Takumi; Kofuku, Yutaka; Matsumoto, Masahiko; Okude, Junya; Kondo, Keita; Shiraishi, Yutaro; Shimada, Ichio

    2015-12-01

    C-C chemokine receptor 1 (CCR1) and CCR5 are involved in various inflammation and immune responses, and regulate the progression of the autoimmune diseases differently. However, the number of residues identified at the binding interface was not sufficient to clarify the differences in the CCR1- and CCR5-binding modes to MIP-1α, because the NMR measurement time for CCR1 and CCR5 samples was limited to 24 h, due to their low stability. Here we applied a recently developed NMR spectra reconstruction method, Conservation of experimental data in ANAlysis of FOuRier, to the amide-directed transferred cross-saturation experiments of chemokine receptors, CCR1 and CCR5, embedded in lipid bilayers of the reconstituted high density lipoprotein, and MIP-1α. Our experiments revealed that the residues on the N-loop and β-sheets of MIP-1α are close to both CCR1 and CCR5, and those in the C-terminal helix region are close to CCR5. These results suggest that the genetic influence of the single nucleotide polymorphisms of MIP-1α that accompany substitution of residues in the C-terminal helix region, E57 and V63, would provide clues toward elucidating how the CCR5-MIP-1α interaction affects the progress of autoimmune diseases.

  1. Nucleobases and C2 and C4 Imidazolium Acetate Interactions: FTIR-ATR, Raman and NMR Spectra and ab Initio Calculations Insights

    DEFF Research Database (Denmark)

    Araújo, J. M. M.; Ferreira, Rui; Veiga, H.I.M.;

    a Nucleoside, and a nucleoside with one or more phosphate groups attached at the 5’ carbon is called a Nucleotide. Nucleotides comprise the structural units of RNA and DNA. The structural elements of the most common Nucleotides are depicted in the Figure 1. Uracil, a common and naturally occurring pyrimidine...... of the phase behavior. In the present work, we explore the use of RTILs to dissolve Nucleobases, Nucleosides and Nucleotides. Nucleobases are the parts of Nucleic Acids (DNA and RNA) that are involved in pairing. The system of a base covalently bound to the 1’ carbon of a ribose or deoxyribose is called....... The combined use of FTIR, FT-RAMAN and NMR-spectroscopy, as well as computer simulation, will be attain to better understand the solubility mechanism of nucleobases, nucleosides and nucleotides. The results here obtained show the enormous potential of the use of RTILs to dissolve nucleobases, nucleosides...

  2. Solid state NMR of proteins at high MAS frequencies: symmetry-based mixing and simultaneous acquisition of chemical shift correlation spectra

    Energy Technology Data Exchange (ETDEWEB)

    Bellstedt, Peter [Fritz Lipmann Institute, Biomolecular NMR spectroscopy, Leibniz Institute for Age Research (Germany); Herbst, Christian [Ubon Ratchathani University, Department of Physics, Faculty of Science (Thailand); Haefner, Sabine; Leppert, Joerg; Goerlach, Matthias; Ramachandran, Ramadurai, E-mail: raman@fli-leibniz.de [Fritz Lipmann Institute, Biomolecular NMR spectroscopy, Leibniz Institute for Age Research (Germany)

    2012-12-15

    We have carried out chemical shift correlation experiments with symmetry-based mixing sequences at high MAS frequencies and examined different strategies to simultaneously acquire 3D correlation spectra that are commonly required in the structural studies of proteins. The potential of numerically optimised symmetry-based mixing sequences and the simultaneous recording of chemical shift correlation spectra such as: 3D NCAC and 3D NHH with dual receivers, 3D NC Prime C and 3D C Prime NCA with sequential {sup 13}C acquisitions, 3D NHH and 3D NC Prime H with sequential {sup 1}H acquisitions and 3D CANH and 3D C'NH with broadband {sup 13}C-{sup 15}N mixing are demonstrated using microcrystalline samples of the {beta}1 immunoglobulin binding domain of protein G (GB1) and the chicken {alpha}-spectrin SH3 domain.

  3. Engineering a thalamo-cortico-thalamic circuit on SpiNNaker: a preliminary study towards modelling sleep and wakefulness

    Directory of Open Access Journals (Sweden)

    Basabdatta Sen Bhattacharya

    2014-05-01

    Full Text Available We present a preliminary study of a thalamo-cortico-thalamic (TCT implementation on SpiNNaker (Spiking Neural Network architecture, a brain inspired hardware platform designed to incorporate the inherent biological properties of parallelism, fault tolerance and energy efficiency. These attributes make SpiNNaker an ideal platform for simulating biologically plausible computational models. Our focus in this work is to design a TCT framework that can be simulated on SpiNNaker to mimic dynamical behaviour similar to Electroencephalogram (EEG time and power-spectra signatures in sleep-wake transition. The scale of the model is minimised for simplicity in this proof-of-concept study; thus the total number of spiking neurons is approximately 1000 and represents a `mini-column' of the thalamocortical tissue. All data on model structure, synaptic layout and parameters is inspired from previous studies and abstracted at a level that is appropriate to the aims of the current study as well as computationally suitable for model simulation on a small 4-chip SpiNNaker system. The initial results from selective deletion of synaptic connectivity parameters in the model show similarity with EEG time series characteristics of sleep and wakefulness. These observations provide a positive perspective and a basis for future implementation of a very large scale biologically plausible model of thalamo-cortico-thalamic interactivity---the essential brain circuit that regulates the biological sleep-wake cycle and associated EEG rhythms.

  4. Vibrational analysis using FT-IR, FT-Raman spectra and HF-DFT methods and NBO, NLO, NMR, HOMO-LUMO, UV and electronic transitions studies on 2,2,4-trimethyl pentane

    Science.gov (United States)

    Suvitha, A.; Periandy, S.; Govindarajan, M.; Gayathri, P.

    2015-03-01

    In this work, the vibrational spectral analysis was carried out by using Raman and infrared spectroscopy in the range 100-4000 cm-1and 50-4000 cm-1, respectively, for 2,2,4-Trimethyl Pentane, TMP (C8H18) molecule. The molecular structure, fundamental vibrational frequencies and intensity of the vibrational bands are interpreted with the aid of structure optimizations and geometrical parameter calculations based on Hartree Fock (HF) and density functional theory (DFT) method with 6-311++G(d,p) basis set. The scaled B3LYP/6-311++G(d,p) results shows the best agreement with the experimental values over the other method. The calculated HOMO and LUMO energies shows that charge transfer within the molecule. The physical reactions of single bond hydrocarbon TMP were investigated. The results of the calculations were applied to simulate spectra of the title compound, which shows the excellent agreement with observed spectra. Besides, Mulliken atomic charges, UV, frontier molecular orbital (FMO), MEP, NLO activity, Natural Bond-Orbital (NBO) analysis, NMR and thermodynamic properties of title molecule were also performed.

  5. Cumulative "roof effect" in high-resolution in vivo 31P NMR spectra of human calf muscle and the Clebsch-Gordan coefficients of ATP at 1.5 T.

    Science.gov (United States)

    Schröder, Leif; Schmitz, Christian; Bachert, Peter

    2005-05-01

    NMR spectra of non-weakly coupled spin systems exhibit asymmetries in line intensities known as "roof effect" in 1D spectroscopy. Due to limited spectral resolution, this effect has not been paid much attention so far in in vivo spectroscopy. But when high-quality spectra are obtained, this effect should be taken into account to explain the quantum-mechanical fine structure of the system. Adenosine 5'-triphosphate (ATP) represents a 31P spin system with multiple line splittings which are caused by J-couplings of medium strength at 1.5 T. We analyzed the ATP roof effect in vivo, especially for the beta-ATP multiplet. The intensities of its outer resonances deviate by ca. 12.5% from a symmetrical triplet. As this asymmetry reflects the transition from Paschen-Back to Zeeman effect with total spin that is largely broken up, the Clebsch-Gordan coefficients of the system can be indicated in analogy to the hyperfine structure of hydrogen. Taking the roof effect into account, the chi2 of fitting in vivo ATP resonances is reduced by ca. 9% (p<0.005).

  6. Cumulative “roof effect” in high-resolution in vivo 31P NMR spectra of human calf muscle and the Clebsch Gordan coefficients of ATP at 1.5 T

    Science.gov (United States)

    Schröder, Leif; Schmitz, Christian; Bachert, Peter

    2005-05-01

    NMR spectra of non-weakly coupled spin systems exhibit asymmetries in line intensities known as "roof effect" in 1D spectroscopy. Due to limited spectral resolution, this effect has not been paid much attention so far in in vivo spectroscopy. But when high-quality spectra are obtained, this effect should be taken into account to explain the quantum-mechanical fine structure of the system. Adenosine 5'-triphosphate (ATP) represents a 31P spin system with multiple line splittings which are caused by J-couplings of medium strength at 1.5 T. We analyzed the ATP roof effect in vivo, especially for the β-ATP multiplet. The intensities of its outer resonances deviate by ca. 12.5% from a symmetrical triplet. As this asymmetry reflects the transition from Paschen-Back to Zeeman effect with total spin that is largely broken up, the Clebsch-Gordan coefficients of the system can be indicated in analogy to the hyperfine structure of hydrogen. Taking the roof effect into account, the χ2 of fitting in vivo ATP resonances is reduced by ca. 9% ( p < 0.005).

  7. Minimalist Relativistic Force Field: Prediction of Proton-Proton Coupling Constants in (1)H NMR Spectra Is Perfected with NBO Hybridization Parameters.

    Science.gov (United States)

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-05-15

    We previously developed a reliable method for multiparametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. We now report that utilization of NBO hybridization coefficients for carbon atoms in the involved C-H bonds allows for a significant simplification of this parametric scheme, requiring only four general types of SSCCs: geminal, vicinal, 1,3-, and long-range constants. The method is optimized for inexpensive B3LYP/6-31G(d) molecular geometries. A new DU8 basis set, based on a training set of 475 experimental spin-spin coupling constants, is developed for hydrogen and common non-hydrogen atoms (Li, B, C, N, O, F, Si, P, S, Cl, Se, Br, I) to calculate Fermi contacts. On a test set of 919 SSCCs from a diverse collection of natural products and complex synthetic molecules the method gave excellent accuracy of 0.29 Hz (rmsd) with the maximum unsigned error not exceeding 1 Hz.

  8. NBO, NMR, UV, FT-IR, FT-Raman spectra and molecular structure (monomeric and dimeric structures) investigation of 4-Chloro-3,5-Xylenol: A combined experimental and theoretical study

    Science.gov (United States)

    Arivazhagan, M.; Gayathri, R.

    2013-12-01

    In this work, a joint experimental (FTIR and FT-Raman) and theoretical (DFT and ab initio) study on the structure and the vibrations of 4-Chloro-3,5-Xylenol (CXL) are compared and analyzed. CXL is a chlorinated phenolic antiseptic which is a bactericide against most gram-positive bacteria. The first hyperpolarizability (β0) of this novel molecular system and related non-linear properties of CXL are calculated using HF/6-311++G(d,p) method on the finite-field approach. The energy and oscillator strength calculated using absorption spectra (UV-Vis spectrum), this spectral analysis confirms the charge transfer of the molecule. The theoretical 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by Gauge Including Atomic Orbital (GIAO) method, to analyze the molecular environment as well as the delocalization activities of electron clouds. The directly calculated ionization potential (IP), electron affinity (EA), electronegativity (χ), chemical hardness (η), first electron excitation energy (τ) and electrophilicity index (ω) as well as local reactivity (S) analyzed using HOMO and LUMO energies; the energy band gap are also determined. NBO analysis shows that charge in electron density(ED) in the σ* and π* antibonding orbitals and E(2) energies confirms the occurrence of ICT (Intramolecular Charge Transfer) within the molecule. Inter molecular hydrogen bonds exist between -OH group, give the evidence for the formation of dimer entities in the title molecule. The influences of chlorine atom, hydroxyl group and methyl group on the geometry of benzene and its normal modes of vibrations (monomer and dimer of CXL) have also been discussed. Finally the calculated results were applied to simulate Infrared and Raman spectra of the title molecule which show good agreement with observed spectra.

  9. NBO, NMR, UV, FT-IR, FT-Raman spectra and molecular structure (monomeric and dimeric structures) investigation of 4-Chloro-3,5-Xylenol: a combined experimental and theoretical study.

    Science.gov (United States)

    Arivazhagan, M; Gayathri, R

    2013-12-01

    In this work, a joint experimental (FTIR and FT-Raman) and theoretical (DFT and ab initio) study on the structure and the vibrations of 4-Chloro-3,5-Xylenol (CXL) are compared and analyzed. CXL is a chlorinated phenolic antiseptic which is a bactericide against most gram-positive bacteria. The first hyperpolarizability (β0) of this novel molecular system and related non-linear properties of CXL are calculated using HF/6-311++G(d,p) method on the finite-field approach. The energy and oscillator strength calculated using absorption spectra (UV-Vis spectrum), this spectral analysis confirms the charge transfer of the molecule. The theoretical (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by Gauge Including Atomic Orbital (GIAO) method, to analyze the molecular environment as well as the delocalization activities of electron clouds. The directly calculated ionization potential (IP), electron affinity (EA), electronegativity (χ), chemical hardness (η), first electron excitation energy (τ) and electrophilicity index (ω) as well as local reactivity (S) analyzed using HOMO and LUMO energies; the energy band gap are also determined. NBO analysis shows that charge in electron density(ED) in the σ(*) and π(*) antibonding orbitals and E((2)) energies confirms the occurrence of ICT (Intramolecular Charge Transfer) within the molecule. Inter molecular hydrogen bonds exist between -OH group, give the evidence for the formation of dimer entities in the title molecule. The influences of chlorine atom, hydroxyl group and methyl group on the geometry of benzene and its normal modes of vibrations (monomer and dimer of CXL) have also been discussed. Finally the calculated results were applied to simulate Infrared and Raman spectra of the title molecule which show good agreement with observed spectra.

  10. Spectral editing of two-dimensional magic-angle-spinning solid-state NMR spectra for protein resonance assignment and structure determination

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt-Rohr, K.; Fritzsching, K. J.; Liao, S. Y.; Hong Mei, E-mail: mhong@iastate.edu [Iowa State University, Department of Chemistry and Ames Laboratory (United States)

    2012-12-15

    Several techniques for spectral editing of 2D {sup 13}C-{sup 13}C correlation NMR of proteins are introduced. They greatly reduce the spectral overlap for five common amino acid types, thus simplifying spectral assignment and conformational analysis. The carboxyl (COO) signals of glutamate and aspartate are selected by suppressing the overlapping amide N-CO peaks through {sup 13}C-{sup 15}N dipolar dephasing. The sidechain methine (CH) signals of valine, lecuine, and isoleucine are separated from the overlapping methylene (CH{sub 2}) signals of long-chain amino acids using a multiple-quantum dipolar transfer technique. Both the COO and CH selection methods take advantage of improved dipolar dephasing by asymmetric rotational-echo double resonance (REDOR), where every other {pi}-pulse is shifted from the center of a rotor period t{sub r} by about 0.15 t{sub r}. This asymmetry produces a deeper minimum in the REDOR dephasing curve and enables complete suppression of the undesired signals of immobile segments. Residual signals of mobile sidechains are positively identified by dynamics editing using recoupled {sup 13}C-{sup 1}H dipolar dephasing. In all three experiments, the signals of carbons within a three-bond distance from the selected carbons are detected in the second spectral dimension via {sup 13}C spin exchange. The efficiencies of these spectral editing techniques range from 60 % for the COO and dynamic selection experiments to 25 % for the CH selection experiment, and are demonstrated on well-characterized model proteins GB1 and ubiquitin.

  11. Axial ligand modulation of the electronic structures of binuclear copper sites: analysis of paramagnetic 1H NMR spectra of Met160Gln Cu(A).

    Science.gov (United States)

    Fernández, C O; Cricco, J A; Slutter, C E; Richards, J H; Gray, H B; Vila, A J

    2001-11-28

    Cu(A) is an electron-transfer copper center present in heme-copper oxidases and N2O reductases. The center is a binuclear unit, with two cysteine ligands bridging the metal ions and two terminal histidine residues. A Met residue and a peptide carbonyl group are located on opposite sides of the Cu2S2 plane; these weaker ligands are fully conserved in all known Cu(A) sites. The Met160Gln mutant of the soluble subunit II of Thermus thermophilus ba3 oxidase has been studied by NMR spectroscopy. In its oxidized form, the binuclear copper is a fully delocalized mixed-valence pair, as are all natural Cu(A) centers. The faster nuclear relaxation in this mutant suggests that a low-lying excited state has shifted to higher energies compared to that of the wild-type protein. The introduction of the Gln residue alters the coordination mode of His114 but does not affect His157, thereby confirming the proposal that the axial ligand-to-copper distances influence the copper-His interactions (Robinson, H.; Ang, M. C.; Gao, Y. G.; Hay, M. T.; Lu, Y.; Wang, A. H. Biochemistry 1999, 38, 5677). Changes in the hyperfine coupling constants of the Cys beta-CH2 groups are attributed to minor geometrical changes that affect the Cu-S-C(beta)-H(beta) dihedral angles. These changes, in addition, shift the thermally accessible excited states, thus influencing the spectral position of the Cys beta-CH2 resonances. The Cu-Cys bonds are not substantially altered by the Cu-Gln160 interaction, in contrast to the situation found in the evolutionarily related blue copper proteins. It is possible that regulatory subunits in the mitochondrial oxidases fix the relative positions of thermally accessible Cu(A) excited states by tuning axial ligand interactions.

  12. INTEGRAL Spectrometer SPI's GRB detection capabilities. GRBs detected inside SPI's FoV and with the anticoincidence system ACS

    OpenAIRE

    von Kienlin, A.; Beckmann, V.; Rau, A.; Arend, N.; Bennett, K.; McBreen, B.; Connell, P.; Deluit, S.; Hanlon, L.; Kippen, M.; Lichti, G. G.; Moran, L.; Preece, R.; Roques, J. -P.; Schoenfelder, V.

    2003-01-01

    The spectrometer SPI, one of the two main instruments of the INTEGRAL spacecraft, offers significant gamma-ray burst detection capabilities. In its 35 deg (full width) field of view SPI is able to localise gamma-ray bursts at a mean rate of ~ 0.8/month. With its large anticoincidence shield of 512 kg of BGO crystals SPI is able to detect gamma-ray bursts quasi omni-directionally with a very high sensitivity. Burst alerts of the anticoincidence shield are distributed by the INTEGRAL Burst Aler...

  13. The Simplified Psoriasis Index (SPI): a practical tool for assessing psoriasis.

    Science.gov (United States)

    Chularojanamontri, Leena; Griffiths, Christopher E M; Chalmers, Robert J G

    2013-08-01

    The Simplified Psoriasis Index (SPI) is a summary measure of psoriasis with separate components for current severity (SPI-s), psychosocial impact (SPI-p), and past history and interventions (SPI-i). It derives from the Salford Psoriasis Index but replaces Psoriasis Area and Severity Index (PASI) with a composite weighted severity score designed to reflect the impact of psoriasis affecting functionally or psychosocially important body sites. Two complementary versions are available, differing only in that current severity (SPI-s) is either professionally (proSPI-s) or patient self-assessed (saSPI-s). This study examined the criterion and construct validity and response distribution of proSPI-s, saSPI-s, and SPI-p in 100 patients with plaque psoriasis. A further 50 patients were assessed for test-retest reliability of these three components. Interrater reliability of proSPI-s was assessed in 12 patients, each assessed by 12 assessors (144 assessments). There was close correlation between PASI and proSPI-s (r=0.91); SPI-p was closely correlated with the Dermatology Life Quality Index (r=0.89). Strong intrarater (proSPI-s, saSPI-s, SPI-p, and SPI-i) and interrater (proSPI-s) reliability was demonstrated (all intraclass correlation coefficients >0.75). There were wide response distributions for all three components. We believe that both professional (proSPI) and self-assessed (saSPI) versions can readily be introduced into routine clinical practice.

  14. NMR studies of actinide dioxides

    Energy Technology Data Exchange (ETDEWEB)

    Tokunaga, Y. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan)], E-mail: tokunaga.yo@jaea.go.jp; Sakai, H.; Fujimoto, T.; Kambe, S.; Walstedt, R.E.; Ikushima, K.; Yasuoka, H. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Aoki, D.; Homma, Y. [Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan); Haga, Y.; Matsuda, T.D.; Ikeda, S.; Yamamoto, E.; Nakamura, A. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Shiokawa, Y. [Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan); Nakajima, K.; Arai, Y. [Department of Nuclear Energy System, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Onuki, Y. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Department of Physics, Osaka University, Toyonaka, Osaka 560-0043 (Japan)

    2007-10-11

    {sup 17}O NMR measurements have been performed on a series of the actinide dioxides, UO{sub 2}, NpO{sub 2} and PuO{sub 2}. Although the {sup 17}O NMR spectra in these materials are similar at higher temperatures, the low-temperature spectra present are significantly different. In UO{sub 2} we have observed a wide spectrum, forming a rectangular shape below T{sub N}=30 K. In NpO{sub 2}, on the other hand, the spectra broaden rather gradually and exhibit a two-peak structure below T{sub 0}=26 K. In PuO{sub 2}, neither spectrum broadening nor splitting has been observed. We show that these NMR spectra clearly indicate the different nature of the low-temperature magnetic ground states in these actinide compounds.

  15. [Intraoperative graft assessment using fluorescent imaging system (SPY)].

    Science.gov (United States)

    Kawashima, T; Naraoka, S; Kakizaki, T

    2009-07-01

    We investigated the efficacy of intraoperative fluorescent imaging system for the assessment of coronary artery bypass grafting (CABG). We used SPY imaging system in 100 CABG (57 off-pump and 43 on-pump CABG), totalling 287 distal anastomoses. The total graft patency rate on postoperative angiography in this series was 96.2% (276/287). Graft revision was done in 10 cases (10.0%) and 13 anastomoses (4.5%) by SPY imaging, which all resulted in good patency at postoperative angiography. On the other hand, 7 distal anastomoses and 1 mammary graft (2.8%) appeared to be successful on intraoperative SPY imaging, but were revealed to be occluded by postoperative angiography. SPY imaging system is useful for graft validation, and may contribute to improvement of coronary bypass graft patency.

  16. The Spy VI child: a newly discovered Neandertal infant.

    Science.gov (United States)

    Crevecoeur, Isabelle; Bayle, Priscilla; Rougier, Hélène; Maureille, Bruno; Higham, Thomas; van der Plicht, Johannes; De Clerck, Nora; Semal, Patrick

    2010-12-01

    Spy cave (Jemeppe-sur-Sambre, Belgium) is reputed for the two adult Neandertal individuals discovered in situ in 1886. Recent reassessment of the Spy collections has allowed direct radiocarbon dating of these individuals. The sorting of all of the faunal collections has also led to the discovery of the remains of a Neandertal child, Spy VI. This individual is represented by two mandibular corpus fragments. The left fragment is the most complete and both sides preserve the mental foramen. Four deciduous teeth are associated with these mandibular remains: three incisors and one canine. The lower left canine (Spy 645a) conjoins with the corresponding alveolar socket in the left part of the mandible. Following extant standards, the developmental stage of the preserved teeth indicate an age at death of about one and a half years. In addition to performing a classical morphometric comparative study of the mandible and teeth, we have evaluated the dental tissue proportions using high-resolution microtomographic techniques. Our results show that Spy VI generally falls within the Neandertal range of variation. However, this specimen also exhibits particular traits, notably in the dental internal structural organization, which reveals that variation in the immature Neandertal variation is larger than what was variation currently represented by the available fossil record. These observations demonstrate the need for investigating the frequency and expression of immature Neandertal traits in fossil anterior teeth, as well as their temporal and geographic variation. Direct radiocarbon dating of the Spy VI specimen has been conducted in two different laboratories. The results of Spy VI confirm the age previously determined for the two adults, making the Spy Neandertal remains the youngest ever directly dated in northwest Europe.

  17. NMR Dynamic Studies in Living Systems

    Institute of Scientific and Technical Information of China (English)

    闫永彬; 范明杰; 罗雪春; 张日清

    2002-01-01

    Nuclear magnetic resonance (NMR) can noninvasively monitor the intracellular concentrations and kinetic properties of numerous inorganic and organic compounds. These characteristics have made NMR a useful tool for dynamic studies of living systems. Applications of NMR to living systems have successfully extended to many areas, including studies of metabolic regulation, ion transport, and intracellular reaction rates in vivo. The major purpose of this review is to summarize the results that can be obtained by modern NMR techniques in living systems. With the advances of new techniques, NMR measurements of various nuclides have been performed for specific physiological purposes. Although some technical problems still remain and there are still discrepancies between NMR and traditional biochemical results, the abundant and unique information obtained from NMR spectra suggests that NMR will be more extensively applied in future studies of living systems. The fast development of these new techniques is providing many new NMR applications in living systems, as well as in structural biology.

  18. SpIES: The Spitzer IRAC Equatorial Survey

    CERN Document Server

    Timlin, John D; Richards, Gordon T; Lacy, Mark; Ryan, Erin L; Stone, Robert B; Bauer, Franz E; Brandt, W N; Fan, Xiaohui; Glikman, Eilat; Haggard, Daryl; Jiang, Linhua; LaMassa, Stephanie M; Lin, Yen-Ting; Makler, Martin; McGehee, Peregrine; Myers, Adam D; Schneider, Donald P; Urry, C Megan; Wollack, Edward J; Zakamska, Nadia L

    2016-01-01

    We describe the first data release from the Spitzer-IRAC Equatorial Survey (SpIES); a large-area survey of 115 deg^2 in the Equatorial SDSS Stripe 82 field using Spitzer during its 'warm' mission phase. SpIES was designed to probe sufficient volume to perform measurements of quasar clustering and the luminosity function at z > 3 to test various models for "feedback" from active galactic nuclei (AGN). Additionally, the wide range of available multi-wavelength, multi-epoch ancillary data enables SpIES to identify both high-redshift (z > 5) quasars as well as obscured quasars missed by optical surveys. SpIES achieves 5{\\sigma} depths of 6.13 {\\mu}Jy (21.93 AB magnitude) and 5.75 {\\mu}Jy (22.0 AB magnitude) at 3.6 and 4.5 microns, respectively - depths significantly fainter than WISE. We show that the SpIES survey recovers a much larger fraction of spectroscopically-confirmed quasars (98%) in Stripe 82 than are recovered by WISE (55%). This depth is especially powerful at high-redshift (z > 3.5), where SpIES reco...

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

    Science.gov (United States)

    Mills, Nancy S.; Shanklin, Michael

    2011-01-01

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

  20. IDT推出首款多路SPI-3至SPI-4数据包交换IC

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    IDT公司日前发布全新系统信息包接口(SPI)交换产品。新产品包括IDT 88P8344,它可以将虚拟专用网络(VPN)防火墙卡,以太网传输和多业务交换的4个低速SPI-3接口连接到高速SPI-4接口,并进行交换、汇聚、以及速率适配。据称这是行业首个具此功能的系统信息包接口(SPI)交换产品。

  1. Spin-orbit-induced anomalous pH-dependence in (1)H NMR spectra of Co(III) amine complexes: a diagnostic tool for structure elucidation.

    Science.gov (United States)

    Hegetschweiler, Kaspar; Kuppert, Dirk; Huppert, Jochen; Straka, Michal; Kaupp, Martin

    2004-06-02

    The pH-dependent (1)H NMR characteristics of a series of Co(III)-(polyamin)-aqua and Co(III)-(polyamin)-(polyalcohol) complexes, [Co(tach)(ino-kappa(3)-O(1,3,5))](3+) (1(3+)), [Co(tach)(ino-kappa(3)-Omicron(1,2,6))](3+) (2(3+)), [Co(tach)(taci-kappa-Nu(1)-kappa(2)-O(2,6))](3+) (3(3+)), [Co(ditame)(H(2)O)](3+) (4(3+)), and [Co(tren)(H(2)O)(2)](3+) (5(3+)), were studied in D(2)O by means of titration experiments (tach = all-cis-cyclohexane-1,3,5-triamine, ino = cis-inositol, taci = 1,3,5-triamino-1,3,5-trideoxy-cis-inositol, tren = tris(2-aminoethyl)amine, ditame = 2,2,6,6-tetrakis-(aminomethyl)-4-aza-heptane). A characteristic shift was observed for H(-C) hydrogen atoms in the alpha-position of a coordinated amino group upon deprotonation of a coordinated oxygen donor. For a cis-H-C-N-Co-O-H arrangement, deprotonation of the oxygen donor resulted in an additional shielding (shift to lower frequency) of the H(-C) proton, whereas for a trans-H-C-N-Co-O-H arrangement, deprotonation resulted in a deshielding (shift to higher frequency). The effect appears to be of rather general nature: it is observed for primary (1(3+)-5(3+)), secondary (4(3+)), and tertiary (5(3+)) amino groups, and for the deprotonation of an alcohol (1(3+)-3(3+)) or a water (4(3+), 5(3+)) ligand. Spin-orbit-corrected density functional calculations show that the high-frequency deprotonation shift for the trans-position is largely caused by a differential cobalt-centered spin-orbit effect on the hydrogen nuclear shielding. This effect is conformation dependent due to a Karplus-type behavior of the spin-orbit-induced Fermi-contact shift and thus only significant for an approximately antiperiplanar H-C-N-Co arrangement. The differential spin-orbit contribution to the deprotonation shift in the trans-position arises from the much larger spin-orbit shift for the protonated than for the deprotonated state. This is in turn due to a trans-effect of the deprotonated (hydroxo or alkoxo) ligand, which weakens

  2. An experimental and theoretical investigation of Acenaphthene-5-boronic acid: conformational study, NBO and NLO analysis, molecular structure and FT-IR, FT-Raman, NMR and UV spectra.

    Science.gov (United States)

    Karabacak, Mehmet; Sinha, Leena; Prasad, Onkar; Asiri, Abdullah M; Cinar, Mehmet

    2013-11-01

    The solid state Fourier transform infrared (FT-IR) and FT-Raman spectra of Acenaphthene-5-boronic acid (AN-5-BA), have been recorded in the range 4000-400cm(-1) and 4000-10cm(-1), respectively. Density functional theory (DFT), with the B3LYP functional was used for the optimization of the ground state geometry and simulation of the infrared and Raman spectra of the molecule. The vibrational wave numbers and their assignments were examined theoretically using the Gaussian 09 set of quantum chemistry codes and the normal modes were assigned by a scaled quantum mechanical (SQM) force field approach. Hydrogen-bonded dimer of AN-5-BA, optimized by counterpoise correction, has also been studied by B3LYP at the 6-311++G(d,p) level and the effects of molecular association through O-H⋯O hydrogen bonding have been discussed. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by Gauge-Including Atomic Orbital (GIAO) method. Natural bond orbital (NBO) analysis has been applied to study stability of the molecule arising from charge delocalization. UV spectrum of the title compound was also recorded and the electronic properties, such as frontier orbitals, and band gap energies were measured by TD-DFT approach. The first order hyperpolarizability 〈β〉, its components and associated properties such as average polarizability and anisotropy of the polarizability (α and Δα) of AN-5-BA was calculated using the finite-field approach.

  3. Transfer of the cloned Salmonella SPI-1 type III secretion system and characterization of its expression mechanisms in Gram negative bacteria in comparison with cloned SPI-2.

    Science.gov (United States)

    Cangelosi, Chris; Hannagan, Susan; Santiago, Clayton P; Wilson, James W

    2015-11-01

    Cloned type III secretion systems have much potential to be used for bacterial engineering purposes involving protein secretion and substrate translocation directly into eukaryotic cells. We have previously cloned the SPI-1 and SPI-2 type III systems from the Salmonella enterica serovar Typhimurium genome using plasmid R995 which can conveniently capture large genomic segments for transfer between bacterial strains. However, though expressed and functional in Salmonella strains, cloned SPI-1 was previously observed to have a serious expression defect in other Gram negative bacteria including Escherichia coli. Here we show that cloned SPI-1 expression and secretion can be detected in the secretion preps from E. coli and Citrobacter indicating the first observation of non-Salmonella SPI-1 expression. We describe a compatible plasmid system to introduce engineered SPI-1 substrates into cloned SPI-1 strains. However, a SPI-1 translocation defect is still observed in E. coli, and we show that this is likely due to a defect in SipB expression/secretion in this species. In addition, we also examined the requirement for the hilA and ssrAB regulators in the expression of cloned SPI-1 and SPI-2, respectively. We found a strict requirement for hilA for full cloned SPI-1 expression and secretion. However, though we found that ssrAB is required for full cloned SPI-2 expression in a range of media across different bacteria, it is not required for cloned SPI-2 expression in MgM8 inducing media in S. Typhimurium. This suggests that under SPI-2 inducing conditions in S. Typhimurium, other factors can substitute for loss of ssrAB in cloned SPI-2 expression. The results provide key foundational information for the future use of these cloned systems in bacteria.

  4. Assignment of solid-state 13C and 1H NMR spectra of paramagnetic Ni(II) acetylacetonate complexes aided by first-principles computations

    DEFF Research Database (Denmark)

    Rouf, Syed Awais; Jakobsen, Vibe Boel; Mareš, Jiří

    2017-01-01

    Recent advances in computational methodology allowed for first-principles calculations of the nuclear shielding tensor for a series of paramagnetic nickel(II) acetylacetonate complexes, [Ni(acac)2L2] with L = H2O, D2O, NH3, ND3, and PMe2Ph have provided detailed insight into the origin of the par......Recent advances in computational methodology allowed for first-principles calculations of the nuclear shielding tensor for a series of paramagnetic nickel(II) acetylacetonate complexes, [Ni(acac)2L2] with L = H2O, D2O, NH3, ND3, and PMe2Ph have provided detailed insight into the origin...... of the paramagnetic contributions to the total shift tensor. This was employed for the assignment of the solid-state 1,2H and 13C MAS NMR spectra of these compounds. The two major contributions to the isotropic shifts are by orbital (diamagnetic-like) and contact mechanism. The orbital shielding, contact, as well...... as dipolar terms all contribute to the anisotropic component. The calculations suggest reassignment of the 13C methyl and carbonyl resonances in the acac ligand [Inorg. Chem. 53, 2014, 399] leading to isotropic paramagnetic shifts of δ(13C) ≈ 800–1100 ppm and ≈180–300 ppm for 13C for the methyl and carbonyl...

  5. Combination of {sup 15}N reverse labeling and afterglow spectroscopy for assigning membrane protein spectra by magic-angle-spinning solid-state NMR: application to the multidrug resistance protein EmrE

    Energy Technology Data Exchange (ETDEWEB)

    Banigan, James R.; Gayen, Anindita; Traaseth, Nathaniel J., E-mail: traaseth@nyu.edu [New York University, Department of Chemistry (United States)

    2013-04-15

    Magic-angle-spinning (MAS) solid-state NMR spectroscopy has emerged as a viable method to characterize membrane protein structure and dynamics. Nevertheless, the spectral resolution for uniformly labeled samples is often compromised by redundancy of the primary sequence and the presence of helical secondary structure that results in substantial resonance overlap. The ability to simplify the spectrum in order to obtain unambiguous site-specific assignments is a major bottleneck for structure determination. To address this problem, we used a combination of {sup 15}N reverse labeling, afterglow spectroscopic techniques, and frequency-selective dephasing experiments that dramatically improved the ability to resolve peaks in crowded spectra. This was demonstrated using the polytopic membrane protein EmrE, an efflux pump involved in multidrug resistance. Residues preceding the {sup 15}N reverse labeled amino acid were imaged using a 3D NCOCX afterglow experiment and those following were recorded using a frequency-selective dephasing experiment. Our approach reduced the spectral congestion and provided a sensitive way to obtain chemical shift assignments for a membrane protein where no high-resolution structure is available. This MAS methodology is widely applicable to the study of other polytopic membrane proteins in functional lipid bilayer environments.

  6. SpyA is a membrane-bound ADP-ribosyltransferase of Streptococcus pyogenes which modifies a streptococcal peptide, SpyB

    OpenAIRE

    Korotkova, Natalia; Hoff, Jessica S.; Becker, Devon M.; Quinn, John Kyle Heggen; Icenogle, Laura M.; Moseley, Steve L.

    2012-01-01

    All sequenced genomes of Streptococcus pyogenes (Group A Streptococcus, GAS) encode a protein, SpyA, with homology to C3-like ADP-ribosyltransferase toxins. SpyA is a novel virulence factor which plays a role in pathogenesis in a mouse model of soft-tissue infection. In this study we demonstrate that SpyA is a surface-exposed membrane protein which is anchored to the streptococcal membrane by an N-terminal transmembrane sequence. We identified a small gene upstream of spyA, designated spyB, w...

  7. Application of the Standardized Precipitation Index (SPI in Greece

    Directory of Open Access Journals (Sweden)

    Christos A. Karavitis

    2011-08-01

    Full Text Available The main premise of the current effort is that the use of a drought index, such as Standardized Precipitation Index (SPI, may lead to a more appropriate understanding of drought duration, magnitude and spatial extent in semi-arid areas like Greece. The importance of the Index may be marked in its simplicity and its ability to identify the beginning and end of a drought event. Thus, it may point towards drought contingency planning and through it to drought alert mechanisms. In this context, Greece, as it very often faces the hazardous impacts of droughts, presents an almost ideal case for the SPI application. The present approach examines the SPI drought index application for all of Greece and it is evaluated accordingly by historical precipitation data. Different time series of data from 46 precipitation stations, covering the period 1947–2004, and for time scales of 1, 3, 6, 12 and 24 months, were used. The computation of the index was achieved by the appropriate usage of a pertinent software tool. Then, spatial representation of the SPI values was carried out with geo-statistical methods using the SURFER 9 software package. The results underline the potential that the SPI usage exhibits in a drought alert and forecasting effort as part of a drought contingency planning posture.

  8. A Guided Inquiry Approach to NMR Spectroscopy

    Science.gov (United States)

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

    1998-04-01

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

  9. Galactic Positron Annihilation Radiation as observed with INTEGRAL/SPI

    Science.gov (United States)

    Weidenspointner, G.; Lonjou, V.; Knoedlseder, J.; Jean, P.; Allain, M.; von Ballmoos, P.; Harris, M. J.; Skinner, G. K.; Vedrenne, G.; Teegarden, B. J.; Gehrels, N.; Guessoum, N.; Schoenfelder, V.; Chapuis, C.; Durouchoux, P.; Cisana, E.; Valesia, M.

    2004-08-01

    The origin of the positrons whose annihilation gives rise to an appreciable flux of gamma rays from the central regions of our Galaxy is one of the mysteries of high energy astrophysics. SPI, one of the two main instruments on board the INTEGRAL observatory, is uniquely suited to study this positron annihilation radiation. It is a high resolution Ge spectrometer (FWHM 2.1 keV at 511 keV) which can image the sky at an angular resolution of about 3 degrees using a coded mask. Early in the mission, the 511 keV annihilation line has already been detected by SPI from the inner Galaxy. We summarize here 1.5 years of SPI observations of annihilation radiation, and discuss the implications of these results for the origin of positrons in the Galaxy. G.W. acknowledges funding by ESA through an external fellowship.

  10. SPI Conformance Gel Applications in Geothermal Zonal Isolation

    Energy Technology Data Exchange (ETDEWEB)

    Burns, Lyle [Clean Tech Innovations, Bartlesville, OK (United States)

    2017-08-08

    Zonal isolation in geothermal injection and producing wells is important while drilling the wells when highly fractured geothermal zones are encountered and there is a need to keep the fluids from interfering with the drilling operation. Department of Energy’s (DOE) Energy Efficiency and Renewable Energy (EERE) objectives are to advance technologies to make it more cost effective to develop, produce, and monitor geothermal reservoirs and produce geothermal energy. Thus, zonal isolation is critical to well cost, reservoir evaluation and operations. Traditional cementing off of the lost circulation or thief zones during drilling is often done to stem the drilling mud losses. This is an expensive and generally unsuccessful technique losing the potential of the remaining fracture system. Selective placement of strong SPI gels into only the offending fractures can maintain and even improve operational efficiency and resource life. The SPI gel system is a unique silicate based gel system that offers a promising solution to thief zones and conformance problems with water and CO2 floods and potentially geothermal operations. This gel system remains a low viscosity fluid until an initiator (either internal such as an additive or external such as CO2) triggers gelation. This is a clear improvement over current mechanical methods of using packers, plugs, liners and cementing technologies that often severely damage the highly fractured area that is isolated. In the SPI gels, the initiator sets up the fluid into a water-like (not a precipitate) gel and when the isolated zone needs to be reopened, the SPI gel may be removed with an alkaline solution without formation damage occurring. In addition, the SPI gel in commercial quantities is expected to be less expensive than competing mechanical systems and has unique deep placement possibilities. This project seeks to improve upon the SPI gel integrity by modifying the various components to impart temperature stability for use in

  11. SPY AGENT BASED SECURE DATA AGGREGATION IN WSN

    Directory of Open Access Journals (Sweden)

    T. Lathies Bhasker

    2014-12-01

    Full Text Available Wireless sensor network consist lot of sensor devices which are activated by using the battery power. These sensor devices are mostly used in hostile environment, military applications etc. So in this type of environment it is highly difficult to collect and transmit the data to the Sink without any data lost. In this paper we proposed SPY Agent based secure data aggregation scheme. Here one SPY Agent moves around the network and monitors the aggregator nodes i.e, the Cluster Heads for secure data collection. In the Simulation section we have analyzed our proposed architecture for both proactive and reactive protocols.

  12. HPLC-NMR revisited: Using time-slice HPLC-SPE-NMR with database assisted dereplication

    DEFF Research Database (Denmark)

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

    2013-01-01

    Time based trapping of chromatographically separated compounds on to solid-phase extraction cartridges (SPE) and subsequent elution to NMR-tubes was done to emulate the function of HPLC–NMR for dereplication purposes. Sufficient mass sensitivity was obtained by the use of a state-of-the-art HPLC......–SPE–NMR-system with a cryogenically cooled probe head, designed for 1.7 mm NMR-tubes. The resulting 1H NMR spectra (600 MHz) were evaluated against a database of previously acquired and prepared spectra. The in-house developed matching algorithm, based on partitioning of the spectra and allowing for changes in the chemical shifts...... and analogues. The database matching of the resulting spectra positively identified expected compounds, while the number of false positives was few and easily recognized....

  13. High resolution {sup 13}C NMR spectra on oriented lipid bilayers: From quantifying the various sources of line broadening to performing 2D experiments with 0.2-0.3 ppm resolution in the carbon dimension

    Energy Technology Data Exchange (ETDEWEB)

    Soubias, O.; Saurel, O.; Reat, V.; Milon, A. [Institut de Pharmacologie et de Biologie Structurale (France)], E-mail: alain.milon@ipbs.fr

    2002-09-15

    {sup 13}C NMR spectra routinely performed on oriented lipid bilayers display linewidth of 1-2 ppm, although T{sub 2} measurements indicate that 0.1-0.2 ppm could be obtained. We have prepared a DMPC - {sup 13}C{sub 4}-cholesterol (7/3) sample, and oriented the lipid bilayers between glass plates so that the bilayer normal makes an angle of 90 deg. (or of the magic angle) with B{sub 0}. We have measured T{sub 2}s, CSAs, and linewidths for the choline {sup 13}C-{gamma}-methyl, the cholesterol-C{sub 4} carbons and the lipid head group phosphorus, at both angles and 313 K. The magnetic field distribution within the sample was calculated using the surface current formalism. The line shapes were simulated as a function of B{sub 0} field inhomogeneities and sample mosaic spread. Both effects contribute to the experimental linewidth. Using three signals of different CSA, we have quantified both contributions and measured the mosaic spread accurately. Direct shimming on a sample signal is essential to obtain sharp resonances and {sup 13}C labelled choline methyl resonance of DMPC is a good candidate for this task. After optimisation of the important parameters (shimming on the choline resonance, mosaic spread of {+-} 0.30 deg.), {sup 13}C linewidth of 0.2-0.3 ppm have been obtained. This newly achieved resolution on bilayers oriented at 90 deg., has allowed to perform two 2D experiments, with a good sensitivity: 2D PELF (correlation of carbon chemical shifts and C-H dipolar couplings) and 2D D-resolved experiment (correlation of carbon chemical shifts and C-C dipolar couplings). A C-C dipolar coupling of 35 {+-} 2 Hz between the choline methyl carbons was determined.

  14. Editing of H2BC NMR spectra.

    Science.gov (United States)

    Nyberg, Nils T; Duus, Jens Ø; Sørensen, Ole W

    2005-12-01

    New versions of the H2BC pulse sequence (Nyberg NT, Duus JØ, Sørensen OW. J. Am. Chem. Soc. 2005; 127: 6154) that edit into two subspectra according to the number of protons attached to 13C nuclei being odd or even are introduced. These sequences can be useful for resolving spectral overlap, which is demonstrated on the molecule prednisolone [(11 beta)-11,17,21-trihydroxypregna-1,4-diene-3,20-dione].

  15. File list: Oth.ALL.20.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.ALL.20.Spi1.AllCell mm9 TFs and others Spi1 All cell types SRX886478,SRX348405,...430,SRX021429 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.ALL.20.Spi1.AllCell.bed ...

  16. File list: Oth.Bld.10.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.Bld.10.Spi1.AllCell mm9 TFs and others Spi1 Blood SRX886478,SRX348405,SRX310205...99,SRX348406,SRX021429,SRX021430 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.Bld.10.Spi1.AllCell.bed ...

  17. File list: Oth.PSC.05.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.PSC.05.Spi1.AllCell mm9 TFs and others Spi1 Pluripotent stem cell SRX021436,SRX...021435,SRX021438,SRX021437 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.PSC.05.Spi1.AllCell.bed ...

  18. Spi-1/PU.1 activates transcription through clustered DNA occupancy in erythroleukemia.

    Science.gov (United States)

    Ridinger-Saison, Maya; Boeva, Valentina; Rimmelé, Pauline; Kulakovskiy, Ivan; Gallais, Isabelle; Levavasseur, Benjamin; Paccard, Caroline; Legoix-Né, Patricia; Morlé, François; Nicolas, Alain; Hupé, Philippe; Barillot, Emmanuel; Moreau-Gachelin, Françoise; Guillouf, Christel

    2012-10-01

    Acute leukemias are characterized by deregulation of transcriptional networks that control the lineage specificity of gene expression. The aberrant overexpression of the Spi-1/PU.1 transcription factor leads to erythroleukemia. To determine how Spi-1 mechanistically influences the transcriptional program, we combined a ChIP-seq analysis with transcriptional profiling in cells from an erythroleukemic mouse model. We show that Spi-1 displays a selective DNA-binding that does not often cause transcriptional modulation. We report that Spi-1 controls transcriptional activation and repression partially through distinct Spi-1 recruitment to chromatin. We revealed several parameters impacting on Spi-1-mediated transcriptional activation. Gene activation is facilitated by Spi-1 occupancy close to transcriptional starting site of genes devoid of CGIs. Moreover, in those regions Spi-1 acts by binding to multiple motifs tightly clustered and with similar orientation. Finally, in contrast to the myeloid and lymphoid B cells in which Spi-1 exerts a physiological activity, in the erythroleukemic cells, lineage-specific cooperating factors do not play a prevalent role in Spi-1-mediated transcriptional activation. Thus, our work describes a new mechanism of gene activation through clustered site occupancy of Spi-1 particularly relevant in regard to the strong expression of Spi-1 in the erythroleukemic cells.

  19. File list: Oth.ALL.05.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.ALL.05.Spi1.AllCell mm9 TFs and others Spi1 All cell types SRX886478,SRX348405,...924,SRX021429 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.ALL.05.Spi1.AllCell.bed ...

  20. File list: Oth.ALL.10.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.ALL.10.Spi1.AllCell mm9 TFs and others Spi1 All cell types SRX886478,SRX348405,...429,SRX021430 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.ALL.10.Spi1.AllCell.bed ...

  1. File list: Oth.ALL.50.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.ALL.50.Spi1.AllCell mm9 TFs and others Spi1 All cell types SRX886478,SRX310205,...923,SRX122453 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.ALL.50.Spi1.AllCell.bed ...

  2. File list: Oth.PSC.20.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.PSC.20.Spi1.AllCell mm9 TFs and others Spi1 Pluripotent stem cell SRX021436,SRX...021435,SRX021438,SRX021437 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.PSC.20.Spi1.AllCell.bed ...

  3. File list: Oth.PSC.10.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.PSC.10.Spi1.AllCell mm9 TFs and others Spi1 Pluripotent stem cell SRX021436,SRX...021435,SRX021438,SRX021437 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.PSC.10.Spi1.AllCell.bed ...

  4. File list: Oth.Bld.20.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.Bld.20.Spi1.AllCell mm9 TFs and others Spi1 Blood SRX886478,SRX348405,SRX310205...25,SRX700924,SRX021430,SRX021429 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.Bld.20.Spi1.AllCell.bed ...

  5. File list: Oth.Bld.50.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.Bld.50.Spi1.AllCell mm9 TFs and others Spi1 Blood SRX886478,SRX310205,SRX884085...30,SRX021429,SRX700923,SRX122453 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.Bld.50.Spi1.AllCell.bed ...

  6. File list: Oth.Bld.05.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.Bld.05.Spi1.AllCell mm9 TFs and others Spi1 Blood SRX886478,SRX348405,SRX197252...23,SRX700925,SRX700924,SRX021429 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.Bld.05.Spi1.AllCell.bed ...

  7. File list: Oth.PSC.50.Spi1.AllCell [Chip-atlas[Archive

    Lifescience Database Archive (English)

    Full Text Available Oth.PSC.50.Spi1.AllCell mm9 TFs and others Spi1 Pluripotent stem cell SRX021436,SRX...021438,SRX021435,SRX021437 http://dbarchive.biosciencedbc.jp/kyushu-u/mm9/assembled/Oth.PSC.50.Spi1.AllCell.bed ...

  8. Structural basis of divergent cyclin-dependent kinase activation by Spy1/RINGO proteins

    Energy Technology Data Exchange (ETDEWEB)

    McGrath, Denise A.; Fifield, Bre-Anne; Marceau, Aimee H.; Tripathi, Sarvind; Porter, Lisa A.; Rubin, Seth M. (UCSC); (Windsor)

    2017-06-30

    Cyclin-dependent kinases (Cdks) are principal drivers of cell division and are an important therapeutic target to inhibit aberrant proliferation. Cdk enzymatic activity is tightly controlled through cyclin interactions, posttranslational modifications, and binding of inhibitors such as the p27 tumor suppressor protein. Spy1/RINGO (Spy1) proteins bind and activate Cdk but are resistant to canonical regulatory mechanisms that establish cell-cycle checkpoints. Cancer cells exploit Spy1 to stimulate proliferation through inappropriate activation of Cdks, yet the mechanism is unknown. We have determined crystal structures of the Cdk2-Spy1 and p27-Cdk2-Spy1 complexes that reveal how Spy1 activates Cdk. We find that Spy1 confers structural changes to Cdk2 that obviate the requirement of Cdk activation loop phosphorylation. Spy1 lacks the cyclin-binding site that mediates p27 and substrate affinity, explaining why Cdk-Spy1 is poorly inhibited by p27 and lacks specificity for substrates with cyclin-docking sites. We identify mutations in Spy1 that ablate its ability to activate Cdk2 and to proliferate cells. Our structural description of Spy1 provides important mechanistic insights that may be utilized for targeting upregulated Spy1 in cancer.

  9. Planar microcoil-based microfluidic NMR probes.

    NARCIS (Netherlands)

    Massin, C.; Vincent, F.; Homsy, A.; Ehrmann, K.; Boero, G.; Besse, P-A; Daridon, A.; Verpoorte, E.; de Rooij, N.F.; Popovic, R.S.

    2003-01-01

    Microfabricated small-volume NMR probes consisting of electroplated planar microcoils integrated on a glass substrate with etched microfluidic channels are fabricated and tested. 1H NMR spectra are acquired at 300 MHz with three different probes having observed sample volumes of respectively 30, 120

  10. Planar microcoil-based microfluidic NMR probes.

    NARCIS (Netherlands)

    Massin, C.; Vincent, F.; Homsy, A.; Ehrmann, K.; Boero, G.; Besse, P-A; Daridon, A.; Verpoorte, E.; de Rooij, N.F.; Popovic, R.S.

    2003-01-01

    Microfabricated small-volume NMR probes consisting of electroplated planar microcoils integrated on a glass substrate with etched microfluidic channels are fabricated and tested. 1H NMR spectra are acquired at 300 MHz with three different probes having observed sample volumes of respectively 30, 120

  11. Candidate Distributions for Climatological Drought Indices (SPI and SPEI)

    NARCIS (Netherlands)

    Stagge, James H.; Tallaksen, Lena M.; Gudmundsson, Lukas; Loon, Van Anne F.; Stahl, Kerstin

    2015-01-01

    The Standardized Precipitation Index (SPI), a well-reviewed meteorological drought index recommended by the World Meteorological Organization (WMO), and its more recent climatic water balance variant, the Standardized Precipitation-Evapotranspiration Index (SPEI), both rely on selection of a univ

  12. Mission Possible: Spy a Book! 2003 Texas Reading Club Manual.

    Science.gov (United States)

    Heard, Adriana Flores; Ingham, Donna; McDermott, Joe; Meyer, Sally; Parrish, Leila; Schill, Victor; Trevino, Rose

    The purpose of this manual for the 2003 Texas Reading Club, "Mission Possible: Spy a Book!" is to assist library staff who serve youth by suggesting ideas for programs that will attract children to the library. The following chapters are included: (1) Marketing, Cooperation and PR; (2) Serving Children with Disabilities; (3) Theme Songs;…

  13. World War II Spy Kit: "The Great Nazi Intelligence Coup."

    Science.gov (United States)

    Haight, David

    This instructional packet is designed to introduce students to primary source material by having them participate in an historical "what might have been." Students engage in critical thinking and document analysis, and through the process learn about Operation OVERLORD and World War II in general. This spy kit centers on Operation…

  14. Candidate Distributions for Climatological Drought Indices (SPI and SPEI)

    NARCIS (Netherlands)

    Stagge, James H.; Tallaksen, Lena M.; Gudmundsson, Lukas; Loon, Van Anne F.; Stahl, Kerstin

    2015-01-01

    The Standardized Precipitation Index (SPI), a well-reviewed meteorological drought index recommended by the World Meteorological Organization (WMO), and its more recent climatic water balance variant, the Standardized Precipitation-Evapotranspiration Index (SPEI), both rely on selection of a univ

  15. The Sneaky Sneaker Spies and the Mysterious Black Ink

    Science.gov (United States)

    Savran, Michelle

    2012-01-01

    In this article, the author describes the process of making "The Sneaky Sneaker Spies and the Mysterious Black Ink," a six-minute animation starring five art students who form a detective club. This animation is available online for art teachers to use in their own classrooms. After showing this video in class, art teachers could have students try…

  16. Regulation of follicular B cell differentiation by the related E26 transformation-specific transcription factors PU.1, Spi-B, and Spi-C.

    Science.gov (United States)

    DeKoter, Rodney P; Geadah, Marc; Khoosal, Sonam; Xu, Li S; Thillainadesan, Gobi; Torchia, Joseph; Chin, Shu Shien; Garrett-Sinha, Lee Ann

    2010-12-15

    Splenic B-2 cells can be divided into two major subsets: follicular (FO) and marginal zone (MZ) B cells. FO and MZ B cells are generated from immature transitional B cells. Few transcription factors have been identified that regulate FO B cell differentiation. The highly related proteins PU.1, Spi-B, and Spi-C are transcription factors of the E26-transformation-specific family and are important for B cell differentiation and function. To determine whether these proteins play a role in the differentiation of FO B cells, we performed a detailed analysis of splenic B cells in mice with inactivating mutations in the genes encoding PU.1 (Sfpi1) or Spi-B (Spib). Sfpi1(+/-) Spib(-/-) (PUB) mice had a 9-fold reduction in the frequency of CD23(+) FO B cells compared with that of wild-type mice. In contrast, PUB mice had a 2-fold increase in the frequency of MZ B cells that was confirmed by immunofluorescence staining. Expression of Spi-C in Eμ-Spi-C transgenic PUB mice partially rescued frequencies of CD23(+) B cells. Gene expression analysis, in vitro reporter assays, and chromatin immunoprecipitation experiments showed that transcription of the Fcer2a gene encoding CD23 is activated by PU.1, Spi-B, and Spi-C. These results demonstrate that FO B cell differentiation is regulated by the E26-transformation-specific transcription factors PU.1, Spi-B, and Spi-C.

  17. Polymeric proanthocyanidins 13C NMR studies of procyanidins

    Science.gov (United States)

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

    1982-01-01

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

  18. Drought Index Analizes With Rainfall Patern Indicators Use SPI Method (Case Study Bangga Watershed

    Directory of Open Access Journals (Sweden)

    Beti Mayasari

    2017-05-01

    Full Text Available Irregular weather and climate changes caused by El – Nino effect drought in some areas, including in Indonesia. The location of this study lies in the Bangga watershed. The purpose of this study was to determine rainfall patterns, drought level, the worst drought that occurred and the prediction for the future. One method for analysis of drought is using SPI (Standardized Precipitation Index. This method aims to calculate the value of a drought index that would indicate the level of the existing drought in a region. Data used are monthly rainfall from two station for 23 years (year 1993-2015. After analyzing the drought, the projection made with software Makesens 1.0. The study results showed that the worst drought in Bangga watershed occurred in April 2015 with drought index -3516 for one monthly SPI, -2815 for three monthly SPI, -3254 for six monthly SPI, -2171 for nine monthly SPI, and - 2922 for twelve 12 monthly SPI. Once projected until 2050, generally Bangga watershed experiencing dry conditions with the worst drought in July with a value of -3.83 for one monthly SPI, -3.65 for three monthly SPI, -3.44 for six monthly SPI, -2.6 for nine monthly SPI and -2.32 for twelve monthly SPI.

  19. Analysis of {sup 2}H NMR spectra of water molecules on the surface of nano-silica material MCM-41: Deconvolution of the signal into a Lorentzian and a powder pattern line shapes

    Energy Technology Data Exchange (ETDEWEB)

    Hassan, J., E-mail: jamal.hassan@kustar.ac.ae [Applied Mathematics and Sciences, KUSTAR, UAE and Department of Physics and Astronomy, University of Waterloo, Waterloo, Ontario, N2L 3G1 (Canada)

    2012-01-01

    Water {sup 2}H NMR signal on the surface of nano-silica material MCM-41 consists of two overlapping resonances. The {sup 2}H water spectrum shows a superposition of a Lorentzian line shape and the familiar NMR powder pattern line shape, indicating the existence of two spin components. Exchange occurs between these two groups. Decomposition of the two signals is a crucial starting point to study the exchange process. In this article we have determined these spin component populations along with other important parameters for the {sup 2}H water NMR signal over a temperature range between 223 K and 343 K.

  20. Identification of cognate host targets and specific ubiquitylation sites on the Salmonella SPI-1 effector SopB/SigD

    DEFF Research Database (Denmark)

    Rogers, Lindsay D; Kristensen, Anders R; Boyle, Erin C

    2008-01-01

    Salmonella enterica is a bacterial pathogen responsible for enteritis and typhoid fever. Virulence is linked to two Salmonella pathogenicity islands (SPI-1 and SPI-2) on the bacterial chromosome, each of which encodes a type III secretion system. While both the SPI-1 and SPI-2 systems secrete...

  1. Scalar operators in solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Boqin

    1991-11-01

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

  2. 13C-NMR chemical shift databases as a quick tool to evaluate structural models of humic substances

    DEFF Research Database (Denmark)

    Nyrop Albers, Christian; Hansen, Poul Erik

    2010-01-01

    Models for humic and fulvic acids are discussed based on 13C liquid state NMR spectra combined with results from elemental analysis and titration studies. The analysis of NMR spectra is based on a full reconstruction of the NMR spectrum done with help of 13C-NMR data bases by adding up chemical s...

  3. NMR spectroscopy using liquid crystal solvents

    CERN Document Server

    Emsley, JW

    2013-01-01

    NMR Spectroscopy using Liquid Crystal Solvents covers the importance of using a liquid crystal solvent in NMR to derive nuclear dipolar spin-spin coupling constants. This book is composed of ten chapters, and begins with a brief description of the features and benefits of liquid crystal in NMR spectroscopic analysis. The succeeding chapters deal with the mode of operation of nuclear spin Hamiltonian for partially oriented molecules and the analysis of NMR spectra of partially oriented molecules, as well as the determination of rigid molecule structure. These topics are followed by discussions

  4. Solid-state NMR and Membrane Proteins

    Science.gov (United States)

    Opella, Stanley J.

    2015-01-01

    The native environment for a membrane protein is a phospholipid bilayer. Because the protein is immobilized on NMR timescales by the interactions within a bilayer membrane, solid-state NMR methods are essential to obtain high-resolution spectra. Approaches have been developed for both unoriented and oriented samples, however, they all rest on the foundation of the most fundamental aspects solid-state NMR, and the chemical shift and homo- and hetero-nuclear dipole-dipole interactions. Solid-state NMR has advanced sufficiently to enable the structures of membrane proteins to be determined under near-native conditions in phospholipid bilayers. PMID:25681966

  5. NMR molecular photography

    CERN Document Server

    Khitrin, A K; Fung, B M; Khitrin, Anatoly K.; Ermakov, Vladimir L.

    2002-01-01

    A procedure is described for storing a 2D pattern consisting of 32x32 = 1024 bits in a spin state of a molecular system and then retrieving the stored information as a stack of NMR spectra. The system used is a nematic liquid crystal, the protons of which act as spin clusters with strong intramolecular interactions. The technique used is a programmable multi-frequency irradiation with low amplitude. When it is applied to the liquid crystal, a large number of coherent long-lived 1H response signals can be excited, resulting in a spectrum showing many sharp peaks with controllable frequencies and amplitudes. The spectral resolution is enhanced by using a second weak pulse with a 90 phase shift, so that the 1024 bits of information can be retrieved as a set of well-resolved pseudo-2D spectra reproducing the input pattern.

  6. CASD-NMR: critical assessment of automated structure determination by NMR

    NARCIS (Netherlands)

    Rosato, A.; van der Schot, G.; Bonvin, A.M.J.J.

    2009-01-01

    NMR spectroscopy is currently the only technique for determining the solution structure of biological macromolecules. This typically requires both the assignment of resonances and a labor-intensive analysis of multidimensional nuclear Overhauser effect spectroscopy (NOESY) spectra, in which peaks

  7. Optimization and practical implementation of ultrafast 2D NMR experiments

    OpenAIRE

    Queiroz Júnior,Luiz H. K.; Antonio G. Ferreira; Patrick Giraudeau

    2013-01-01

    Ultrafast 2D NMR is a powerful methodology that allows recording of a 2D NMR spectrum in a fraction of second. However, due to the numerous non-conventional parameters involved in this methodology its implementation is no trivial task. Here, an optimized experimental protocol is carefully described to ensure efficient implementation of ultrafast NMR. The ultrafast spectra resulting from this implementation are presented based on the example of two widely used 2D NMR experiments, COSY and HSQC...

  8. NMR GHZ

    CERN Document Server

    Laflamme, R; Zurek, W H; Catasti, P; Mariappan, S V S

    1998-01-01

    We describe the creation of a Greenberger-Horne-Zeilinger (GHZ) state of the form |000>+|111> (three maximally entangled quantum bits) using Nuclear Magnetic Resonance (NMR). We have successfully carried out the experiment using the proton and carbon spins of trichloroethylene, and confirmed the result using state tomography. We have thus extended the space of entangled quantum states explored systematically to three quantum bits, an essential step for quantum computation.

  9. American Who Spied against Their Country Since World War 2

    Science.gov (United States)

    1992-05-01

    officers were John Walker Jr., Joseph Helmich , Jr., and James Hall Il1. Stephen Baba, the youngest officer, was a junior electronics material officer...seven spies who were paid between $100,000 and $1,000,000 were William Bell, James Hall Il1, James Harper, Jr., Joseph Helmich , Jr., Edward Howard...Conrad, Nelson Drummond, George French, George Gessner, James Harper, Jr., Joseph Helmich , Jr., Daulton Lee, Ronald Pelton, Jonathan Pollard, Arthur

  10. The Spies and the Gran Turco (XVI Century

    Directory of Open Access Journals (Sweden)

    Gennaro Varriale

    2016-04-01

    Full Text Available This present essay focuses on the information that Hispanic spies collected in the Levant during the sixteenth-century. Based on archival and literary sources, the study is built around the typical structure of a lyric opera to show the worth of the secret correspondence such as archetype of European perception about the Ottoman Empire and, more generally, about all the Islam.

  11. Super Spy variants implicate flexibility in chaperone action.

    Science.gov (United States)

    Quan, Shu; Wang, Lili; Petrotchenko, Evgeniy V; Makepeace, Karl At; Horowitz, Scott; Yang, Jianyi; Zhang, Yang; Borchers, Christoph H; Bardwell, James Ca

    2014-01-01

    Experimental study of the role of disorder in protein function is challenging. It has been proposed that proteins utilize disordered regions in the adaptive recognition of their various binding partners. However apart from a few exceptions, defining the importance of disorder in promiscuous binding interactions has proven to be difficult. In this paper, we have utilized a genetic selection that links protein stability to antibiotic resistance to isolate variants of the newly discovered chaperone Spy that show an up to 7 fold improved chaperone activity against a variety of substrates. These "Super Spy" variants show tighter binding to client proteins and are generally more unstable than is wild type Spy and show increases in apparent flexibility. We establish a good relationship between the degree of their instability and the improvement they show in their chaperone activity. Our results provide evidence for the importance of disorder and flexibility in chaperone function. DOI: http://dx.doi.org/10.7554/eLife.01584.001.

  12. 基于 FPGA 的SPI 总线接口的实现

    Institute of Scientific and Technical Information of China (English)

    黄威; 于梦磊

    2012-01-01

      FPGA 具有快速稳定、高效率等优点.SPI 接口具有全双工操作、协议简单、数据传输速率较高等优点.将FPGA 编程的灵活性和 SPI 总线的易用性结合,利用 Verilog 语言编程实 SPI 的接口功能.

  13. Inhibition of cellular Shp2 activity by a methyl ester analog of SPI-112.

    Science.gov (United States)

    Chen, Liwei; Pernazza, Daniele; Scott, Latanya M; Lawrence, Harshani R; Ren, Yuan; Luo, Yunting; Wu, Xin; Sung, Shen-Shu; Guida, Wayne C; Sebti, Said M; Lawrence, Nicholas J; Wu, Jie

    2010-09-15

    The protein tyrosine phosphatase (PTP) Shp2 (PTPN11) is an attractive target for anticancer drug discovery because it mediates growth factor signaling and its gain-of-function mutants are causally linked to leukemias. We previously synthesized SPI-112 from a lead compound of Shp2 inhibitor, NSC-117199. In this study, we demonstrated that SPI-112 bound to Shp2 by surface plasmon resonance (SPR) and displayed competitive inhibitor kinetics to Shp2. Like some other compounds in the PTP inhibitor discovery efforts, SPI-112 was not cell permeable, precluding its use in biological studies. To overcome the cell permeation issue, we prepared a methyl ester SPI-112 analog (SPI-112Me) that is predicted to be hydrolyzed to SPI-112 upon entry into cells. Fluorescence uptake assay and confocal imaging suggested that SPI-112Me was taken up by cells. Incubation of cells with SPI-112Me inhibited epidermal growth factor (EGF)-stimulated Shp2 PTP activity and Shp2-mediated paxillin dephosphorylation, Erk1/2 activation, and cell migration. SPI-112Me treatment also inhibited Erk1/2 activation by a Gab1-Shp2 chimera. Treatment of Shp2(E76K) mutant-transformed TF-1 myeloid cells with SPI-112Me resulted in inhibition of Shp2(E76K)-dependent cell survival, which is associated with inhibition of Shp2(E76K) PTP activity, Shp2(E76K)-induced Erk1/2 activation, and Bcl-XL expression. Furthermore, SPI-112Me enhanced interferon-gamma (IFN-gamma)-stimulated STAT1 tyrosine phosphorylation, ISRE-luciferase reporter activity, p21 expression, and the anti-proliferative effect. Thus, the SPI-112 methyl ester analog was able to inhibit cellular Shp2 PTP activity.

  14. Penerapan Metoda Serial Peripheral Interface (SPI pada Rancang Bangun Data Logger berbasis SD card

    Directory of Open Access Journals (Sweden)

    RATNA SUSANA

    2016-08-01

    Full Text Available ABSTRAK Serial Peripheral Interface (SPI adalah protokol komunikasi yang dapat digunakan sebagai interface komunikasi antara mikrokontroler dengan SD Card. Dengan menerapkan metoda SPI pada data logger berbasis SD Card, maka dapat diketahui karakteristik protokol komunikasi SPI antara mikrokontroler dengan SD Card. SD Card diformat dengan tipe FAT 16, dan data di dalam SD Card berupa sekumpulan paket data sensor yang diambil secara periodik dan disimpan dalam bentuk file dengan format.csv. Berdasarkan format paket data sensor yang dibuat, dapat dihitungwaktu perekaman data yang diperlukan agar kapasitas SD Card terisi penuh oleh data sensor. Hasil penelitian menunjukkan,bahwa metoda SPI yang diterapkan pada penelitian ini memiliki sifat akan melakukan pemeriksaan berulang pada pin MISO terhadap command yang dikirimkan oleh mikrokontroler melalui pin MOSI. Proses read/write data pada SD Card data logger memiliki keberhasilan 100%, karena SD Card telah terinisialisasi dalam mode SPI melalui perintah reset dan init SD Card. Komunikasi ini dapat dilakukan dengan menggunakan crystal 4 Mhz – 20 Mhz. Untuk pengujian konfigurasi SPI, hanya Independent Slave Configuration yang dapat digunakan pada komunikasi SPI dengan 2 SD card sebagai slave. Kata kunci: Serial Peripheral Interface (SPI, Data Logger, SD card, FAT16 ABSTRACT Serial Peripheral Interface (SPI is a communication protocol that can be applied as a communication interface between microcontroller to SD Card. By implementing the SPI method to a data logger based on SD Card, it can be known the characteristics of the SPI communications protocol between microcontroller to SD Card. SD Card formatted in FAT 16 type, and data on the SD Card is the form of sensor data packets collection which be captured periodically and saved in .csv format file. Based on the sensor data packet format is created, it can be calculated recording time data required so that the SD Card capacity completely filled by the

  15. The ectromelia virus SPI-2 protein causes lethal mousepox by preventing NK cell responses.

    Science.gov (United States)

    Melo-Silva, Carolina R; Tscharke, David C; Lobigs, Mario; Koskinen, Aulikki; Wong, Yik Chun; Buller, R Mark; Müllbacher, Arno; Regner, Matthias

    2011-11-01

    Ectromelia virus (ECTV) is a natural pathogen of mice that causes mousepox, and many of its genes have been implicated in the modulation of host immune responses. Serine protease inhibitor 2 (SPI-2) is one of these putative ECTV host response modifier proteins. SPI-2 is conserved across orthopoxviruses, but results defining its mechanism of action and in vivo function are lacking or contradictory. We studied the role of SPI-2 in mousepox by deleting the SPI-2 gene or its serine protease inhibitor reactive site. We found that SPI-2 does not affect viral replication or cell-intrinsic apoptosis pathways, since mutant viruses replicate in vitro as efficiently as wild-type virus. However, in the absence of SPI-2 protein, ECTV is attenuated in mousepox-susceptible mice, resulting in lower viral loads in the liver, decreased spleen pathology, and substantially improved host survival. This attenuation correlates with more effective immune responses in the absence of SPI-2, including an earlier serum gamma interferon (IFN-γ) response, raised serum interleukin 18 (IL-18), increased numbers of granzyme B(+) CD8(+) T cells, and, most notably, increased numbers and activation of NK cells. Both virus attenuation and the improved immune responses associated with SPI-2 deletion from ECTV are lost when mice are depleted of NK cells. Consequently, SPI-2 renders mousepox lethal in susceptible strains by preventing protective NK cell defenses.

  16. SPI Based Meteorological Drought Assessment over a Humid Basin: Effects of Processing Schemes

    Directory of Open Access Journals (Sweden)

    Han Zhou

    2016-08-01

    Full Text Available Meteorological drought monitoring is important for drought early warning and disaster prevention. Regional meteorological drought can be evaluated and analyzed with standardized precipitation index (SPI. Two main processing schemes are frequently adopted: (1 mean of all SPI calculated from precipitation at individual stations (SPI-mean; and (2 SPI calculated from all-station averaged precipitation (precipitation-mean. It yet remains unclear if two processing schemes could make difference in drought assessment, which is of significance to reliable drought monitoring. Taking the Poyang Lake Basin with monthly precipitation recorded by 13 national stations for 1957–2014, this study examined two processing schemes. The precipitation mean and SPI mean were respectively calculated with the Thiessen Polygon weighting approach. Our results showed that the two SPI series individually constructed from two schemes had similar features and monitoring trends of regional meteorological droughts. Both SPI series had a significantly positive correlation (p < 0.005 with the number of precipitation stations. The precipitation-mean scheme reduced the extent of precipitation extremes and made the precipitation data more clustered in some certain, it made less precipitation deviate from the precipitation-mean series farther when less precipitation occurred universally, which would probably change the drought levels. Alternatively, the SPI-mean scheme accurately highlighted the extremes especially for those with wide spatial distribution over the region. Therefore, for regional meteorological drought monitoring, the SPI-mean scheme is recommended for its more suitable assessment of historical droughts.

  17. Discovery of new natural products by application of X-hitting, a novel algorithm for automated comparison of full UV-spectra, combined with structural determination by NMR spectroscophy

    DEFF Research Database (Denmark)

    Larsen, Thomas Ostenfeld; Petersen, Bent O.; Duus, Jens Øllgaard;

    2005-01-01

    X-hitting, a newly developed algorithm for automated comparison of UV data, has been used for the tracking of two novel spiro-quinazoline metabolites, lapatins A (1)andB(2), in a screening study targeting quinazolines. The structures of 1 and 2 were elucidated by analysis of spectroscopic data, p......, primarily 2D NMR....

  18. 2D-NMR (HSQC) difference spectra between specifically 13C-enriched and unenriched protolignin of Ginkgo biloba obtained in the solution state of whole cell wall material

    Science.gov (United States)

    Noritsugu Terashima; Takuya Akiyama; Sally Ralph; Dmitry Evtuguin; Carlos Neto Pascoal; Jim Parkas; Magnus Paulsson; Ulla Westermark; John Ralph

    2009-01-01

    In the structural analysis of lignins by 13C-NMR, signal overlap limits definitive assignment and accurate intensity measurement. Selective labeling by 13C-enrichment of a specific carbon in lignin enhances its signal intensity in the spectrum. Further enhancement of the specifically labeled carbons can be realized via...

  19. High-resolution NMR spectroscopy under the fume hood.

    Science.gov (United States)

    Küster, Simon K; Danieli, Ernesto; Blümich, Bernhard; Casanova, Federico

    2011-08-07

    This work reports the possibility to acquire high-resolution (1)H NMR spectra with a fist-sized NMR magnet directly installed under the fume hood. The small NMR sensor based on permanent magnets was used to monitor the trimerization of propionaldehyde catalyzed by indium trichloride in real time by continuously circulating the reaction mixture through the magnet bore in a closed loop with the help of a peristaltic pump. Thanks to the chemical selectivity of NMR spectroscopy the progress of the reaction can be monitored on-line by determining the concentrations of both reactant and product from the area under their respective lines in the NMR spectra as a function of time. This in situ measurement demonstrates that NMR probes can be used in chemistry laboratories, e.g. for reaction optimization, or installed at specific points of interest along industrial process lines. Therefore, it will open the door for the implementation of feedback control based on spectroscopic NMR data.

  20. The Influence of Glycerin on Static Rheological Properties of SPI Solution%SPI/甘油水溶液流变性的研究

    Institute of Scientific and Technical Information of China (English)

    孔洁静; 叶晓文; 叶君; 熊犍

    2012-01-01

    The influence of glycerin on static theological properties and the rehological behaviors of SPI solutions were investigated. The change of shear viscosity of SPI with concentration and temperature after adding glycerin was discussed, specially comparing with SPI control solution. The results have indicated that SPI/glycerin solutions presented a typical behavior of pseudoplastic fluid, and glycerin not only reduced the viscosity and weakened pseudoplastic behavior of SPI but also improve its thermal stability.%采用流变仪初步研究了甘油对大豆分离蛋白(SPI)静态流变性能的影响及其溶液性质,讨论了添加甘油后,SPI水溶液剪切粘度随浓度和温度的变化,并与没添加甘油的SPI水溶液对比.结果表明:SPI/甘油水溶液体系呈现剪切变稀性,甘油不仅降低了体系的粘度和减弱其剪切变稀性,同时还提高了体系的抗热性能.

  1. Assigning the NMR Spectrum of Glycidol: An Advanced Organic Chemistry Exercise

    Science.gov (United States)

    Helms, Eric; Arpaia, Nicholas; Widener, Melissa

    2007-01-01

    Various one- and two-dimensional NMR experiments have been found to be extremely useful for assigning the proton and carbon NMR spectra of glycidol. The technique provides extremely valuable information aiding in the complete assignment of the peaks.

  2. Understanding surveillance technologies spy devices, their origins & applications

    CERN Document Server

    Petersen, JK

    2001-01-01

    From electronic wire taps to baby monitors and long-distance video and listening devices, startling changes occur everyday in how we gather, interpret, and transmit information. An extraordinary range of powerful new technologies has come into existence to meet the requirements of this expanding field.Your search for a comprehensive resource for surveillance devices is over. Understanding Surveillance Technologies: Spy Devices, Their Origins and Applications serves as a provocative, broad-based, and visually appealing reference that introduces and describes the technologies rapidly moving into

  3. [Nurses and spies during the First World War].

    Science.gov (United States)

    Halioua, Bruno

    2014-06-01

    During the First World War, some nurses distinguished themselves by playing a significant role in spy networks, using their activity as a cover. They took an active part in the setting up of escape routes for allied prisoners of war and the gathering of intelligence on the positions of German troops, in particular in Belgium and northern France. Among them Edith Cavell, Gabrielle Petit, Louise de Bettignies, Marie-Léonie Vanhoutte, Marthe Cocknaert and Emilienne-Rose Ducimetière are considered as heroines.

  4. Minox Digital Spy Camera数码相机

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Digital Spy Camera是一种间谍框机,看起来更像是一个小MP3,重量只有60g,非常便携.非常迷你,内置320万像素cmos传感器.42mm定焦镜头最大光圈130.还有一个外接的闪光灯.其外形尺寸86mm×29mm×20mm.呈现细长形结构.

  5. Spying by American Archaeologists in World War I

    Directory of Open Access Journals (Sweden)

    David L. Browman

    2011-11-01

    Full Text Available I am interested in detailing two aspects linked to the issue of several archaeologists working for the U.S. Office of Naval Intelligence (ONI during the First World War. These spying activities were part of the controversy surrounding the censure of Franz Boas by the American Anthropological Association (AAA for his published letter of October 1919, in which Boas claimed that four unnamed researchers were involved in espionage activities using archaeological research as a front. As they were unnamed, who were these four archaeologists?

  6. Covariance NMR spectroscopy by singular value decomposition.

    Science.gov (United States)

    Trbovic, Nikola; Smirnov, Serge; Zhang, Fengli; Brüschweiler, Rafael

    2004-12-01

    Covariance NMR is demonstrated for homonuclear 2D NMR data collected using the hypercomplex and TPPI methods. Absorption mode 2D spectra are obtained by application of the square-root operation to the covariance matrices. The resulting spectra closely resemble the 2D Fourier transformation spectra, except that they are fully symmetric with the spectral resolution along both dimensions determined by the favorable resolution achievable along omega2. An efficient method is introduced for the calculation of the square root of the covariance spectrum by applying a singular value decomposition (SVD) directly to the mixed time-frequency domain data matrix. Applications are shown for 2D NOESY and 2QF-COSY data sets and computational benchmarks are given for data matrix dimensions typically encountered in practice. The SVD implementation makes covariance NMR amenable to routine applications.

  7. Oriented solid-state NMR spectrosocpy

    DEFF Research Database (Denmark)

    Bertelsen, Kresten

    This thesis is concerned with driving forward oriented solid-state NMR spectroscopy as a viable technique for studying peptides in membrane bilayers. I will show that structural heterogeneity is an intrinsic part of the peptide/lipid system and that NMR can be used to characterize static...... and dynamic structural features of the peptides and its local surroundings. In fact one need to take into account the dynamical features of the system in order to correctly predict the structure from oriented solid-state NMR spectra.      ...

  8. Graphical programming for pulse automated NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

    Belmonte, S.B. [Universidade do Estado, Rio de Janeiro, RJ (Brazil); Oliveira, I.S.; Guimaraes, A.P. [Centro Brasileiro de Pesquisas Fisicas (CBPF), Rio de Janeiro, RJ (Brazil)

    1999-01-01

    We describe a software program designed to control a broadband pulse Nuclear Magnetic Resonance (NMR) spectrometer used in zero-field NMR studies of magnetic metals. The software is written in the graphical language LabVIEW. This type of programming allows modifications and the inclusion of new routines to be easily made by the non-specialist, without changing the basic structure of the program. The program corrects for differences in the gain of the two acquisition channels [U (phase) and V (quadrature)], and automatic baseline subtraction. We present examples of measurements of NMR spectra, spin-echo decay (T{sub 2}), and quadrupolar oscillations, performed in magnetic intermetallic compounds. (author)

  9. Direct 13C NMR Detection in HPLC Hyphenation Mode

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  10. Long-Term Monitoring of the Black Hole Candidate Swift J1753.5-0127 with INTEGRAL/SPI

    CERN Document Server

    Rodi, James; Roques, Jean-Pierre

    2015-01-01

    The black hole candidate Swift J1753.5-0127 went into outburst in 2005 June. Rather than fade into quiescence as most black-hole-candidate transients do, it has remained in a low hard spectral state for most of the $\\sim$ 9 years after outburst. The persistent emission while in a hard state is reminiscent of the black hole Cyg X-1 and the black hole candidates 1E 1740.7-2942 and GRS 1758-258. Thus far hard X-ray/soft gamma-ray results have focused mainly on the 2005 flare, with a few additional observations during 2007. Here, we present results from INTEGRAL/SPI observations from 2005 - 2010 spanning the 22 - 650 keV energy range. Spectral analysis shows a weak high-energy excess ( $\\sim$ 2.9 $\\sigma$) above a cutoff powerlaw model that is well fit by a powerlaw suggesting an additional spectral component. Observations of Cyg X-1, 1E 1740.7-2942, and GRS 1758-258 have shown similar spectra requiring an additional high-energy component The SPI results are compared to previously reported results for Swift J1753...

  11. Imaging with the coded aperture gamma-ray spectrometer SPI aboard INTEGRAL

    Science.gov (United States)

    Wunderer, Cornelia B.; Strong, Andrew W.; Attie, David; von Ballmoos, Peter; Connell, Paul; Cordier, Bertrand; Diehl, Roland; Hammer, J. Wolfgang; Jean, Pierre; von Kienlin, Andreas; Knoedlseder, Juergen; Lichti, Giselher G.; Mandrou, Pierre; Paul, Jaques; Paul, Philippe; Reglero, Victor; Roques, Jean-Pierre; Sanchez, Filomeno; Schanne, Stephane; Schoenfelder, Volker; Shrader, Chris; Skinner, Gerald K.; Sturner, Steven J.; Teegarden, Bonnard J.; Vedrenne, Gilbert; Weidenspointner, Georg

    2003-03-01

    ESA's INTErnational Gamma-Ray Astrophysics Laboratory (INTEGRAL) will be launched in October 2002. Its two main instruments are the imager IBIS and the spectrometer SPI. Both emply coded apertures to obtain directional information on the incoming radiation. SPI's detection plane consists of 19 hexagonal Ge detectors, its coded aperture has 63 tungsten-alloy elements of 30 mm thickness.

  12. A "Brutus" model checking of a spi-calculus dialect (Extended Abstract)

    NARCIS (Netherlands)

    Gnesi, S.; Latella, D.; Lenzini, G.

    2000-01-01

    This paper proposes a preliminary framework in which protocols, expressed in a dialect of the spi-calculus, can be verified using model checking algorithms. In particular we define a formal semantics for a dialect of the spi-calculus based on labeled transition systems in such a way that the model c

  13. Identification of a negative regulatory role for spi-C in the murine B cell lineage.

    Science.gov (United States)

    Li, Stephen K H; Solomon, Lauren A; Fulkerson, Patricia C; DeKoter, Rodney P

    2015-04-15

    Spi-C is an E26 transformation-specific family transcription factor that is highly related to PU.1 and Spi-B. Spi-C is expressed in developing B cells, but its function in B cell development and function is not well characterized. To determine whether Spi-C functions as a negative regulator of Spi-B (encoded by Spib), mice were generated that were germline knockout for Spib and heterozygous for Spic (Spib(-/-)Spic(+/-)). Interestingly, loss of one Spic allele substantially rescued B cell frequencies and absolute numbers in Spib(-/-) mouse spleens. Spib(-/-)Spic(+/-) B cells had restored proliferation compared with Spib(-/-) B cells in response to anti-IgM or LPS stimulation. Investigation of a potential mechanism for the Spib(-/-)Spic(+/-) phenotype revealed that steady-state levels of Nfkb1, encoding p50, were elevated in Spib(-/-)Spic(+/-) B cells compared with Spib(-/-) B cells. Spi-B was shown to directly activate the Nfkb1 gene, whereas Spi-C was shown to repress this gene. These results indicate a novel role for Spi-C as a negative regulator of B cell development and function.

  14. LEGO-NMR spectroscopy: a method to visualize individual subunits in large heteromeric complexes.

    Science.gov (United States)

    Mund, Markus; Overbeck, Jan H; Ullmann, Janina; Sprangers, Remco

    2013-10-18

    Seeing the big picture: Asymmetric macromolecular complexes that are NMR active in only a subset of their subunits can be prepared, thus decreasing NMR spectral complexity. For the hetero heptameric LSm1-7 and LSm2-8 rings NMR spectra of the individual subunits of the complete complex are obtained, showing a conserved RNA binding site. This LEGO-NMR technique makes large asymmetric complexes accessible to detailed NMR spectroscopic studies.

  15. Spy1 Protein Mediates Phosphorylation and Degradation of SCG10 Protein in Axonal Degeneration*

    Science.gov (United States)

    Liu, Yonghua; Wang, Youhua; Chen, Ying; Li, Xiaohong; Yang, Jiao; Liu, Yang; Shen, Aiguo

    2015-01-01

    Axon loss is a destructive consequence of a wide range of neurological diseases without a clearly defined mechanism. Recent data demonstrate that SCG10 is a novel axonal maintenance factor and that rapid SCG10 loss after injury requires JNK activity; how JNK induces degradation of SCG10 is not well known. Here we showed that SCG10 was a binding partner of Spy1, a Speedy/RINGO family protein, which participated in cellular response to sciatic nerve injury. During the early stage of axonal injury, Spy1 expression was inversely correlated with SCG10. Spy1 mediated SCG10 phosphorylation and degradation partly in a JNK-dependent manner. Inhibition of Spy1 attenuated SCG10 phosphorylation and delayed injury-induced axonal degeneration. Taken together, these data suggest that Spy1 is an important regulator of SCG10 and can be targeted in future axo-protective therapeutics. PMID:25869138

  16. Zebrafish SPI-1 (PU.1) marks a site of myeloid development independent of primitive erythropoiesis : Implications for axial patterning

    NARCIS (Netherlands)

    Lieschke, GJ; Oates, AC; Paw, BH; Thompson, MA; Hall, NE; Ward, AC; Ho, RK; Zon, LI; Layton, JE

    2002-01-01

    The mammalian transcription factor SPI-1 (synonyms: SPI1, PU.1, or Sfpi1) plays a critical role in myeloid development. To examine early myeloid commitment in the zebrafish embryo, we isolated a gene from zebrafish that is a SPI-1 orthologue on the basis of homology and phylogenetic considerations.

  17. Engine Operating Conditions and Fuel Properties on Pre-Spark Heat Release and SPI Promotion in SI Engines

    Energy Technology Data Exchange (ETDEWEB)

    Splitter, Derek A [ORNL; Kaul, Brian C [ORNL; Szybist, James P [ORNL; Jatana, Gurneesh S [ORNL

    2017-01-01

    This work explores the dependence of fuel ignition delay on stochastic pre-ignition (SPI). Findings are based on bulk gas thermodynamic state, where the effects of kinetically controlled bulk gas pre-spark heat release (PSHR) are correlated to SPI tendency and magnitude. Specifically, residual gas and low temperature PSHR chemistry effects and observations are explored, which are found to be indicative of bulk gas conditions required for strong SPI events. Analyzed events range from non-knocking SPI to knocking SPI and even detonation SPI events in excess of 325 bar peak cylinder pressure. The work illustrates that singular SPI event count and magnitude are found to be proportional to PSHR of the bulk gas mixture and residual gas fraction. Cycle-to-cycle variability in trapped residual mass and temperature are found to impose variability in singular SPI event count and magnitude. However, clusters and short lived bursts of multiple SPI events are found to better correlate with fuel-wall interaction. The results highlight the interplay of bulk gas thermodynamics and SPI ignition source, on SPI event magnitude and cluster tendency. Moreover, the results highlight fundamental fuel reactivity and associated hypersensitivity to operating conditions at SPI prone operating conditions.

  18. Metal Abundances of Subdwarf B Stars from SPY - a Pattern Emerges

    CERN Document Server

    Geier, S; Napiwotzki, R

    2008-01-01

    The formation of sdBs is still puzzling, as is the chemical composition of their atmospheres. While helium and other light elements are depleted relative to solar values, heavy elements are highly enriched. Diffusion processes in the hot, radiative atmosphere of these stars are the most likely explanation. Although several attempts were made, it was not yet possible to model all the observed features of sdB atmospheres. A setback of most prior studies was the small sample size. We present a detailed abundance analysis of 68 sdBs. From high resolution spectra obtained with the VLT/UVES instrument in the course of the ESO Supernova Progenitor Survey (SPY) we measured elemental abundances of up to 24 different ions per star. A general trend of enrichment was found with increasing temperature for most of the heavier elements. The lighter elements like carbon, oxygen and nitrogen are depleted irrespective of the temperature. Although there is considerable scatter from one star to another, the general abundance pat...

  19. The binary fraction, separation distribution, and merger rate of white dwarfs from the SPY sample

    CERN Document Server

    Maoz, Dan

    2016-01-01

    From a sample of spectra of 439 white dwarfs (WDs) from the ESO-VLT Supernova-Ia Progenitor surveY (SPY), we measure the maximal changes in radial-velocity (DRVmax) between epochs (generally two epochs, separated by up to 470d), and model the observed DRVmax statistics via Monte-Carlo simulations, to constrain the population characteristics of double WDs (DWDs). The DWD fraction among WDs is fbin=0.103+/-0.017 (1-sigma, random) +/-0.015 (systematic), in the separation range ~<4AU within which the data are sensitive to binarity. Assuming the distribution of binary separation, a, is a power-law, dN/dt ~ a^alpha, at the end of the last common-envelope phase and the start of solely gravitational-wave-driven binary evolution, the constraint by the data is alpha=-1.4+/-0.4 (1-sigma). If these parameters extend to small separations, the implied Galactic WD merger rate per unit stellar mass is R_merge=1.4e-13 to 1.3e-11 /yr/Msun (2-sigma), with a likelihood-weighted mean of R_merge=(7.3+/-2.7)e-13 /yr/Msun (1-sigm...

  20. Studies on irradiation stability of polystyrene by NMR

    Institute of Scientific and Technical Information of China (English)

    ZHAO Xin; SUN Wan-Fu; XIE Cheng-Xi

    2004-01-01

    The irradiation stability of polystyrene (PS) was studied by 13C and 1H NMR spectra, Nuclear Overhauser Relaxation (NOE) and 13C NMR spin-lattice relaxation time (T1). The results indicate that 13C and 1H NMR chemical shifts, NOE and T1 were almost invariant with the increase of irradiation dose. This shows that polystyrene is particularly stable within 2.5 kGy doses and the mechanism of its stability is discussed.

  1. Direct 13C NMR Detection in HPLC Hyphenation Mode

    DEFF Research Database (Denmark)

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

    2012-01-01

    Solid phase extraction (SPE) was introduced as a crucial step in the HPLC-SPE-NMR technique to enable online analyte enrichment from which proton-detected NMR experiments on submicrogram amounts from complex mixtures were possible. However, the significance of direct-detected (13)C NMR experiments......, and an acquisition time of 13 h resulted in spectra with adequate signal-to-noise ratios to detect all C-13 signals....

  2. Research and Implementation of SPI FLASH Mode Based on P2020%基于P2020的SPI FLASH模式的研究与实现

    Institute of Scientific and Technical Information of China (English)

    王军; 胡明

    2013-01-01

    PowerPC P2020 is a high-performance processor of Freescale Semiconductor,which has a wide range of applications in areas such as telecommunications,military,network. As an important boot media,SPI FLASH is one of the most used methods when users de-sign their hardware. It can enrich the user’s choice for the boot mode. At the same time,as a backup boot mode,it can also improve the stability of the system. In view of the importance of SPI FLASH boot mode,based on the P2020 platform,conduct a research on the im-plementation of booting from SPI FLASH. Firstly,describe the two boot stages of SPI FLASH after P2020 power on. Secondly,introduce the process of building the SPI FLASH image used for booting. Thirdly,for some of the problems encountered in the actual operation on SPI FLASH,give effective solutions. Finally,after the transplantation of uboot and linux,implement the booting from SPI FLASH. After power on,the system can boot the uboot and load linux successfully,and run within a stable condition.%  PowerPC P2020是Freescale 公司一款性能优良的处理器,在电信、军事、网络等领域都有着广泛的应用。 SPI FLASH作为一种重要的启动方式,是用户在进行硬件设计时经常采用的方法之一。它不仅可以丰富用户对于启动方式的选择,同时也可以作为备份启动模式,提高系统的稳定性。鉴于SPI FLASH启动方式的重要性,文中以P2020为硬件平台,对SPI FLASH启动方式的实现进行了研究。首先,描述了P2020处理器上电之后SPI FLASH两个阶段的启动过程;其次,介绍了SPI FLASH启动镜像的制作过程;再次,针对实际操作SPI FLASH中遇到的一些问题,文中进行了有效地解决;最后,在完成uboot及linux的移植后,最终成功实现了SPI FLASH启动方式。系统上电之后,可成功启动uboot并加载linux,且可以稳定运行。

  3. On the use of Standardized Precipitation Index(SPI) for drought intensity assessment

    CERN Document Server

    Kumar, M Naresh; Sai, M V R Sesha; Roy, P S

    2015-01-01

    Monthly rainfall data from June to October for 39 years was used to generate Standardized Precipitation Index (SPI) values based on Gamma distribution for a low rainfall and a high rainfall district of Andhra Pradesh state, India. Comparison of SPI, with actual rainfall and rainfall deviation from the mean indicated that SPI values under-estimate the intensity of dryness/wetness when the rainfall is very low/very high respectively. As a result, the SPI in the worst drought years of 2002 and 2006 in the low rainfall district has indicated only moderate dryness instead of extreme dryness. The range of SPI values of the high rainfall district indicated better stretching, compared to that of the low rainfall district. Further, the SPI values of longer time scale (2-, 3- and 4- months) showed an extended range compared to 1-month, but the sensitivity in drought years has not improved significantly. To ascertain whether non normality of SPI is a possible reason, normality tests were conducted. The Shapiro-Wilk stat...

  4. Spying on photons with photons: quantum interference and information

    Science.gov (United States)

    Ataman, Stefan

    2016-07-01

    The quest to have both which-path knowledge and interference fringes in a double-slit experiment dates back to the inception of quantum mechanics (QM) and to the famous Einstein-Bohr debates. In this paper we propose and discuss an experiment able to spy on one photon's path with another photon. We modify the quantum state inside the interferometer as opposed to the traditional physical modification of the "wave-like" or "particle-like" experimental setup. We are able to show that it is the ability to harvest or not which-path information that finally limits the visibility of the interference pattern and not the "wave-like" or "particle-like" experimental setups. Remarkably, a full "particle-like" experimental setup is able to show interference fringes with 100% visibility if the quantum state is carefully engineered.

  5. Spying on photons with photons: quantum interference and information

    CERN Document Server

    Ataman, Stefan

    2016-01-01

    The quest to have both which-path knowledge and interference fringes in a double-slit experiment dates back to the inception of quantum mechanics (QM) and to the famous Einstein-Bohr debates. In this paper we propose and discuss an experiment able to spy on one photon's path with another photon. We modify the quantum state inside the interferometer as opposed to the traditional physical modification of the "wave-like" or "particle-like" experimental setup. We are able to show that it is the ability to harvest or not which-path information that finally limits the visibility of the interference pattern and not the "wave-like" or "particle-like" experimental setups. Remarkably, a full "particle-like" experimental setup is able to show interference fringes with 100 % visibility if the quantum state is carefully engineered.

  6. Capturing a Dynamic Chaperone-Substrate Interaction Using NMR-Informed Molecular Modeling.

    Science.gov (United States)

    Salmon, Loïc; Ahlstrom, Logan S; Horowitz, Scott; Dickson, Alex; Brooks, Charles L; Bardwell, James C A

    2016-08-10

    Chaperones maintain a healthy proteome by preventing aggregation and by aiding in protein folding. Precisely how chaperones influence the conformational properties of their substrates, however, remains unclear. To achieve a detailed description of dynamic chaperone-substrate interactions, we fused site-specific NMR information with coarse-grained simulations. Our model system is the binding and folding of a chaperone substrate, immunity protein 7 (Im7), with the chaperone Spy. We first used an automated procedure in which NMR chemical shifts inform the construction of system-specific force fields that describe each partner individually. The models of the two binding partners are then combined to perform simulations on the chaperone-substrate complex. The binding simulations show excellent agreement with experimental data from multiple biophysical measurements. Upon binding, Im7 interacts with a mixture of hydrophobic and hydrophilic residues on Spy's surface, causing conformational exchange within Im7 to slow down as Im7 folds. Meanwhile, the motion of Spy's flexible loop region increases, allowing for better interaction with different substrate conformations, and helping offset losses in Im7 conformational dynamics that occur upon binding and folding. Spy then preferentially releases Im7 into a well-folded state. Our strategy has enabled a residue-level description of a dynamic chaperone-substrate interaction, improving our understanding of how chaperones facilitate substrate folding. More broadly, we validate our approach using two other binding partners, showing that this approach provides a general platform from which to investigate other flexible biomolecular complexes through the integration of NMR data with efficient computational models.

  7. Solvent effect in implicit/explicit model on FT-IR, 1H, 13C and 19F NMR, UV-vis and fluorescence spectra, linear, second- and third-nonlinear optical parameters of 2-(trifluoromethyl)benzoic acid: Experimental and computational study

    Science.gov (United States)

    Avcı, Davut; Altürk, Sümeyye; Tamer, Ömer; Kuşbazoğlu, Mustafa; Atalay, Yusuf

    2017-09-01

    FT-IR, 1H, 13C and 19F NMR, UV-vis and fluorescence spectra for 2-(trifluoromethyl)benzoic acid (2-TFMBA) were recorded. DFT//B3LYP/6-31++G(d,p) calculations were used to determine the optimized molecular geometry, vibrational frequencies, 1H, 13C and 19F GIAO-NMR chemical shifts of 2-TFMBA. The detailed assignments of vibrational frequencies were carried out on the basis of potential energy distribution (PED) by using VEDA program. TD-DFT/B3LYP/6-31++G(d,p) calculations with the PCM (polarizable continuum model) in ethanol and DMSO solvents based on implicit/explicit model and gas phase in the excited state were employed to investigate UV-vis absorption and fluorescence emission wavelengths. The UV-vis and emission spectra were given in ethanol and DMSO solvents, and the major contributions to the electronic transitions were obtained. In addition, the NLO parameters (β, γ and χ(3)) and frontier molecular orbital energies of 2-TFMBA were calculated by using B3LYP/6-31++G(d,p) level. The NLO parameters of 2-TFMBA were compared with that of para-Nitroaniline (pNA) and urea which are the typical NLO materials. The refractive index (n) is calculated by using the Lorentz-Lorenz equation to observe polarization behavior of 2-TFMBA in DMSO and ethanol solvents. In order to investigate intramolecular and hydrogen bonding interactions, NBO calculations were also performed by the same level. To sum up, considering the well-known biological role, photochemical properties of 2-TFMBA were discussed.

  8. Lorentz-to-Gauss multiplication (LGM) in FT NMR

    Energy Technology Data Exchange (ETDEWEB)

    Makhiyanov, N. [Production Association ``Nizhnekamskneftekhym``, Nizhnekamsk, Tatarstan (Russian Federation); Kupka, T. [Uniwersytet Slaski, Katowice (Poland)]|[Zaklad Fizyki Ciala Stalego, Polska Akademia Nauk, Zabrze (Poland); Pasterna, G. [Institute of Nuclear Physics, Cracow (Poland); Dziegielewski, J.O. [Uniwersytet Slaski, Katowice (Poland)

    1994-12-31

    High resolution proton and carbon NMR spectra of macromolecules and biomolecules are often overcrowded and with many partly overlapped signals. Several data processing methods to resolve partly overlapped NMR peaks have been reported. Among the Lorentz-to-Gauss and CDRE (Convulsion Difference Resolution Enhancement) methods are wide used. In this work calculation of the best set of parameters were carried out from a raw spectral data (initial FID and the corresponding untreated spectrum) and a method of prediction of optimal Lorentz-to-Gauss method parameters are suggested. The feasibility of this approach to improve the quality of NMR spectra from various resonating nuclei was shown too. 8 refs, 1 fig.

  9. FT-IR, FT-Raman, UV, NMR spectra, molecular structure, ESP, NBO and HOMO-LUMO investigation of 2-methylpyridine 1-oxide: a combined experimental and DFT study.

    Science.gov (United States)

    Shoba, D; Periandi, S; Boomadevi, S; Ramalingam, S; Fereyduni, E

    2014-01-24

    In this paper, the equilibrium geometry, bonding features, vibrational frequencies, (1)H and (13)C chemical shift values, molecular electrostatic potential maps, HOMO-LUMO energies and several thermodynamic parameters of title compound in the ground state have been calculated by using the density functional method with 6-31G(d,p) and 6-311G(d,p) basis sets. A detailed interpretation of the infrared and Raman spectra of 2-methylpyridine 1-oxide was reported. Furthermore, natural bond orbitals were performed in this work. The theoretical results showed an excellent agreement with the experimental values.

  10. PREPARATION AND CHARACTERIZATION OF SOY PROTEIN ISOLATE (SPI)/MONTMORILLONITE (MMT) BIONANOCOMPOSITES

    Institute of Scientific and Technical Information of China (English)

    Lixue Xiang; Chang-yu Tang; Jing Can; Chao-yu Wang; Ke Wang; Qin Zhang; Qiang Fu; Shu-gao Zhao

    2009-01-01

    The bionanocomposites of soy protein isolate (SPI)/montmorillonite (MMT) have been prepared successfully via simple melt mixing, in which MMT was used as nanofiller and glycerol was used as plasticizer. Their structures and properties were characterized with X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), thermogravimetric analysis and tensile testing. XRD, TEM and SEM results indicated that the MMT layers could be easily intercalated by the SPI matrix even by simple melt processing. The exfoliated MMT layers were randomly dispersed in the protein matrix as MMT content was low (less than 5 wt%), an incomplete exfoliation was evident from SEM results, and some primary particles were observed as the MMT content was high (from 5 wt% to 9 wt%). A significant improvement of the mechanical strength and thermal stability of SPI/MMT nanocomposites has been achieved. Our work suggests that simple melt processing is an efficient way to prepare SPI/MMT nanocomposites with exfoliated structure.

  11. STANDARDIZED PRECIPITATION INDEX (SPI CALCULATED WITH THE USE OF LOG-NORMAL DISTRIBUTION

    Directory of Open Access Journals (Sweden)

    Edward Gąsiorek

    2014-10-01

    Full Text Available The problem analyzed in this paper is the continuation of research conducted on data from Wrocław-Swojec agro- and hydrometeorology observatory in 1964–2009 period and published in “Infrastruktura i Ekologia Terenów Wiejskich” nr 3/III/2012, pp. 197–208. The paper concerns two methods of calculation of standardized precipitation index (SPI. The first one extracts SPI directly from gamma distribution, since monthly precipitation sums in the 1964–2009 period in Wrocław are gamma distributed. The second method is based on the transformations of data leading to normal distribution. The authors calculate SPI with the use of log-normal distribution and confront it with values obtained by gamma and normal distributions. The aim of this paper is to comparatively assess the SPI values obtained with those three different methods.

  12. Genetic selection designed to stabilize proteins uncovers a chaperone called Spy.

    Science.gov (United States)

    Quan, Shu; Koldewey, Philipp; Tapley, Tim; Kirsch, Nadine; Ruane, Karen M; Pfizenmaier, Jennifer; Shi, Rong; Hofmann, Stephan; Foit, Linda; Ren, Guoping; Jakob, Ursula; Xu, Zhaohui; Cygler, Miroslaw; Bardwell, James C A

    2011-03-01

    To optimize the in vivo folding of proteins, we linked protein stability to antibiotic resistance, thereby forcing bacteria to effectively fold and stabilize proteins. When we challenged Escherichia coli to stabilize a very unstable periplasmic protein, it massively overproduced a periplasmic protein called Spy, which increases the steady-state levels of a set of unstable protein mutants up to 700-fold. In vitro studies demonstrate that the Spy protein is an effective ATP-independent chaperone that suppresses protein aggregation and aids protein refolding. Our strategy opens up new routes for chaperone discovery and the custom tailoring of the in vivo folding environment. Spy forms thin, apparently flexible cradle-shaped dimers. The structure of Spy is unlike that of any previously solved chaperone, making it the prototypical member of a new class of small chaperones that facilitate protein refolding in the absence of energy cofactors.

  13. Positive results for drug combo in I-SPY 2 trial.

    Science.gov (United States)

    2014-02-01

    In results from one part of the I-SPY 2 trial announced at the 2013 San Antonio Breast Cancer Symposium, neoadjuvant veliparib plus carboplatin improved outcomes for women with triple-negative breast cancer.

  14. IDT推出三端口SPI-4信息包交换器件

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    IDT公司日前宣布推出新型信息包接口(SPI)套件,扩充其信息包交换流量控制管理(FCM)产品系列。该系列FCM方案支持10 Gbps信息包处理,并为逻辑端口密度和缓冲容量提供宽的可选范围,按照SPI-4数据超额预定及汇聚要求设计的复杂流量控制设计,能保证低延迟的SPI-4到SPI-4的交换。

  15. Perfusion Assessment with the SPY System after Arterial Venous Reversal for Upper Extremity Ischemia

    Directory of Open Access Journals (Sweden)

    Darrell Brooks, MD

    2014-07-01

    Conclusions: AVR effectively reestablished blood flow in patients with terminal upper extremity ischemia. ICG angiography with SPY technology revealed that, in most cases, kinetic curves, timing, and patterns of perfusion gradually normalized over several PODs.

  16. A Half-Day Workshop on ``Smarter Investment by Aligning SPI Initiatives, Capabilities and Stakeholder Values''

    Science.gov (United States)

    Selioukova, Yana; Frühwirth, Christian

    Software companies who want to improve software process capabilities (SPCs)a systematic method to make informed investment decisions on software process improvement (SPI) initiatives. Such decisions should aim at creating maximum stakeholder values. To address this problem, we present a method with tool support that may help companies align stakeholder values with SPCs and SPI initiatives. The proposed method has been developed based on the well-established “Quality Function Deployment” (QFD) approach. The experience with the proposed method suggests that it particularly helps to reduce the risk of misalignment by identifying those SPI initiatives that are most beneficial to stakeholders. The tool support provided with the proposed method also generated positive experiences in increasing the usability of the method and helped companies in the elicitation and prioritization of stakeholder values. Therefore, we propose a workshop for the method work out named “Smarter Investment by Aligning SPI Initiatives, Capabilities and Stakeholder Values” in hypothetical case company.

  17. The SPI-1-like Type III secretion system: more roles than you think.

    Science.gov (United States)

    Egan, Frank; Barret, Matthieu; O'Gara, Fergal

    2014-01-01

    The type III secretion system (T3SS) is a protein delivery system which is involved in a wide spectrum of interactions, from mutualism to pathogenesis, between Gram negative bacteria and various eukaryotes, including plants, fungi, protozoa and mammals. Various phylogenetic families of the T3SS have been described, including the Salmonella Pathogenicity Island 1 family (SPI-1). The SPI-1 T3SS was initially associated with the virulence of enteric pathogens, but is actually found in a diverse array of bacterial species, where it can play roles in processes as different as symbiotic interactions with insects and colonization of plants. We review the multiple roles of the SPI-1 T3SS and discuss both how these discoveries are changing our perception of the SPI-1 family and what impacts this has on our understanding of the specialization of the T3SS in general.

  18. Optimization and practical implementation of ultrafast 2D NMR experiments

    Directory of Open Access Journals (Sweden)

    Luiz H. K. Queiroz Júnior

    2013-01-01

    Full Text Available Ultrafast 2D NMR is a powerful methodology that allows recording of a 2D NMR spectrum in a fraction of second. However, due to the numerous non-conventional parameters involved in this methodology its implementation is no trivial task. Here, an optimized experimental protocol is carefully described to ensure efficient implementation of ultrafast NMR. The ultrafast spectra resulting from this implementation are presented based on the example of two widely used 2D NMR experiments, COSY and HSQC, obtained in 0.2 s and 41 s, respectively.

  19. Optimization and practical implementation of ultrafast 2D NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

    Queiroz Junior, Luiz H. K., E-mail: professorkeng@gmail.com [Universidade Federal de Sao Carlos (UFSC), SP (Brazil). Departamento de Quimica; Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Inst. de Quimica; Ferreira, Antonio G. [Universidade Federal de Sao Carlos (UFSC), SP (Brazil). Departamento de Quimica; Giraudeau, Patrick [Universite de Nantes (France). CNRS, Chimie et Interdisciplinarite: Synthese, Analyse, Modelisation

    2013-09-01

    Ultrafast 2D NMR is a powerful methodology that allows recording of a 2D NMR spectrum in a fraction of second. However, due to the numerous non-conventional parameters involved in this methodology its implementation is no trivial task. Here, an optimized experimental protocol is carefully described to ensure efficient implementation of ultrafast NMR. The ultrafast spectra resulting from this implementation are presented based on the example of two widely used 2D NMR experiments, COSY and HSQC, obtained in 0.2 s and 41 s, respectively. (author)

  20. Mapping of SPI drought index in South-Eastern Europe, theory and practice

    Science.gov (United States)

    Bihari, Z.; Szentimrey, T.; Lakatos, M.; Gregorič, G.; Likso, T.

    2010-09-01

    In recent decades drought has a major impact on the economy in South-Eastern Europe (SEE). The annual precipitation has decreased from the beginning of 20th century. Additional problem is that the intensity of precipitation increases in average. The part of runoff became larger, and greater part of the precipitation runs to the rivers, streamlets, and less part infiltrates into the soil. Therefore, the available water reduces for vegetation. Summarized, the drought tendency increases in the region. The Drought Management Centre for South East Europe was established to deal with these events and try to improve drought management and policy. One method to calculate the extent of a drought event is the application of drought indices. Several indices are used for this purpose, one of them is the Standard Precipitation Index (SPI) developed by McKee et al. The SPI is based only on precipitation and can be used to monitor conditions on a variety of time scales. The SPI calculation for any location is based on long-term precipitation record for a desired period. This long-term record is fitted to a gamma probability distribution, which is then transformed into the standard normal distribution. In the practice SPI is calculated mainly for 1, 3, 6 months. The SPI calculator which is offered on the project page of DMCSEE is applied for SPI calculations in this study. For the interpolation of SPI we use the MISH interpolation method developed at Hungarian Meteorological Service (Meteorological Interpolation based on Surface Homogenized Data Basis; Szentimrey, Bihari, 2007). The interpolation can be realized in to ways: 1. The SPI values are calculated in grid points after gridding (by gridding part of MISH) the station precipitation data series 2. The station based SPI values are interpolated by method MISH One of the main feature of MISH is that it use longtime data series for modelling of the necessary climate statistical parameters while the SPI calculations are also based

  1. Organic Spectroscopy Laboratory: Utilizing IR and NMR in the Identification of an Unknown Substance

    Science.gov (United States)

    Glagovich, Neil M.; Shine, Timothy D.

    2005-01-01

    A laboratory experiment that emphasizes the interpretation of both infrared (IR) and nuclear magnetic resonance (NMR) spectra in the elucidation of the structure of an unknown compound was developed. The method helps students determine [to the first power]H- and [to the thirteenth power]C-NMR spectra from the structures of compounds and to…

  2. NMR system and method having a permanent magnet providing a rotating magnetic field

    Science.gov (United States)

    Schlueter, Ross D [Berkeley, CA; Budinger, Thomas F [Berkeley, CA

    2009-05-19

    Disclosed herein are systems and methods for generating a rotating magnetic field. The rotating magnetic field can be used to obtain rotating-field NMR spectra, such as magic angle spinning spectra, without having to physically rotate the sample. This result allows magic angle spinning NMR to be conducted on biological samples such as live animals, including humans.

  3. Epigenetic silencing of Bim transcription by Spi-1/PU.1 promotes apoptosis resistance in leukaemia.

    Science.gov (United States)

    Ridinger-Saison, M; Evanno, E; Gallais, I; Rimmelé, P; Selimoglu-Buet, D; Sapharikas, E; Moreau-Gachelin, F; Guillouf, C

    2013-09-01

    Deregulation of transcriptional networks contributes to haematopoietic malignancies. The transcription factor Spi-1/PU.1 is a master regulator of haematopoiesis and its alteration leads to leukaemia. Spi-1 overexpression inhibits differentiation and promotes resistance to apoptosis in erythroleukaemia. Here, we show that Spi-1 inhibits mitochondrial apoptosis in vitro and in vivo through the transcriptional repression of Bim, a proapoptotic factor. BIM interacts with MCL-1 that behaves as a major player in the survival of the preleukaemic cells. The repression of BIM expression reduces the amount of BIM-MCL-1 complexes, thus increasing the fraction of potentially active antiapoptotic MCL-1. We then demonstrate that Spi-1 represses Bim transcription by binding to the Bim promoter and by promoting the trimethylation of histone 3 on lysine 27 (H3K27me3, a repressive histone mark) on the Bim promoter. The PRC2 repressive complex of Polycomb is directly responsible for the deposit of H3K27me3 mark at the Bim promoter. SUZ12 and the histone methyltransferase EZH2, two PRC2 subunits bind to the Bim promoter at the same location than H3K27me3, distinct of the Spi-1 DNA binding site. As Spi-1 interacts with SUZ12 and EZH2, these results indicate that Spi-1 modulates the activity of PRC2 without directly recruiting the complex to the site of its activity on the chromatin. Our results identify a new mechanism whereby Spi-1 represses transcription and provide mechanistic insights on the antiapoptotic function of a transcription factor mediated by the epigenetic control of gene expression.

  4. PREPARATION AND CHARACTERIZATION OF SOY PROTEIN ISOLATE(SPI)/MONTMORILLONITE(MMT) BIONANOCOMPOSITES

    Institute of Scientific and Technical Information of China (English)

    傅强

    2009-01-01

    The bionanocomposites of soy protein isolate(SPI)/montmorillonite(MMT) have been prepared successfully via simple melt mixing,in which MMT was used as nanofiller and glycerol was used as plasticizer.Their structures and properties were characterized with X-ray diffraction(XRD),differential scanning calorimetry(DSC),scanning electron microscopy(SEM),thermogravimetric analysis and tensile testing.XRD、TEM and SEM results indicated that the MMT layers could be easily intercalated by the SPI matrix even by si...

  5. Mysteries and Conspiracies: Detective Stories, Spy Novels And The Making Of Modern Societies

    DEFF Research Database (Denmark)

    Ossandón, José

    2016-01-01

    Book review of: Mysteries and Conspiracies: Detective Stories, Spy Novels and the Making of Modern Societies. By Luc Boltanski (trans. C Porter). Cambridge: Polity Press, 2014. xviii+340 pp. £18.99/€23.80. ISBN: 9780745664057.......Book review of: Mysteries and Conspiracies: Detective Stories, Spy Novels and the Making of Modern Societies. By Luc Boltanski (trans. C Porter). Cambridge: Polity Press, 2014. xviii+340 pp. £18.99/€23.80. ISBN: 9780745664057....

  6. Spi-B is critical for plasmacytoid dendritic cell function and development.

    Science.gov (United States)

    Sasaki, Izumi; Hoshino, Katsuaki; Sugiyama, Takahiro; Yamazaki, Chihiro; Yano, Takahiro; Iizuka, Akihiko; Hemmi, Hiroaki; Tanaka, Takashi; Saito, Masuyoshi; Sugiyama, Masanaka; Fukuda, Yuri; Ohta, Tomokazu; Sato, Katsuaki; Ainai, Akira; Suzuki, Tadaki; Hasegawa, Hideki; Toyama-Sorimachi, Noriko; Kohara, Hiroshi; Nagasawa, Takashi; Kaisho, Tsuneyasu

    2012-12-01

    Plasmacytoid dendritic cells (pDCs), originating from hematopoietic progenitor cells in the BM, are a unique dendritic cell subset that can produce large amounts of type I IFNs by signaling through the nucleic acid-sensing TLR7 and TLR9 (TLR7/9). The molecular mechanisms for pDC function and development remain largely unknown. In the present study, we focused on an Ets family transcription factor, Spi-B, that is highly expressed in pDCs. Spi-B could transactivate the type I IFN promoters in synergy with IFN regulatory factor 7 (IRF-7), which is an essential transcription factor for TLR7/9-induced type I IFN production in pDCs. Spi-B-deficient pDCs and mice showed defects in TLR7/9-induced type I IFN production. Furthermore, in Spi-B-deficient mice, BM pDCs were decreased and showed attenuated expression of a set of pDC-specific genes whereas peripheral pDCs were increased; this uneven distribution was likely because of defective retainment of mature nondividing pDCs in the BM. The expression pattern of cell-surface molecules in Spi-B-deficient mice indicated the involvement of Spi-B in pDC development. The developmental defects of pDCs in Spi-B-deficient mice were more prominent in the BM than in the peripheral lymphoid organs and were intrinsic to pDCs. We conclude that Spi-B plays critical roles in pDC function and development.

  7. NMR of lignins

    Science.gov (United States)

    John Ralph; Larry L. Landucci

    2010-01-01

    This chapter will consider the basic aspects and findings of several forms of NMR spectroscopy, including separate discussions of proton, carbon, heteronuclear, and multidimensional NMR. Enhanced focus will be on 13C NMR, because of its qualitative and quantitative importance, followed by NMR’s contributions to our understanding of lignin...

  8. Inequality spectra

    Science.gov (United States)

    Eliazar, Iddo

    2017-03-01

    Inequality indices are widely applied in economics and in the social sciences as quantitative measures of the socioeconomic inequality of human societies. The application of inequality indices extends to size-distributions at large, where these indices can be used as general gauges of statistical heterogeneity. Moreover, as inequality indices are plentiful, arrays of such indices facilitate high-detail quantification of statistical heterogeneity. In this paper we elevate from arrays of inequality indices to inequality spectra: continuums of inequality indices that are parameterized by a single control parameter. We present a general methodology of constructing Lorenz-based inequality spectra, apply the general methodology to establish four sets of inequality spectra, investigate the properties of these sets, and show how these sets generalize known inequality gauges such as: the Gini index, the extended Gini index, the Rényi index, and hill curves.

  9. Line-narrowing in proton-detected nitrogen-14 NMR.

    Science.gov (United States)

    Cavadini, Simone; Vitzthum, Veronika; Ulzega, Simone; Abraham, Anuji; Bodenhausen, Geoffrey

    2010-01-01

    In solids spinning at the magic angle, the indirect detection of single-quantum (SQ) and double-quantum (DQ) (14)N spectra (I=1) via spy nuclei S=1/2 such as protons can be achieved in the manner of heteronuclear single- or multiple-quantum correlation (HSQC or HMQC) spectroscopy. The HMQC method relies on the excitation of two-spin coherences of the type T(11)(I)T(11)(S) and T(21)(I)T(11)(S) at the beginning of the evolution interval t(1). The spectra obtained by Fourier transformation from t(1) to omega(1) may be broadened by the homogenous decay of the transverse terms of the spy nuclei S. This broadening is mostly due to homonuclear dipolar S-S' interactions between the proton spy nuclei. In this work we have investigated the possibility of inserting rotor-synchronized symmetry-based C or R sequences and decoupling schemes such as Phase-Modulated Lee-Goldburg (PMLG) sequences in the evolution period. These schemes reduce the homonuclear proton-proton interactions and lead to an enhancement of the resolution of both SQ and DQ proton-detected (14)N HMQC spectra. In addition, we have investigated the combination of HSQC with symmetry-based sequences and PMLG and shown that the highest resolution in the (14)N dimension is achieved by using HSQC in combination with symmetry-based sequences of the R-type. We show improvements in resolution in samples of l-alanine and the tripeptide ala-ala-gly (AAG). In particular, for l-alanine the width of the (14)N SQ peak is reduced from 2 to 1.2 kHz, in agreement with simulations. We report accurate measurements of quadrupolar coupling constants and asymmetry parameters for amide (14)N in AAG peptide bonds.

  10. Growth response of oaks, beech and pine to Standardized Precipitation Index (SPI)

    Science.gov (United States)

    Stojanovic, Dejan; Levanič, Tom; Matović, Bratislav; Orlović, Saša

    2017-04-01

    Climate change may have various consequences on forests, from more frequent forest fires and windstorms to pest and disease outbreaks. Standardized Precipitation Index (SPI) was chosen for the evaluation of climate change impact to radial forest growth, after comprehensive testing of different climate parameters from CARPATCLIM database. SPI was calculated for periods between 3 and 36 months for different forest stands (lowland and mountainous parts of Serbia, Southeast Europe). Observed were following tree species: Quercus robur, Q. cerris, Fagus sylvatica and Pinus sylvestris. Bootstrapped Pearson's correlation between SPI monthly indices and tree-ring widths was calculated and ranked for all species. We found that 12-month SPI for summer months may be a good predictor for growth of different species at different sites. The strongest positive correlation between tree-ring width indices and SPI was particularly from the year of growth, since the strongest negative correlation for all four species was exclusively from the year prior to growth. The strongest positive correlation were between 12 and 14-month SPI from June to September, which suggests that the high growth rates are expected when autumn of previous-year, winter, spring and summer of the current year are with high precipitation rates.

  11. The low temperature oxidation of Athabasca oil sand asphaltene observed from {sup 13}C, {sup 19}F, and pulsed field gradient spin-echo proton n.m.r. spectra

    Energy Technology Data Exchange (ETDEWEB)

    Desando, M.A.; Lahanjar, G.; Ripmeester, J.A.; Zupancic, I. [National Research Council of Canada, Ottawa, ON (Canada). Division of Chemistry

    1999-01-01

    Carbon-13 and fluorine-19 nuclear magnetic resonance spectra of chemically derivatized, by phase transfer methylation and trifluoroacetylation, Athabasca oil sand asphaltene, reveal a broad site distribution of different types of hydroxyl-containing functional groups, viz., carboxylic acids, phenols, and alcohols. The low temperature air oxidation of asphaltene, at ca. 130{degree}C for 3 days, generates a few additional carboxyl and phenolic groups. These results are consistent with a mechanism in which diaryl methylene and ether moieties react with oxygen. Self-diffusion coefficients, from the pulsed field gradient spin-echo proton magnetic resonance technique, suggest that low temperature oxidation does not appreciably alter the average particle size and diffusion properties of asphaltene in deuterochloroform. 55 refs., 9 figs., 3 tabs.

  12. Using INTEGRAL/SPI to study the Sun

    CERN Document Server

    Rodríguez-Gasén, R; Tatischeff, V; Hamadache, C; Klein, K -L; Vilmer, N

    2013-01-01

    Solar energetic particle (SEP) events are a prime opportunity to probe astrophysical particle acceleration by combining in-situ measurements of particles in space with remote sensing of the hard X-ray (HXR) and \\gamma-ray emitting particles in the solar atmosphere. For the space environment SEPs are among the biggest hazards, particularly for spacecraft and human exploration of the solar system. Unfortunately our current understanding of the acceleration and transport of SEPs is weak. With the increasing onset of the space age it is vitally important that we increase our knowledge of the physical mechanisms related to SEPs. In this direction, the SEPServer project aims at building an on-line server that will provide the space research community with SEP data and related observations of solar electromagnetic emission. INTEGRAL/SPI acquires observations from many X-ray/\\gamma-ray flares associated with SEP events. To make this data accessible for SEP studies we have undertaken a major effort to specify the sola...

  13. U-2 Spy Plane With Fictitious NASA Markings

    Science.gov (United States)

    1960-01-01

    After Francis Gary Powers was shot down over the Soviet Union during a CIA spy flight on May 1. 1960, NASA issued a press release with a cover story about a U-2 conducting weather research that may have strayed off course after the pilot reported difficulties with his oxygen equipment. To bolster the cover-up, a U-2 was quickly painted in NASA markings, with a fictitious NASA serial number, and put on display for the news media at the NASA Flight Research Center at Edwards Air Force Base on May 6, 1960. The U-2 cover story in 1956 was that it was an NACA plane to conduct high-altitude weather research. But various observers doubted this story from the beginning. Certainly the Soviets did not believe it once the aircraft began overflying their territory. The NASA cover story quickly blew up in the agency's face when both Gary Powers and aircraft wreckage were displayed by the Soviet Union, proving that it was a reconnaissance aircraft. This caused embarrassment for several top NASA officials.

  14. The binary fraction, separation distribution, and merger rate of white dwarfs from SPY

    Science.gov (United States)

    Maoz, Dan; Hallakoun, Na'ama

    2017-01-01

    From a sample of spectra of 439 white dwarfs (WDs) from the ESO-VLT Supernova-Ia Progenitor surveY (SPY), we measure the maximal changes in radial-velocity (ΔRVmax) between epochs (generally two epochs, separated by up to 470 d), and model the observed ΔRVmax statistics via Monte-Carlo simulations, to constrain the population characteristics of double WDs (DWDs). The DWD fraction among WDs is fbin=0.100 ± 0.020 (1σ, random) +0.02 (systematic), in the separation range ≲ 4 AU within which the data are sensitive to binarity. Assuming the distribution of binary separation, a, is a power-law, dN/da∝aα, at the end of the last common-envelope phase and the start of solely gravitational-wave-driven binary evolution, the constraint by the data is α = -1.3 ± 0.2 (1σ) ±0.2 (systematic). If these parameters extend to small separations, the implied Galactic WD merger rate per unit stellar mass is Rmerge = (1 - 80) × 10-13 yr^{-1} M_⊙ ^{-1} (2σ), with a likelihood-weighted mean of Rmerge = (7 ± 2) × 10-13 yr^{-1} M_⊙ ^{-1} (1σ). The Milky Way's specific Type-Ia supernova (SN Ia) rate is likely RIa ≈ 1.1 × 10-13 yr^{-1} M_⊙ ^{-1} and therefore, in terms of rates, a possibly small fraction of all merging DWDs (e.g. those with massive-enough primary WDs) could suffice to produce most or all SNe Ia.

  15. The binary fraction, separation distribution, and merger rate of white dwarfs from SPY

    Science.gov (United States)

    Maoz, Dan; Hallakoun, Na'ama

    2017-05-01

    From a sample of spectra of 439 white dwarfs (WDs) from the ESO-VLT Supernova-Ia Progenitor Survey (SPY), we measure the maximal changes in radial velocity (ΔRVmax) between epochs (generally two epochs, separated by up to 470 d), and model the observed ΔRVmax statistics via Monte Carlo simulations, to constrain the population characteristics of double WDs (DWDs). The DWD fraction among WDs is fbin = 0.10 ± 0.02 (1σ, random) +0.02 (systematic), in the separation range ≲4 au within which the data are sensitive to binarity. Assuming the distribution of binary separation, a, is a power law, dN/da ∝ aα, at the end of the last common-envelope phase and the start of solely gravitational-wave-driven binary evolution, the constraint by the data is α = -1.3 ± 0.2 (1σ) ±0.2 (systematic). If these parameters extend to small separations, the implied Galactic WD merger rate per unit stellar mass is Rmerge = (1-80) × 10-13 yr^{-1} M_{⊙}^{-1} (2σ), with a likelihood-weighted mean of Rmerge = (7 ± 2) × 10-13 yr^{-1} M_{⊙}^{-1} (1σ). The Milky Way's specific Type Ia supernova (SN Ia) rate is likely RIa ≈ 1.1 × 10-13 yr^{-1} M_{⊙}^{-1} and therefore, in terms of rates, a possibly small fraction of all merging DWDs (e.g. those with massive-enough primary WDs) could suffice to produce most or all SNe Ia.

  16. SPY Imaging Assessment Correlates With Transesophageal Echocardiogram Assessment of Ventricular Function During Off-Pump Coronary Artery Bypass Grafting.

    Science.gov (United States)

    Anderson, Curtis A; Kypson, Alan P; Hudson, Wes; Ferguson, Bruce; Rodriguez, Evelio

    2008-05-01

    Intraoperative assessment of graft anastomoses is commonly performed after off-pump coronary artery bypass grafting (OPCAB). The SPY imaging system allows intraoperative graft assessment. We document correlation between intraoperative SPY images and wall motion abnormality by transesophageal echocardiogram (TEE) during OPCAB. A 79-year-old female underwent OPCAB. Intraoperative graft patency assessment was performed with the SPY and left ventricular wall motion was assessed by TEE. SPY imaging demonstrated poor flow trough the distal vein graft anastomosis to the posterior descending artery, which correlated with a new posterior wall motion hypokinesis. After graft revision, SPY imaging demonstrated good distal flow and the TEE demonstrated normalization of the left ventricular posterior wall motion. SPY technology allows the surgeon to accurately assess graft patency intraoperatively and allows immediate correction of a technical problem.

  17. Transcriptional and Post-Transcriptional Modulation of SPI1 and SPI2 Expression by ppGpp, RpoS and DksA in Salmonella enterica sv Typhimurium.

    Science.gov (United States)

    Rice, Christopher J; Ramachandran, Vinoy K; Shearer, Neil; Thompson, Arthur

    2015-01-01

    The expression of genes within Salmonella Pathogenicity Islands 1 and 2 (SPI1, SPI2) is required to facilitate invasion and intracellular replication respectively of S. Typhimurium in host cell lines. Control of their expression is complex and occurs via a variety of factors operating at transcriptional and post-transcriptional levels in response to the environmental stimuli found within the host. Several of the factors that modulate SPI1 and SPI2 expression are involved in the redistribution or modification of RNA polymerase (RNAP) specificity. These factors include the bacterial alarmone, ppGpp, the alternative sigma factor, RpoS, and the RNAP accessory protein, DksA. In this report we show not only how these three factors modulate SPI1 and SPI2 expression but also how they contribute to the 'phased' expression of SPI1 and SPI2 during progress through late-log and stationary phase in aerobic rich broth culture conditions. In addition, we demonstrate that the expression of at least one SPI1-encoded protein, SipC is subject to DksA-dependent post-transcriptional control.

  18. Transcriptional and Post-Transcriptional Modulation of SPI1 and SPI2 Expression by ppGpp, RpoS and DksA in Salmonella enterica sv Typhimurium.

    Directory of Open Access Journals (Sweden)

    Christopher J Rice

    Full Text Available The expression of genes within Salmonella Pathogenicity Islands 1 and 2 (SPI1, SPI2 is required to facilitate invasion and intracellular replication respectively of S. Typhimurium in host cell lines. Control of their expression is complex and occurs via a variety of factors operating at transcriptional and post-transcriptional levels in response to the environmental stimuli found within the host. Several of the factors that modulate SPI1 and SPI2 expression are involved in the redistribution or modification of RNA polymerase (RNAP specificity. These factors include the bacterial alarmone, ppGpp, the alternative sigma factor, RpoS, and the RNAP accessory protein, DksA. In this report we show not only how these three factors modulate SPI1 and SPI2 expression but also how they contribute to the 'phased' expression of SPI1 and SPI2 during progress through late-log and stationary phase in aerobic rich broth culture conditions. In addition, we demonstrate that the expression of at least one SPI1-encoded protein, SipC is subject to DksA-dependent post-transcriptional control.

  19. Salmonella Typhimurium induces SPI-1 and SPI-2 regulated and strain dependent downregulation of MHC II expression on porcine alveolar macrophages.

    Science.gov (United States)

    Van Parys, Alexander; Boyen, Filip; Verbrugghe, Elin; Leyman, Bregje; Bram, Flahou; Haesebrouck, Freddy; Pasmans, Frank

    2012-06-13

    Foodborne salmonellosis is one of the most important bacterial zoonotic diseases worldwide. Salmonella Typhimurium is the serovar most frequently isolated from persistently infected slaughter pigs in Europe. Circumvention of the host's immune system by Salmonella might contribute to persistent infection of pigs. In the present study, we found that Salmonella Typhimurium strain 112910a specifically downregulated MHC II, but not MHC I, expression on porcine alveolar macrophages in a Salmonella pathogenicity island (SPI)-1 and SPI-2 dependent way. Salmonella induced downregulation of MHC II expression and intracellular proliferation of Salmonella in macrophages were significantly impaired after opsonization with Salmonella specific antibodies prior to inoculation. Furthermore, the capacity to downregulate MHC II expression on macrophages differed significantly among Salmonella strains, independently of strain specific differences in invasion capacity, Salmonella induced cytotoxicity and altered macrophage activation status. The fact that strain specific differences in MHC II downregulation did not correlate with the extent of in vitro SPI-1 or SPI-2 gene expression indicates that other factors are involved in MHC II downregulation as well. Since Salmonella strain dependent interference with the pig's immune response through downregulation of MHC II expression might indicate that certain Salmonella strains are more likely to escape serological detection, our findings are of major interest for Salmonella monitoring programs primarily based on serology.

  20. Salmonella Typhimurium induces SPI-1 and SPI-2 regulated and strain dependent downregulation of MHC II expression on porcine alveolar macrophages

    Directory of Open Access Journals (Sweden)

    Van Parys Alexander

    2012-06-01

    Full Text Available Abstract Foodborne salmonellosis is one of the most important bacterial zoonotic diseases worldwide. Salmonella Typhimurium is the serovar most frequently isolated from persistently infected slaughter pigs in Europe. Circumvention of the host’s immune system by Salmonella might contribute to persistent infection of pigs. In the present study, we found that Salmonella Typhimurium strain 112910a specifically downregulated MHC II, but not MHC I, expression on porcine alveolar macrophages in a Salmonella pathogenicity island (SPI-1 and SPI-2 dependent way. Salmonella induced downregulation of MHC II expression and intracellular proliferation of Salmonella in macrophages were significantly impaired after opsonization with Salmonella specific antibodies prior to inoculation. Furthermore, the capacity to downregulate MHC II expression on macrophages differed significantly among Salmonella strains, independently of strain specific differences in invasion capacity, Salmonella induced cytotoxicity and altered macrophage activation status. The fact that strain specific differences in MHC II downregulation did not correlate with the extent of in vitro SPI-1 or SPI-2 gene expression indicates that other factors are involved in MHC II downregulation as well. Since Salmonella strain dependent interference with the pig’s immune response through downregulation of MHC II expression might indicate that certain Salmonella strains are more likely to escape serological detection, our findings are of major interest for Salmonella monitoring programs primarily based on serology.

  1. Phosphorus NMR of isolated perfused morris hepatomas

    Energy Technology Data Exchange (ETDEWEB)

    Graham, R.A.; Meyer, R.A.; Brown, T.R.; Sauer, L.A.

    1986-03-05

    The authors are developing techniques for the study of perfused solid tumors by NMR. Tissue-isolated solid hepatomas were grown to 1-2 cm diameter as described previously. The arterial supply was isolated and the tumors perfused (0.5 - 1.0 ml/min) in vitro at 25 C with a 15% suspension of red blood cells in Krebs-Henseliet solution. /sup 31/P-NMR spectra were acquired at 162 MHz in a specially-designed NMR probe using a solenoidal coil. Intracellular pH (monitored from the chemical shift of inorganic phosphate) and ATP levels were stable for up to 6 hrs during perfusion. During 30 min of global ischemia, ATP decreased by 75% and pH fell from 7.0 to 6.7. These changes were reversed by 1 hr reperfusion. In addition to ATP and phosphate, the spectra included a large resonance due to phosphomonoesters, as well as peaks consistent with glycerylphosphocholine, glyceryl-phosphoethanolamine, phosphocreatine, NAD, and UDPG. However, the most novel feature of the spectra was the presence of an unidentified peak in the phosphonate region (+ 16.9 ppm). The peak was not present in spectra of muscle, liver, brain, kidney, or fat tissues excised from the same animals. They are presently attempting to identify the compound that gives rise to this peak and to establish its metabolic origin.

  2. SpyB, a small heme-binding protein, affects the composition of the cell wall in Streptococcus pyogenes

    Directory of Open Access Journals (Sweden)

    Rebecca J Edgar

    2016-10-01

    Full Text Available Streptococcus pyogenes (Group A Streptococcus or GAS is a haemolytic human pathogen associated with a wide variety of infections ranging from minor skin and throat infections to life-threatening invasive diseases. The cell wall of GAS consists of peptidoglycan sacculus decorated with a carbohydrate comprising a polyrhamnose backbone with immunodominant N-acetylglucosamine side-chains. All GAS genomes contain the spyBA operon, which encodes a 35-amino-acid membrane protein SpyB, and a membrane-bound C3-like ADP-ribosyltransferase SpyA. In this study we addressed the function of SpyB in GAS. Phenotypic analysis of a spyB deletion mutant revealed increased bacterial aggregation, and reduced sensitivity to β-lactams of the cephalosporin class and peptidoglycan hydrolase PlyC. Glycosyl composition analysis of cell wall isolated from the spyB mutant suggested an altered carbohydrate structure compared with the wild-type strain. Furthermore, we found that SpyB associates with heme and protoporphyrin IX. Heme binding induces SpyB dimerization, which involves disulfide bond formation between the subunits. Thus, our data suggest the possibility that SpyB activity is regulated by heme.

  3. SpyB, a Small Heme-Binding Protein, Affects the Composition of the Cell Wall in Streptococcus pyogenes.

    Science.gov (United States)

    Edgar, Rebecca J; Chen, Jing; Kant, Sashi; Rechkina, Elena; Rush, Jeffrey S; Forsberg, Lennart S; Jaehrig, Bernhard; Azadi, Parastoo; Tchesnokova, Veronika; Sokurenko, Evgeni V; Zhu, Haining; Korotkov, Konstantin V; Pancholi, Vijay; Korotkova, Natalia

    2016-01-01

    Streptococcus pyogenes (Group A Streptococcus or GAS) is a hemolytic human pathogen associated with a wide variety of infections ranging from minor skin and throat infections to life-threatening invasive diseases. The cell wall of GAS consists of peptidoglycan sacculus decorated with a carbohydrate comprising a polyrhamnose backbone with immunodominant N-acetylglucosamine side-chains. All GAS genomes contain the spyBA operon, which encodes a 35-amino-acid membrane protein SpyB, and a membrane-bound C3-like ADP-ribosyltransferase SpyA. In this study, we addressed the function of SpyB in GAS. Phenotypic analysis of a spyB deletion mutant revealed increased bacterial aggregation, and reduced sensitivity to β-lactams of the cephalosporin class and peptidoglycan hydrolase PlyC. Glycosyl composition analysis of cell wall isolated from the spyB mutant suggested an altered carbohydrate structure compared with the wild-type strain. Furthermore, we found that SpyB associates with heme and protoporphyrin IX. Heme binding induces SpyB dimerization, which involves disulfide bond formation between the subunits. Thus, our data suggest the possibility that SpyB activity is regulated by heme.

  4. Advanced solid-state NMR spectroscopy of natural organic matter.

    Science.gov (United States)

    Mao, Jingdong; Cao, Xiaoyan; Olk, Dan C; Chu, Wenying; Schmidt-Rohr, Klaus

    2017-05-01

    Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially a systematic approach to NOM characterization, and their applications to the study of NOM. We discuss some basics of how to acquire high-quality and quantitative solid-state (13)C NMR spectra, and address some common technical mistakes that lead to unreliable spectra of NOM. The identification of specific functional groups in NOM, primarily based on (13)C spectral-editing techniques, is described and the theoretical background of some recently-developed spectral-editing techniques is provided. Applications of solid-state NMR to investigating nitrogen (N) in NOM are described, focusing on limitations of the widely used (15)N CP/MAS experiment and the potential of improved advanced NMR techniques for characterizing N forms in NOM. Then techniques used for identifying proximities, heterogeneities and domains are reviewed, and some examples provided. In addition, NMR techniques for studying segmental dynamics in NOM are reviewed. We also briefly discuss applications of solid-state NMR to NOM from various sources, including soil organic matter, aquatic organic matter, organic matter in atmospheric particulate matter, carbonaceous meteoritic organic matter, and fossil fuels. Finally, examples of NMR-based structural models and an outlook are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. NMR at 900 MHz

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    @@ An important factor in the development of solutionstate NMR has always been th e ability to produce stable and homogeneous magnetic fields. As higher and higher field strengths are reached the pressure is growing on manufacturers to produce NMR systems with greatly improved spectral resolution and signal to noise ratio. The introduction of the Varian 900 MHz INOVA system in August 2000 featuring Oxford Instruments 21.1 T magnet represents the latest pioneering development in NMR technology.

  6. Spy: a new group of eukaryotic DNA transposons without target site duplications.

    Science.gov (United States)

    Han, Min-Jin; Xu, Hong-En; Zhang, Hua-Hao; Feschotte, Cédric; Zhang, Ze

    2014-06-24

    Class 2 or DNA transposons populate the genomes of most eukaryotes and like other mobile genetic elements have a profound impact on genome evolution. Most DNA transposons belong to the cut-and-paste types, which are relatively simple elements characterized by terminal-inverted repeats (TIRs) flanking a single gene encoding a transposase. All eukaryotic cut-and-paste transposons so far described are also characterized by target site duplications (TSDs) of host DNA generated upon chromosomal insertion. Here, we report a new group of evolutionarily related DNA transposons called Spy, which also include TIRs and DDE motif-containing transposase but surprisingly do not create TSDs upon insertion. Instead, Spy transposons appear to transpose precisely between 5'-AAA and TTT-3' host nucleotides, without duplication or modification of the AAATTT target sites. Spy transposons were identified in the genomes of diverse invertebrate species based on transposase homology searches and structure-based approaches. Phylogenetic analyses indicate that Spy transposases are distantly related to IS5, ISL2EU, and PIF/Harbinger transposases. However, Spy transposons are distinct from these and other DNA transposon superfamilies by their lack of TSD and their target site preference. Our findings expand the known diversity of DNA transposons and reveal a new group of eukaryotic DDE transposases with unusual catalytic properties.

  7. Involvement of multiple transcription factors for metal-induced spy gene expression in Escherichia coli.

    Science.gov (United States)

    Yamamoto, Kaneyoshi; Ogasawara, Hiroshi; Ishihama, Akira

    2008-01-20

    Bacteria are directly exposed to metals in environment. To maintain the intracellular metal homeostasis, Escherichia coli contain a number of gene regulation systems, each for response to a specific metal. A periplasmic protein Spy of E. coli was found to be induced upon short-exposure to copper ion in CpxAR-dependent manner. Transcription of the spy gene was also induced by long-exposure to zinc ion. This induction, however, depended on another two-component system BaeSR. Using DNase-I footprinting assay, we identified two BaeR-binding regions on the spy promoter with a direct repeat of the BaeR-box sequence, TCTNCANAA. The zinc-responsive BaeR-binding sites were separated from copper-responsive CpxR-binding site, implying that the spy promoter responds to two species of metal independently through different using sensor-response regulator systems. Since BaeSR-dependent zinc response requires longer time, the induction of spy gene transcription by external zinc may include multiple steps such as through sensing the zinc-induced envelope disorder by BaeSR.

  8. SPI drought class prediction using log-linear models applied to wet and dry seasons

    Science.gov (United States)

    Moreira, Elsa E.

    2016-08-01

    A log-linear modelling for 3-dimensional contingency tables was used with categorical time series of SPI drought class transitions for prediction of monthly drought severity. Standardized Precipitation Index (SPI) time series in 12- and 6-month time scales were computed for 10 precipitation time series relative to GPCC datasets with 2.5° spatial resolution located over Portugal and with 112 years length (1902-2014). The aim was modelling two-month step class transitions for the wet and dry seasons of the year and then obtain probability ratios - Odds - as well as their respective confidence intervals to estimate how probable a transition is compared to another. The prediction results produced by the modelling applied to wet and dry season separately, for the 6- and the 12-month SPI time scale, were compared with the results produced by the same modelling without the split, using skill scores computed for the entire time series length. Results point to good prediction performances ranging from 70 to 80% in the percentage of corrects (PC) and 50-70% in the Heidke skill score (HSS), with the highest scores obtained when the modelling is applied to the SPI12. The adding up of the wet and dry seasons introduced in the modelling brought improvements in the predictions, of about 0.9-4% in the PC and 1.3-6.8% in the HSS, being the highest improvements obtained in the SPI6 application.

  9. Reliability and validity of the Korean standard pattern identification for stroke (K-SPI-Stroke questionnaire

    Directory of Open Access Journals (Sweden)

    Kang Byoung-Kab

    2012-04-01

    Full Text Available Abstract Background The present study was conducted to examine the reliability and validity of the ‘Korean Standard Pattern Identification for Stroke (K-SPI-Stroke’, which was developed and evaluated within the context of traditional Korean medicine (TKM. Methods Between September 2006 and December 2010, 2,905 patients from 11 Korean medical hospitals were asked to complete the K-SPI-Stroke questionnaire as a part of project ' Fundamental study for the standardization and objectification of pattern identification in traditional Korean medicine for stroke (SOPI-Stroke. Each patient was independently diagnosed by two TKM physicians from the same site according to one of four patterns, as suggested by the Korea Institute of Oriental Medicine: 1 a Qi deficiency pattern, 2 a Dampness-phlegm pattern, 3 a Yin deficiency pattern, or 4 a Fire-heat pattern. We estimated the internal consistency using Cronbach’s α coefficient, the discriminant validity using the means score of patterns, and the predictive validity using the classification accuracy of the K-SPI-Stroke questionnaire. Results The K-SPI-Stroke questionnaire had satisfactory internal consistency (α = 0.700 and validity, with significant differences in the mean of scores among the four patterns. The overall classification accuracy of this questionnaire was 65.2 %. Conclusion These results suggest that the K-SPI-Stroke questionnaire is a reliable and valid instrument for estimating the severity of the four patterns.

  10. Solid-state NMR of polymers

    Energy Technology Data Exchange (ETDEWEB)

    Mirau, P

    2001-07-01

    Nuclear magnetic resonance (NMR) spectroscopy has emerged as one of the most important methods for the solid-state characterisation of polymers. The popularity of NMR is due to the fact that many molecular level features can be measured from the NMR spectra, including the polymer chain conformation, the morphology and the dynamics. The spectral features and relaxation times are affected by local interactions, so they provide information about the structure of polymers on a length scale (2-200 A) that is difficult to measure by other methods. In favourable cases, the NMR experiments provide a molecular-level explanation for the transitions observed by differential scanning calorimetry (DSC) and other methods, and the NMR properties can often be related to the bulk properties. Solid-state NMR has long been of interest in polymer science, and the first solid-state NMR studies of polymers were reported approximately a year after the discovery of nuclear resonance in bulk matter. It was reported in this initial study that the proton line width for natural rubber at room temperature is more like that of a mobile liquid than of a solid, but that the resonance broadens near the glass transition temperature (T{sub g}). This was recognised as being related to a change in chain dynamics above and below the T{sub g}. NMR methods developed rapidly after these initial observations, first for polymers in solution and, more recently, for polymers in the solid-state. Solid-state NMR studies of polymers were developed more slowly than their solution-state counterparts because solid-state NMR requires more specialised equipment. Solid-state NMR is now such an important tool that most modern spectrometers are capable of performing these studies. The interest in the NMR of solid polymers is due in part to the fact that most polymers are used in the solid state, and in many cases the NMR properties can be directly related to the macroscopic properties. Polymers have restricted mobility

  11. Conformation of the nootropic agents 1-(4-methoxybenzoyl)-5-oxo-2-pyrrolidinepropanoic acid (CI-933) and 4-hydroxymethyl-1-benzyl-pyrrolidin-2-one (WEB-1868): X-ray crystal structures, theoretical MO calculations (AM-1) and 600 MHZ 1H NMR spectra

    Science.gov (United States)

    Amato, Maria E.; Bandoli, Giuliano; Djedaïni, Florence; Dolmella, Alessandro; Grassi, Antonio; Pappalardo, Giuseppe C.

    1990-05-01

    The crystal and molecular structures of the cognition activators 1-(4-methoxybenzoyl)-5-oxo-2-pyrrolidinepropanoic acid (CI-933) ( 1) and 4-hydroxymethyl-1-benzyl-pyrrolidin-2-one (WEB-1868) ( 2) have been determined by X-ray analysis. The conformations of the isolated molecules 1 and 2 have been deduced from AM1-type theoretical calculations. Whilst in 1 there are no hydrogen bonds, in 2 stabilization of the crystal occurs through effective inter- and intramolecular ? bonds. The five-membered ring in both 1 and 2 adopts an envelope conformation in the solid with C(3) at the flap displaced from the C(1), C(2), C(4), N(5) mean plane. Bond distances and angles are normal and comparable with previously known similar structures. In the crystal, the torsion angles C(1)-N(5)-C(6)-C(7) and N(5)-C(6)-C(7)-C(8) in 1 are 43.1° and 44.8°, respectively; the same torsion angles in 2 are -101° and 42°, respectively. Results of theoretical calculations correlate well with the conformation of 1 in the solid, whilst in the case of 2 these indicate that the conformation in the crystal should not be retained by the isolated molecule. The complete analysis of the very high field (600 MHz) 1H NMR spectra of both compounds in CDCl 3, gives results well in line with the above established conformational features.

  12. MEASURING VARIABILITY SOURCES IN NMR METABOLOMIC STUDIES

    OpenAIRE

    Rozet, Eric; de Tullio, Pascal; Hubert, Philippe; Govaerts., B.

    2013-01-01

    Due to the huge amount of information available in NMR spectra obtained from the analysis of metabolomic experiments, multivariate analysis such as Principal Component Analysis (PCA) are required to understand the influence of treatments over the metabolites [1]. However, many experiments in metabolomics studies have more complexes variability structures than simply comparing several treatments: they may include time effects, biological effects such as diet or hormonal status, and other bloc...

  13. First Observation of the Decay B0->psi(2S)pi0

    CERN Document Server

    Chobanova, V; Kiesling, C; Abdesselam, A; Adachi, I; Aihara, H; Asner, D M; Aushev, T; Ayad, R; Babu, V; Badhrees, I; Bahinipati, S; Bakich, A M; Barberio, E; Behera, P; Bhardwaj, V; Bhuyan, B; Biswal, J; Bobrov, A; Bozek, A; Bračko, M; Browder, T E; Červenkov, D; Chekelian, V; Chen, A; Cheon, B G; Chistov, R; Cho, K; Choi, Y; Cinabro, D; Dash, N; Doležal, Z; Drásal, Z; Drutskoy, A; Eidelman, S; Farhat, H; Fast, J E; Ferber, T; Fulsom, B G; Gaur, V; Gabyshev, N; Garmash, A; Gillard, R; Goh, Y M; Goldenzweig, P; Golob, B; Grzymkowska, O; Haba, J; Hara, T; Hayasaka, K; Hayashii, H; Hou, W -S; Iijima, T; Inami, K; Ishikawa, A; Iwasaki, Y; Jaegle, I; Jeon, H B; Joffe, D; Joo, K K; Julius, T; Kato, E; Katrenko, P; Kawasaki, T; Kim, D Y; Kim, H J; Kim, J B; Kim, K T; Kim, M J; Kim, S H; Kim, Y J; Kinoshita, K; Kodyš, P; Korpar, S; Križan, P; Krokovny, P; Kuhr, T; Kumar, R; Kumita, T; Kuzmin, A; Kwon, Y -J; Lee, I S; Li, H; Li, L; Li, Y; Gioi, L Li; Libby, J; Liventsev, D; Masuda, M; Matvienko, D; Miyata, H; Mizuk, R; Mohanty, G B; Mohanty, S; Moll, A; Moon, H K; Mori, T; Mussa, R; Nakano, E; Nakao, M; Nanut, T; Natkaniec, Z; Nayak, M; Nisar, N K; Nishida, S; Ogawa, S; Pakhlov, P; Pakhlova, G; Pal, B; Park, C W; Park, H; Paul, S; Pedlar, T K; Pestotnik, R; Petrič, M; Piilonen, L E; Pulvermacher, C; Rauch, J; Ribežl, E; Ritter, M; Ryu, S; Sahoo, H; Sakai, Y; Sandilya, S; Sanuki, T; Savinov, V; Schlüter, T; Schneider, O; Schnell, G; Schwanda, C; Schwartz, A J; Seino, Y; Senyo, K; Seon, O; Sevior, M E; Shebalin, V; Shibata, T -A; Shiu, J -G; Shwartz, B; Simon, F; Singh, J B; Sohn, Y -S; Sokolov, A; Solovieva, E; Starič, M; Stypula, J; Sumihama, M; Sumisawa, K; Sumiyoshi, T; Tamponi, U; Teramoto, Y; Trabelsi, K; Uchida, M; Uehara, S; Uglov, T; Unno, Y; Uno, S; Urquijo, P; Usov, Y; Van Hulse, C; Vanhoefer, P; Varner, G; Vinokurova, A; Vorobyev, V; Wagner, M N; Wang, C H; Wang, M -Z; Wang, P; Wang, X L; Watanabe, M; Watanabe, Y; Williams, K M; Won, E; Yamaoka, J; Yashchenko, S; Ye, H; Yelton, J; Yuan, C Z; Yusa, Y; Zhang, Z P; Zhilich, V; Zhulanov, V; Zupanc, A

    2015-01-01

    We report a measurement of the $B^0\\rightarrow\\psi(2S)\\pi^0$ branching fraction based on the full $\\Upsilon(4S)$ data set of $772\\times10^{6}$ $B\\bar{B}$ pairs collected by the Belle detector at the KEKB asymmetric-energy $e^+e^-$ collider. We obtain $B(B^0\\rightarrow\\psi(2S)\\pi^0) = (1.17\\pm0.17\\text{(stat)}\\pm0.08\\text{(syst)})\\times10^{-5}$. The result has a significance of 7.2 standard deviations and is the first observation of the decay $B^0\\rightarrow\\psi(2S)\\pi^0$.

  14. A novel approach for modelling the cluster detector and the SPI spectrometer

    Indian Academy of Sciences (India)

    Ritesh Kshetri; Pintu Bhattachary

    2014-11-01

    A probabilistic approach has been presented in six recent papers (R Kshetri, J. Instrum. 2012 7 P04008; ibid., P07006; ibid., P07008; ibid., P08015; ibid., P12007; Appl. Radiat. Isotopes 2013 75 30) for modelling a general composite detector. In this paper, a simplistic view has been presented on the application of our formalism to composite detectors consisting of hexagonal closely packed encapsulated HPGe detector modules.We have presented modified calculations for the peak-to-total (PT) and peak-to-background (PB) ratios of the cluster and spectrometer for integral satellite (SPI) for the first time considering up to four-fold events. Instead of using an empirical method or simulation, we present a novel approach for calculating the peak-to-total ratio of the SPI spectrometer for high energies. Our work can provide guidance for designing new composite detectors and for performing experimental studies with the SPI spectrometer for high-energy -rays.

  15. Substrate protein folds while it is bound to the ATP-independent chaperone Spy.

    Science.gov (United States)

    Stull, Frederick; Koldewey, Philipp; Humes, Julia R; Radford, Sheena E; Bardwell, James C A

    2016-01-01

    Chaperones assist in the folding of many proteins in the cell. Although the most well-studied chaperones use cycles of ATP binding and hydrolysis to assist in protein folding, a number of chaperones have been identified that promote folding in the absence of high-energy cofactors. Precisely how ATP-independent chaperones accomplish this feat is unclear. Here we characterized the kinetic mechanism of substrate folding by the small ATP-independent chaperone Spy from Escherichia coli. Spy rapidly associates with its substrate, immunity protein 7 (Im7), thereby eliminating Im7's potential for aggregation. Remarkably, Spy then allows Im7 to fully fold into its native state while it remains bound to the surface of the chaperone. These results establish a potentially widespread mechanism whereby ATP-independent chaperones assist in protein refolding. They also provide compelling evidence that substrate proteins can fold while being continuously bound to a chaperone.

  16. New data on the late Neandertals: direct dating of the Belgian Spy fossils.

    Science.gov (United States)

    Semal, Patrick; Rougier, Hélène; Crevecoeur, Isabelle; Jungels, Cécile; Flas, Damien; Hauzeur, Anne; Maureille, Bruno; Germonpré, Mietje; Bocherens, Hervé; Pirson, Stéphane; Cammaert, Laurence; De Clerck, Nora; Hambucken, Anne; Higham, Thomas; Toussaint, Michel; van der Plicht, Johannes

    2009-04-01

    In Eurasia, the period between 40,000 and 30,000 BP saw the replacement of Neandertals by anatomically modern humans (AMH) during and after the Middle to Upper Paleolithic transition. The human fossil record for this period is very poorly defined with no overlap between Neandertals and AMH on the basis of direct dates. Four new (14)C dates were obtained on the two adult Neandertals from Spy (Belgium). The results show that Neandertals survived to at least approximately 36,000 BP in Belgium and that the Spy fossils may be associated to the Lincombian-Ranisian-Jerzmanowician, a transitional techno-complex defined in northwest Europe and recognized in the Spy collections. The new data suggest that hypotheses other than Neandertal acculturation by AMH may be considered in this part of Europe.

  17. Malus pumila 'Spy 227' and Apple stem pitting virus: graft incompatibility and epinasty.

    Science.gov (United States)

    Brakta, Ajay; Handa, Anil; Thakur, P D; Tomar, Manica; Kumar, Pardeep

    2015-06-01

    Apple stem pitting foveavirus (ASPV) is one of the most important and widespread virus infecting apples in the world. Of late, the virus has been found to be invariably associated with most of the apple plantations of Shimla district of Himachal Pradesh based on DAS-ELISA results. Bioassay of viruses in vegetatively propagated crops including apple is considered to be an essential component in indexing programmes for the production of virus free propagating material. Woody indicator Malus pumila 'Spy 227' was used for the detection of ASPV through double grafting method. Graft incompatibility and epinasty symptoms were observed on Malus pumila Spy 227 indicator plants. Further, molecular identification of the virus isolate was done by cloning and sequencing of the test isolate. Partial sequence analysis of the coat protein gene showed 89 % nucleotide identity in BLASTN analysis with ASPV isolate from China (Accession No. JF895517). This is the first record of ASPV producing Graft incompatibility on Spy 227 indicator plants.

  18. Assessment Tools as Drivers for SPI: Short-term Benefits and Long-term Challenges

    DEFF Research Database (Denmark)

    Mûller, Sune Dueholm; Nørbjerg, Jacob; Cho, Hiu Ngan

    2007-01-01

    Full scale software process maturity assessments are costly, can have large organizational impact, and are carried out at long (12-24 months) intervals. Consequently, there is a need for techniques and tools to monitor and help manage an SPI project through inexpensive, ongoing progress assessments....... In this paper we present findings from two cases of using such a tool. We have found that the tool does provide useful snapshots of the status of SPI projects, but that long-term use of the tool introduces costs and challenges related to modifying and tailoring the tool to both the organizational context...... and the SPI implementation approach. Also, persistent use of an assessment tool may jeopardize assessment reliability due to wear-out and routinization....

  19. Assessment Tools as Drivers for SPI: Short-term Benefits and Long-term Challenges

    DEFF Research Database (Denmark)

    Mûller, Sune Dueholm; Nørbjerg, Jacob; Cho, Hiu Ngan

    2007-01-01

    Full scale software process maturity assessments are costly, can have large organizational impact, and are carried out at long (12-24 months) intervals. Consequently, there is a need for techniques and tools to monitor and help manage an SPI project through inexpensive, ongoing progress assessment....... In this paper we present findings from two cases of using such a tool We have found that the tool does provide useful snapshots of the status of an SPI projects, but that long-term use of the tool introduces costs and challenges related to modifying and tailoring the tool to both the organizational context...... and the SPI implementation approach. Also, persistent use of an assessment tool may jeopardize assessment reliability due to wear-out and routinization....

  20. WebSpy: An Architecture for Monitoring Web Server Availability in a Multi-Platform Environment

    Directory of Open Access Journals (Sweden)

    Madhan Mohan Thirukonda

    2002-01-01

    Full Text Available For an electronic business (e-business, customer satisfaction can be the difference between long-term success and short-term failure. Customer satisfaction is highly impacted by Web server availability, as customers expect a Web site to be available twenty-four hours a day and seven days a week. Unfortunately, unscheduled Web server downtime is often beyond the control of the organization. What is needed is an effective means of identifying and recovering from Web server downtime in order to minimize the negative impact on the customer. An automated architecture, called WebSpy, has been developed to notify administration and to take immediate action when Web server downtime is detected. This paper describes the WebSpy architecture and differentiates it from other popular Web monitoring tools. The results of a case study are presented as a means of demonstrating WebSpy's effectiveness in monitoring Web server availability.

  1. Intuitiveness 3D objects Interaction in Augmented Reality Using S-PI Algorithm

    Directory of Open Access Journals (Sweden)

    Ajune Wanis Ismail

    2013-07-01

    Full Text Available Numbers of researchers have developed interaction techniques in Augmented Reality (AR application. Some of them proposed new technique for user interaction with different types of interfaces which could bring great promise for intuitive user interaction with 3D data naturally. This paper will explore the 3D object manipulation performs in single-point interaction (S-PI technique in AR environment. The new interaction algorithm, S-PI technique, is point-based intersection designed to detect the interaction’s behaviors such as translate, rotate, clone and for intuitive 3D object handling. The S-PI technique is proposed with marker-based tracking in order to improve the trade-off between the accuracy and speed in manipulating 3D object in real-time. The method is robust required to ensure both elements of real and virtual can be combined relative to the user’s viewpoints and reduce system lag.  

  2. Gastro protective properties of the novel prostone SPI-8811 against acid-injured porcine mucosa

    Institute of Scientific and Technical Information of China (English)

    Meghali Nighot; Adam Moeser; Ryuji Ueno; Anthony Blikslager

    2012-01-01

    AIM:To evaluate the protective properties of novel prostone CIC-2 agonist SPI-8811 in porcine model of gastric acid injury.METHODS:Porcine gastric mucosa was mounted in Ussing chambers and injured by bathing mucosal tissues in an HCl Ringer's solution (pH =1.5) with or without SP1-8811 (1 μmol/L),cystic fibrosis transmembrane conductance regulator (CFTR) inhibitor (inhibitor 172,10 μmol/L,apical) and CIC-2 inhibitor ZnCl2,300 μmol/L,apical),on the apical surface of tissues.Transepithelial resistance and mucosal-to-serosal 3H-mannitol fluxes were measured over a 90-min period.Tissues were analyzed by morph metric techniques,Immunofluorescence and by western blots.RESULTS:Compared with control tissues,acid exposure decreased transepithelial electrical resistance (TER)and increased 3H-mannitol flux.Pretreatment of gastric mucosa with SPI-8811 was protective against acidinduced decreases in TER (TER,50 Ω.cm2 vs 100 Ω'cm2)and abolished increases in flux (3H-mannitol flux,0.10 μmol/L.cm2 vs 0.04 μmol/L.cm2).Evidence of histological damage in the presence of acid was markedly attenuated by SPI-0811.Immunofluorescence and western analysis for occludin revealed enhanced localization to the region of the tight junction (TJ) after treatment with SPI-8811.Pretreatment with the CIC-2 inhibitor ZnCl2,but not the selective CFTR inhibitor 172,attenuated SPI-8811-mediated mucosal protection,suggesting a role for CIC-2.Prostone may serve both protective and reparative roles in injured tissues.CONCLUSION:CIC-2 agonist SPI-8811 stimulated enhancement of mucosal barrier function by protecting TJ protein occludin in porcine gastric mucosa and thus protected the gastric acid injury in porcine stomach.

  3. Synapse-Centric Mapping of Cortical Models to the SpiNNaker Neuromorphic Architecture.

    Science.gov (United States)

    Knight, James C; Furber, Steve B

    2016-01-01

    While the adult human brain has approximately 8.8 × 10(10) neurons, this number is dwarfed by its 1 × 10(15) synapses. From the point of view of neuromorphic engineering and neural simulation in general this makes the simulation of these synapses a particularly complex problem. SpiNNaker is a digital, neuromorphic architecture designed for simulating large-scale spiking neural networks at speeds close to biological real-time. Current solutions for simulating spiking neural networks on SpiNNaker are heavily inspired by work on distributed high-performance computing. However, while SpiNNaker shares many characteristics with such distributed systems, its component nodes have much more limited resources and, as the system lacks global synchronization, the computation performed on each node must complete within a fixed time step. We first analyze the performance of the current SpiNNaker neural simulation software and identify several problems that occur when it is used to simulate networks of the type often used to model the cortex which contain large numbers of sparsely connected synapses. We then present a new, more flexible approach for mapping the simulation of such networks to SpiNNaker which solves many of these problems. Finally we analyze the performance of our new approach using both benchmarks, designed to represent cortical connectivity, and larger, functional cortical models. In a benchmark network where neurons receive input from 8000 STDP synapses, our new approach allows 4× more neurons to be simulated on each SpiNNaker core than has been previously possible. We also demonstrate that the largest plastic neural network previously simulated on neuromorphic hardware can be run in real time using our new approach: double the speed that was previously achieved. Additionally this network contains two types of plastic synapse which previously had to be trained separately but, using our new approach, can be trained simultaneously.

  4. Synapse-centric mapping of cortical models to the SpiNNaker neuromorphic architecture

    Directory of Open Access Journals (Sweden)

    James Courtney Knight

    2016-09-01

    Full Text Available While the adult human brain has approximately 8.8x10^10 neurons, this number is dwarfed by its 1x10^15 synapses. From the point of view of neuromorphic engineering and neural simulation in general this makes the simulation of these synapses a particularly complex problem. SpiNNaker is a digital, neuromorphic architecture designed for simulating large-scale spiking neural networks at speeds close to biological real-time. Current solutions for simulating spiking neural networks on SpiNNaker are heavily inspired by work on distributed high-performance computing. However, while SpiNNaker shares many characteristics with such distributed systems, its component nodes have much more limited resources and, as the system lacks global synchronization, the computation performed on each node must complete within a fixed time step. We first analyze the performance of the current SpiNNaker neural simulation software and identify several problems that occur when it is used to simulate networks of the type often used to model the cortex which contain large numbers of sparsely connected synapses. We then present a new, more flexible approach for mapping the simulation of such networks to SpiNNaker which solves many of these problems. Finally we analyze the performance of our new approach using both benchmarks, designed to represent cortical connectivity, and larger, functional cortical models. In a benchmark network where neurons receive input from 8000 STDP synapses, our new approach allows more neurons to be simulated on each SpiNNaker core than has been previously possible. We also demonstrate that the largest plastic neural network previously simulated on neuromorphic hardware can be run in real time using our new approach: double the speed that was previously achieved. Additionally this network contains two types of plastic synapse which previously had to be trained separately but, using our new approach, can be trained simultaneously.

  5. Radiation damping in microcoil NMR probes.

    Science.gov (United States)

    Krishnan, V V

    2006-04-01

    Radiation damping arises from the field induced in the receiver coil by large bulk magnetization and tends to selectively drive this magnetization back to equilibrium much faster than relaxation processes. The demand for increased sensitivity in mass-limited samples has led to the development of microcoil NMR probes that are capable of obtaining high quality NMR spectra with small sample volumes (nL-microL). Microcoil probes are optimized to increase sensitivity by increasing either the sample-to-coil ratio (filling factor) of the probe or quality factor of the detection coil. Though radiation damping effects have been studied in standard NMR probes, these effects have not been measured in the microcoil probes. Here a systematic evaluation of radiation damping effects in a microcoil NMR probe is presented and the results are compared with similar measurements in conventional large volume samples. These results show that radiation-damping effects in microcoil probe is much more pronounced than in 5 mm probes, and that it is critically important to optimize NMR experiments to minimize these effects. As microcoil probes provide better control of the bulk magnetization, with good RF and B0 inhomogeneity, in addition to negligible dipolar field effects due to nearly spherical sample volumes, these probes can be used exclusively to study the complex behavior of radiation damping.

  6. The IL-8 Protease SpyCEP/ScpC of Group A Streptococcus Promotes Resistance to Neutrophil Killing

    Science.gov (United States)

    Zinkernagel, Annelies S.; Timmer, Anjuli M.; Pence, Morgan A.; Locke, Jeffrey B.; Buchanan, John T.; Turner, Claire E.; Mishalian, Inbal; Sriskandan, Shiranee; Hanski, Emanuel; Nizet, Victor

    2009-01-01

    SUMMARY Interleukin-8 (IL-8) promotes neutrophil-mediated host defense through its chemoattractant and immunostimulatory activities. The Group A Streptococcus (GAS) protease SpyCEP (also called ScpC) cleaves IL-8, and SpyCEP expression is strongly upregulated in vivo in the M1T1 GAS strains associated with life-threatening systemic disease including necrotizing fasciitis. Coupling allelic replacement with heterologous gene expression, we show that SpyCEP is necessary and sufficient for IL-8 degradation. SpyCEP decreased IL-8-dependent neutrophil endothelial transmigration and bacterial killing, the latter by reducing neutrophil extracellular trap formation. The knockout mutant lacking SpyCEP was attenuated for virulence in murine infection models, and SpyCEP expression conferred protection to coinfecting bacteria. We also show that the zoonotic pathogen Streptococcus iniae possesses a functional homolog of SpyCEP (Cepl) that cleaves IL-8, promotes neutrophil resistance, and contributes to virulence. By inactivating the multifunctional host defense peptide IL-8, the SpyCEP protease impairs neutrophil clearance mechanisms, contributing to the pathogenesis of invasive streptococcal infection. PMID:18692776

  7. Status of Vi gene, its expression and Salmonella Pathogenicity Island (SPI-7) in Salmonella Typhi in India.

    Science.gov (United States)

    Maurya, Pushpa; Gulati, Anil K; Nath, Gopal

    2010-07-01

    Salmonella enterica serotype Typhi (S. Typhi) is a causative organism of typhoid fever. A number of Salmonella serovars express a capsular polysaccharide antigen known as Vi, the biosynthetic and export proteins of which are encoded within the viaB locus of Salmonella Pathogenicity Island -7 (SPI-7). SPI-7 is inserted between two partially duplicated copies of tRNA -pheU gene. We have investigated the frequency of viaB operon deletion and loss of SPI-7 due to storage of strains collected during the period 1987-2006 by PCR amplification of fliC (for confirmation of serotype Typhi), tviB (for status of viaB operon) and tRNA -pheU (for absence of SPI-7). All 111 isolates were observed with positive amplification of 495 bp amplicon for fliC. A total of 36 isolates were negative for Vi by agglutination while 39 were negative for viaB operon. Interestingly, 106 isolates were found to have SPI-7. The 5 SPI-7 negative isolates were isolated during recent years. Long-term storage and repeated culture had little or no effect on SPI-7, as none of the 18 isolates recovered from blood before 1997 lacked SPI-7. On the other hand, loss of viaB operon was directly proportional to duration of storage. Thus, it is proposed that stability of Vi gene is dependent on the presence of selection pressure.

  8. Preparation of Monoclonal Antibodies Against SpiC Protein Secreted by T3SS-2 of Salmonella spp.

    Science.gov (United States)

    Geng, Shizhong; Qian, Shanshan; Pan, Zhiming; Sun, Lin; Chen, Xiang; Jiao, Xinan

    2015-12-01

    SpiC protein, a member of Salmonella spp. type III secretion system (T3SS)-2, is necessary for the survival of Salmonella within macrophages, and it plays a vital role in Salmonella pathogenesis. To develop and test monoclonal antibodies (MAbs) against SpiC protein, two recombinant proteins, rHis-SpiC and rGST-SpiC, were expressed in vitro in the prokaryotic expression vectors pET-30(a) and pGEX-6p-1, respectively, and rHis-SpiC protein used to immunize mice. Hybridomas were generated from the splenocytes of these mice and the monoclonal antibodies produced by these cells were assessed using indirect enzyme-linked immunosorbent assay (ELISA) with rGST-SpiC as the coating antigen. An immunoblotting analysis indicated that all seven of the MAbs developed in this study could specifically recognize the SpiC protein. These MAbs will be very useful in the study of SpiC function and for use in the immunodiagnosis of Salmonella infection.

  9. Rovibrational and temperature effects in theoretical studies of NMR parameters

    DEFF Research Database (Denmark)

    Faber, Rasmus; Kaminsky, Jakub; Sauer, Stephan P. A.

    2016-01-01

    The demand for high precision calculations of NMR shieldings (or their related values, chemical shifts δ) and spin-spin coupling constants facilitating and supporting detailed interpretations of NMR spectra increases hand in hand with the development of computational techniques and hardware...... for molecular equilibrium geometries creates a demand for zero point vibrational and temperature corrections. In this chapter we describe briefly the theory behind rovibrational corrections and review then some important contributions to this field....

  10. NMR logging apparatus

    Energy Technology Data Exchange (ETDEWEB)

    Walsh, David O; Turner, Peter

    2014-05-27

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

  11. NMR logging apparatus

    Science.gov (United States)

    Walsh, David O; Turner, Peter

    2014-05-27

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

  12. NMR studies of metalloproteins.

    Science.gov (United States)

    Li, Hongyan; Sun, Hongzhe

    2012-01-01

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

  13. ASSESSMENT OF ACCURACY OF PRECIPITATION INDEX (SPI DETERMI-NED BY DIFFERENT PROBABILITY DISTRIBUTIONS

    Directory of Open Access Journals (Sweden)

    Edward Gąsiorek

    2014-11-01

    Full Text Available The use of different calculating methods to compute the standardized precipitation index (SPI results in various approximations. Methods based on normal distribution and its transformations, as well as on gamma distribution, give similar results and may be used equally, whereas the lognormal distribution fitting method is significantly discrepant, especially for extreme values of SPI. Therefore, it is problematic which method gives the distribution optimally fitted to empirical data. The aim of this study is to categorize the above mentioned methods according to the degree of approximation to empirical data from the Observatory of Agro- and Hydrometeorology in Wrocław-Swojec from 1964–2009 years.

  14. I-SPY 2: an adaptive breast cancer trial design in the setting of neoadjuvant chemotherapy.

    Science.gov (United States)

    Barker, A D; Sigman, C C; Kelloff, G J; Hylton, N M; Berry, D A; Esserman, L J

    2009-07-01

    I-SPY 2 (investigation of serial studies to predict your therapeutic response with imaging and molecular analysis 2) is a process targeting the rapid, focused clinical development of paired oncologic therapies and biomarkers. The framework is an adaptive phase II clinical trial design in the neoadjuvant setting for women with locally advanced breast cancer. I-SPY 2 is a collaborative effort among academic investigators, the National Cancer Institute, the US Food and Drug Administration, and the pharmaceutical and biotechnology industries under the auspices of the Foundation for the National Institutes of Health Biomarkers Consortium.

  15. UC Merced NMR Instrumentation Acquisition

    Science.gov (United States)

    2015-06-18

    UC Merced NMR Instrumentation Acquisition For the UC Merced NMR Instrumentation Acquisition proposal, a new 400 MHz and an upgraded 500 MHz NMR ...UC Merced NMR Instrumentation Acquisition Report Title For the UC Merced NMR Instrumentation Acquisition proposal, a new 400 MHz and an upgraded 500...MHz NMR have been delivered, installed, and incorporated into research and two lab courses. While no results from these instruments have been

  16. Structural analysis of N,N-diacyl-1,4-dihydropyrazine by variable-temperature NMR and DFT calculation

    Science.gov (United States)

    Song, Xiu-qing; Tan, Hong-bo; Yan, Hong; Chang, Yu

    2017-04-01

    N,N-diacyl-1,4-dihydropyrazine derivatives (1) were prepared via an efficient microwave-assisted synthesis. 1 was isolated and unambiguously confirmed by NMR spectra and high-resolution mass spectrometry. The NMR spectra of 1 showed complicated rather than conventional spectroscopy. Variable-temperature experiments and DFT calculation (PES) were used to investigate this phenomenon. DFT calculations confirmed that the structures of the two rotamers of 1 correspond to those determined by NMR in solution, and gave the syn-anti interconversion barriers of rotamers. The results showed that two isomers exist in solution (deuterated solvent) at room temperature, resulting in complicated NMR spectra.

  17. NMR studies on polyphosphide Ce6Ni6P17

    Science.gov (United States)

    Koyama, T.; Yamada, H.; Ueda, K.; Mito, T.; Aoyama, Y.; Nakano, T.; Takeda, N.

    2016-02-01

    We report the result of 31P nuclear magnetic resonance (NMR) studies on Ce6Ni6P17. The observed NMR spectra show a Lorentzian-type and an asymmetric shapes, reflecting the local symmetry around each P site in the cubic unit cell. We have identified the observed NMR lines corresponding to three inequivalent P sites and deduced the temperature dependence of the Knight shift for each site. The Knight shifts increase with decreasing temperature down to 1.5 K, indicating a localized spin system of Ce6Ni6P17. Antiferromagnetic correlation between 4f spins is suggested from the negative sign of the Weiss-temperature.

  18. Structural biology applications of solid state MAS DNP NMR

    Science.gov (United States)

    Akbey, Ümit; Oschkinat, Hartmut

    2016-08-01

    Dynamic Nuclear Polarization (DNP) has long been an aim for increasing sensitivity of nuclear magnetic resonance (NMR) spectroscopy, delivering spectra in shorter experiment times or of smaller sample amounts. In recent years, it has been applied in magic angle spinning (MAS) solid-state NMR to a large range of samples, including biological macromolecules and functional materials. New research directions in structural biology can be envisaged by DNP, facilitating investigations on very large complexes or very heterogeneous samples. Here we present a summary of state of the art DNP MAS NMR spectroscopy and its applications to structural biology, discussing the technical challenges and factors affecting DNP performance.

  19. Investigating sorption on iron-oxyhydroxide soil minerals by solid-state NMR spectroscopy: a 6Li MAS NMR study of adsorption and absorption on goethite

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Paik, Younkee; Julmis, Keinia;

    2005-01-01

    High-resolution 2H MAS NMR spectra can be obtained for nanocrystalline particles of goethite (alpha-FeOOH, particle size approximately 4-10 nm) at room temperature, facilitating NMR studies of sorption under environmentally relevant conditions. Li sorption was investigated as a function of pH, th...

  20. Crosstalk between virulence loci: regulation of Salmonella enterica pathogenicity island 1 (SPI-1) by products of the std fimbrial operon.

    Science.gov (United States)

    López-Garrido, Javier; Casadesús, Josep

    2012-01-01

    Invasion of intestinal epithelial cells is a critical step in Salmonella infection and requires the expression of genes located in Salmonella pathogenicity island 1 (SPI-1). A key factor for SPI-1 expression is DNA adenine (Dam) methylation, which activates synthesis of the SPI-1 transcriptional activator HilD. Dam-dependent regulation of hilD is postranscriptional (and therefore indirect), indicating the involvement of unknown cell functions under Dam methylation control. A genetic screen has identified the std fimbrial operon as the missing link between Dam methylation and SPI-1. We show that all genes in the std operon are part of a single transcriptional unit, and describe three previously uncharacterized ORFs (renamed stdD, stdE, and stdF). We present evidence that two such loci (stdE and stdF) are involved in Dam-dependent control of Salmonella SPI-1: in a Dam(-) background, deletion of stdE or stdF suppresses SPI-1 repression; in a Dam(+) background, constitutive expression of StdE and/or StdF represses SPI-1. Repression of SPI-1 by products of std operon explains the invasion defect of Salmonella Dam(-) mutants, which constitutively express the std operon. Dam-dependent repression of std in the ileum may be required to permit invasion, as indicated by two observations: constitutive expression of StdE and StdF reduces invasion of epithelial cells in vitro (1,000 fold) and attenuates Salmonella virulence in the mouse model (>60 fold). In turn, crosstalk between std and SPI-1 may play a role in intestinal infections by preventing expression of SPI-1 in the caecum, an intestinal compartment in which the std operon is known to be expressed.

  1. NMR data visualization, processing, and analysis on mobile devices.

    Science.gov (United States)

    Cobas, Carlos; Iglesias, Isaac; Seoane, Felipe

    2015-08-01

    Touch-screen computers are emerging as a popular platform for many applications, including those in chemistry and analytical sciences. In this work, we present our implementation of a new NMR 'app' designed for hand-held and portable touch-controlled devices, such as smartphones and tablets. It features a flexible architecture formed by a powerful NMR processing and analysis kernel and an intuitive user interface that makes full use of the smart devices haptic capabilities. Routine 1D and 2D NMR spectra acquired in most NMR instruments can be processed in a fully unattended way. More advanced experiments such as non-uniform sampled NMR spectra are also supported through a very efficient parallelized Modified Iterative Soft Thresholding algorithm. Specific technical development features as well as the overall feasibility of using NMR software apps will also be discussed. All aspects considered the functionalities of the app allowing it to work as a stand-alone tool or as a 'companion' to more advanced desktop applications such as Mnova NMR.

  2. Carbon abundances of sdO stars from SPY

    Science.gov (United States)

    Hirsch, Heiko; Heber, Uli

    2009-06-01

    Ströer et al. (2007) recently suggested a classification of sdOs according to supersolar and subsolar helium abundances, with only the helium-enriched stars showing signes of carbon and/or nitrogen in their optical spectra. We aim to derive reliable carbon and nitrogen abundances by fitting synthetic spectra to data obtained with the UVES spectrograph at ESO. Here we present our first results of the analysis of carbon abundances in hot subdwarf O stars. By constructing a grid of model atmospheres consisting of hydrogen, helium and carbon we were able to derive atmospheric parameters of nine carbon rich sdOs. We find log(NC/Ntotal) up to ten times higher than the solar value, while the mean value for the effective temperature and the surface gravity is slightly lower than derived by helium-hydrogen models only. Surprisingly, we also find three fast rotators among our program stars.

  3. Gamma-ray bursts observed by the INTEGRAL-SPI anticoincidence shield: A study of individual pulses and temporal variability

    DEFF Research Database (Denmark)

    Ryde, F.; Borgonovo, L.; Larsson, S.

    2003-01-01

    self-similar in shape. There is also a weak tendency for the pulses with steep power-law decays to be more asymmetric. Third, the variability of the complex light-curves is studied by analyzing their power-density-spectra (PDS) and their RMS variability. The averaged PDS, of the whole sample......We study a set of 28 GRB light-curves detected between 15 December 2002 and 9 June 2003 by the anti-coincidence shield of the spectrometer (SPI) of INTEGRAL. During this period it has detected 50 bursts, that have been confirmed by other instruments, with a time resolution of 50 ms. First, we...... derive the basic characteristics of the bursts: various duration measures, the count peak flux and the count fluence. Second, a sub-sample of 11 bursts with 12 individual, well-separated pulses is studied. We fit the pulse shape with a model by Kocevski et al. (2003) and find that the pulses are quite...

  4. Search for 511 keV Emission in Satellite Galaxies of the Milky Way with INTEGRAL/SPI

    CERN Document Server

    Siegert, Thomas; Vincent, Aaron C; Guglielmetti, Fabrizia; Krause, Martin G H; Boehm, Celine

    2016-01-01

    The positron annihilation gamma-ray signal in the Milky Way (MW) shows a puzzling morphology: a very bright bulge and a very low surface-brightness disk. A coherent explanation of the positron origin, propagation through the Galaxy and subsequent annihilation in the interstellar medium has not yet been found. Tentative explanations involve positrons from radioactivity, X-ray binaries, and dark matter (DM). Dwarf satellite galaxies (DSGs) are believed to be DM-dominated and hence promising candidates in the search for 511 keV emission as a result of DM annihilation into electron-positron pairs. The goal of this study is to constrain possible 511 keV gamma-ray signals from 39 DSGs of the MW and to test the annihilating DM scenario. We use the spectrometer SPI on INTEGRAL to extract individual spectra for the studied objects. As the diffuse galactic emission dominates the signal, the large scale morphology of the MW has been modelled accordingly and was included in a maximum likelihood analysis. Alternatively, a...

  5. RUNX1 induces DNA replication independent of active DNA demethylation at SPI1 regulatory regions.

    Science.gov (United States)

    Goyal, Shubham; Suzuki, Takahiro; Li, Jing-Ru; Maeda, Shiori; Kishima, Mami; Nishimura, Hajime; Shimizu, Yuri; Suzuki, Harukazu

    2017-04-04

    SPI1 is an essential transcription factor (TF) for the hematopoietic lineage, in which its expression is tightly controlled through a -17-kb upstream regulatory region and a promoter region. Both regulatory regions are demethylated during hematopoietic development, although how the change of DNA methylation status is performed is still unknown. We found that the ectopic overexpression of RUNX1 (another key TF in hematopoiesis) in HEK-293T cells induces almost complete DNA demethylation at the -17-kb upstream regulatory region and partial but significant DNA demethylation at the proximal promoter region. This DNA demethylation occurred in mitomycin-C-treated nonproliferating cells at both regulatory regions, suggesting active DNA demethylation. Furthermore, ectopic RUNX1 expression induced significant endogenous SPI1 expression, although its expression level was much lower than that of natively SPI1-expressing monocyte cells. These results suggest the novel role of RUNX1 as an inducer of DNA demethylation at the SPI1 regulatory regions, although the mechanism of RUNX1-induced DNA demethylation remains to be explored.

  6. FID-SPI pulse sequence for quantitative MRI of fluids in porous media.

    Science.gov (United States)

    Marica, Florea; Goora, Frédéric G; Balcom, Bruce J

    2014-03-01

    MRI has great potential for providing quantitative, spatially resolved information about fluids imbibed in porous media. The pure phase encode SPRITE technique has proven to be a very general method for the generation of density images in porous media; however, low flip-angle RF pulses and broad filter widths, required by short encoding times, yield sub-optimal S/N images. A 1-D phase-encoding sequence for T2(∗) mapping, named FID-SPI, is presented and analyzed in terms of image quality and accuracy of fluid content distribution in porous media. Extension to 2-D and 3-D imaging was straightforward and images of heterogeneous samples are presented. The FID-SPI measurement results in a series of individual T2(∗) weighted images acquired following RF excitation and pulsed phase-encoding gradients. Key to the performance of the FID-SPI method is high quality control of the magnetic field gradient pulse to ensure each FID point has identical spatial encoding. FID-SPI is intended for a quantitative determination of the spatially resolved fluid content in heterogeneous porous media, having the ability to determine the T2(∗) decay for each image pixel. T2(∗) mapping aids in estimation of the local fluid content.

  7. Epigenetic control of SPI1 gene by CTCF and ISWI ATPase SMARCA5.

    Directory of Open Access Journals (Sweden)

    Martina Dluhosova

    Full Text Available CCCTC-binding factor (CTCF can both activate as well as inhibit transcription by forming chromatin loops between regulatory regions and promoters. In this regard, Ctcf binding on non-methylated DNA and its interaction with the Cohesin complex results in differential regulation of the H19/Igf2 locus. Similarly, a role for CTCF has been established in normal hematopoietic development; however its involvement in leukemia remains elusive. Here, we show that Ctcf binds to the imprinting control region of H19/Igf2 in AML blasts. We also demonstrate that Smarca5, which also associates with the Cohesin complex, facilitates Ctcf binding to its target sites on DNA. Furthermore, Smarca5 supports Ctcf functionally and is needed for enhancer-blocking effect at ICR. We next asked whether CTCF and SMARCA5 control the expression of key hematopoiesis regulators. In normally differentiating myeloid cells both CTCF and SMARCA5 together with members of the Cohesin complex are recruited to the SPI1 gene, a key hematopoiesis regulator and leukemia suppressor. Due to DNA methylation, CTCF binding to the SPI1 gene is blocked in AML blasts. Upon AZA-mediated DNA demethylation of human AML blasts, CTCF and SMARCA5 are recruited to the -14.4 Enhancer of SPI1 gene and block its expression. Our data provide new insight into complex SPI1 gene regulation now involving additional key epigenetic factors, CTCF and SMARCA5 that control PU.1 expression at the -14.4 Enhancer.

  8. [Off-pump coronary artery bypass grafting using donut and SPY].

    Science.gov (United States)

    Takahashi, M; Ishikawa, T; Higashidani, K; Katoh, H

    2003-07-01

    Off-pump coronary artery bypass grafting (OPCAB) has been rapidly increased, because of its less invasiveness with low complications. However, graft patency rate highly depends on operators' capability due to technical difficulties. In this article, detail operative procedures are introduced to perform OPCAB in 100% for isolated coronary patients. Selecting better stabilizer may be a key of success. Donut Heart Stabilizer can make a still and stable operative field to anastomose less than 1 mm coronary artery. It is very useful to achieve complete revascularization for all stenosed coronary branches. OPCAB with 9 arterial grafts could be done using Donut. SPY Intra-operative Imaging System is also important to get 100% patency rate of the grafts. Using SPY, we can avoid graft trouble during operation in operation room (OR). SPY image is the best key information for operators to decide revision of the failed grafting. Donut 2 Heart Stabilizer has been improved to make more wide and stable operative field. Donut and SPY is the best combination for OPCAB.

  9. Google and the "Twisted Cyber Spy" Affair: US-Chinese Communication in an Age of Globalization

    Science.gov (United States)

    Hartnett, Stephen John

    2011-01-01

    The "twisted cyber spy" affair began in 2010, when Google was attacked by Chinese cyber-warriors charged with stealing Google's intellectual property, planting viruses in its computers, and hacking the accounts of Chinese human rights activists. In the ensuing international embroglio, the US mainstream press, corporate leaders, and White…

  10. An Evaluation of the SPIES Video Series (Strategies for Preschool Intervention in Everyday Settings).

    Science.gov (United States)

    Utley, Ginger; Qian, April; Eastmond, Nick

    The Strategies for Preschool Intervention in Everyday Settings (SPIES), funded by the State of Utah in conjunction with the Center for Persons with Disabilities at Utah State University, is an attempt to orient parents and teachers of preschool children to ways of dealing with children with disabilities. The primary vehicle for providing this…

  11. The evaluation of scientific monograph and publisher's role: the spanish project Scholarly Publishers Indicators (SPI

    Directory of Open Access Journals (Sweden)

    Andrea Capaccioni

    2016-05-01

    Full Text Available This paper aims to examine the issue about the quality assessment of scientific monograph and the role of publishers in the field of Humanities and Social Sciences, focusing on the Spanish project Scholarly Publishers Indicators (SPI. This project was born to identify and explore specific quality indicators for scientific books, starting from the opinion of SSH Spanish experts.

  12. The zebrafish spi1 promoter drives myeloid-specific expression in stable transgenic fish

    NARCIS (Netherlands)

    Ward, AC; McPhee, DO; Condron, MM; Varma, S; Cody, SH; Onnebo, SMN; Paw, BH; Zon, LI; Lieschke, GJ

    2003-01-01

    The spi1 (pu.1) gene has recently been identified as a useful marker of early myeloid cells in zebrafish. To enhance the versatility of this organism as a model for studying myeloid development, the promoter of this gene has been isolated and characterized. Transient transgenesis revealed that a 5.3

  13. Feasibility and effects of Science Education for Parents through the Internet (SPI) in Korea

    Science.gov (United States)

    Yoon, Jiyoon

    This study is to evaluate the feasibility and the effectiveness of Science Education for Parents through the Internet (SPI) in Korea. The SPI is a website that helps parents teach science to their 3rd grade children at home, avoiding the limitations of time, place, and educational resources and cultural/language differences. The subjects for the study are 15 Korean parents and 44 Korean students in Gaemung Elementary School. The feasibility was measured using the interview results from parents who used SPI, and the effectiveness was determined by the parents' self-efficacy beliefs and students' attitudinal and achievement outcomes. Parents' self-efficacy beliefs were assessed using the modified Science Teaching Efficacy Beliefs Instrument (STEBI). Students' attitudes toward science were evaluated by an instrument that combines the Test of Science-Related Attitudes (TOSRA) and a modified version of the Science Experiences Survey (SES), and the achievement was measured using scales from the Korean National Standard Test instrument. Descriptive statistics confirmed the feasibility and the effects of SPI for science education. Qualitative data were collected by interviewing the parents over the Internet. These data indicated that parent science education over the Internet gave parents the opportunity to increase their beliefs in teaching their children by interacting with the teacher in school, other parents in their neighborhood, and educational resources over the Internet, as well as to promote children's achievements in science and positive attitudes toward science.

  14. Quantifying Relationships between Water Quality and Aquatic Life Use Attainment using Sediment Profile Imagery (SPI)

    Science.gov (United States)

    We present results from a monthly SPI and water quality survey of nine stations along a transect in the Pensacola Bay estuary spanning the salinity gradient from Escambia River to the Gulf of Mexico. We evaluated Benthic Habitat Quality (Nilsson and Rosenberg 1997) derived from s...

  15. Quantifying Relationships between Water Quality and Aquatic Life Use Attainment using Sediment Profile Imagery (SPI)

    Science.gov (United States)

    We present results from a monthly SPI and water quality survey of nine stations along a transect in the Pensacola Bay estuary spanning the salinity gradient from Escambia River to the Gulf of Mexico. We evaluated Benthic Habitat Quality (Nilsson and Rosenberg 1997) derived from s...

  16. INTEGRAL SPI Limits on Electron-Positron Annihilation Radiation from the Galactic Plane

    DEFF Research Database (Denmark)

    Teegarden, B. J.; Watanabe, K.; Jean, P.;

    2005-01-01

    ‐Ray Astrophysics Laboratory) mission, launched in 2002 October, is the detailed study of this radiation. The Spectrometer on INTEGRAL (SPI) is a high‐resolution, coded‐aperture gamma‐ray telescope with an unprecedented combination of sensitivity, angular resolution, and energy resolution. We report results from...

  17. FID-SPI pulse sequence for quantitative MRI of fluids in porous media

    Science.gov (United States)

    Marica, Florea; Goora, Frédéric G.; Balcom, Bruce J.

    2014-03-01

    MRI has great potential for providing quantitative, spatially resolved information about fluids imbibed in porous media. The pure phase encode SPRITE technique has proven to be a very general method for the generation of density images in porous media; however, low flip-angle RF pulses and broad filter widths, required by short encoding times, yield sub-optimal S/N images. A 1-D phase-encoding sequence for T2∗ mapping, named FID-SPI, is presented and analyzed in terms of image quality and accuracy of fluid content distribution in porous media. Extension to 2-D and 3-D imaging was straightforward and images of heterogeneous samples are presented. The FID-SPI measurement results in a series of individual T2∗ weighted images acquired following RF excitation and pulsed phase-encoding gradients. Key to the performance of the FID-SPI method is high quality control of the magnetic field gradient pulse to ensure each FID point has identical spatial encoding. FID-SPI is intended for a quantitative determination of the spatially resolved fluid content in heterogeneous porous media, having the ability to determine the T2∗ decay for each image pixel. T2∗ mapping aids in estimation of the local fluid content.

  18. Integration of a complex regulatory cascade involving the SirA/BarA and Csr global regulatory systems that controls expression of the Salmonella SPI-1 and SPI-2 virulence regulons through HilD.

    Science.gov (United States)

    Martínez, Luary C; Yakhnin, Helen; Camacho, Martha I; Georgellis, Dimitris; Babitzke, Paul; Puente, José L; Bustamante, Víctor H

    2011-06-01

    Salmonella pathogenicity islands 1 and 2 (SPI-1 and SPI-2) play key roles in the pathogenesis of Salmonella enterica. Previously, we showed that when Salmonella grows in Luria-Bertani medium, HilD, encoded in SPI-1, first induces the expression of hilA, located in SPI-1, and subsequently of the ssrAB operon, located in SPI-2. These genes code for HilA and the SsrA/B two-component system, the positive regulators of the SPI-1 and SPI-2 regulons respectively. In this study, we demonstrate that CsrA, a global regulatory RNA binding protein, post-transcriptionally regulates hilD expression by directly binding near the Shine-Dalgarno and translation initiation codon sequences of the hilD mRNA, preventing its translation and leading to its accelerated turnover. Negative regulation is counteracted by the global SirA/BarA two-component system, which directly activates the expression of CsrB and CsrC, two non-coding regulatory RNAs that sequester CsrA, thereby preventing it from binding to its target mRNAs. Our results illustrate the integration of global and specific regulators into a multifactorial regulatory cascade controlling the expression of virulence genes acquired by horizontal transfer events.

  19. Experimental and theoretical study of the intramolecular C-H···N and C-H···S hydrogen bonding effects in the 1H and 13C NMR spectra of the 2-(alkylsulfanyl)-5-amino-1-vinylpyrroles: a particular state of amine nitrogen.

    Science.gov (United States)

    Afonin, Andrei V; Pavlov, Dmitry V; Albanov, Alexander I; Tarasova, Ol'ga A; Nedolya, Nina A

    2013-07-01

    In the (1)H NMR spectra of the 1-vinylpyrroles with amino- and alkylsulfanyl groups in 5 and 2 positions, an extraordinarily large difference between resonance positions of the HA and HB terminal methylene protons of the vinyl group is discovered. Also, the one-bond (1)J(C(β),H(B)) coupling constant is surprisingly greater than the (1)J(C(β),H(A)) coupling constant in pyrroles under investigation, while in all known cases, there was a reverse relationship between these coupling constants. These spectral anomalies are substantiated by quantum chemical calculations. The calculations show that the amine nitrogen lone pair is removed from the conjugation with the π-system of the pyrrole ring so that it is directed toward the HB hydrogen. These factors are favorable to the emergence of the intramolecular C-HB •••N hydrogen bonding in the s-cis(N) conformation. On the other hand, the spatial proximity of the sulfur to the HB hydrogen provides an opportunity of the intramolecular C-HB •••S hydrogen bonding in the s-cis(S) conformation. Presence of the hydrogen bond critical points as well as ring critical point for corresponding chelate ring revealed by a quantum theory of atoms in molecules (QTAIM) approach confirms the existence of the weak intramolecular C-H•••N and C-H•••S hydrogen bonding. Therefore, an unusual high-frequency shift of the HB signal and the increase in the (1)J(C(β),H(B)) coupling constant can be explained by the effects of hydrogen bonding. Copyright © 2013 John Wiley & Sons, Ltd.

  20. Benford distributions in NMR

    CERN Document Server

    Bhole, Gaurav; Mahesh, T S

    2014-01-01

    Benford's Law is an empirical law which predicts the frequency of significant digits in databases corresponding to various phenomena, natural or artificial. Although counter intuitive at the first sight, it predicts a higher occurrence of digit 1, and decreasing occurrences to other larger digits. Here we report the Benford analysis of various NMR databases and draw several interesting inferences. We observe that, in general, NMR signals follow Benford distribution in time-domain as well as in frequency domain. Our survey included NMR signals of various nuclear species in a wide variety of molecules in different phases, namely liquid, liquid-crystalline, and solid. We also studied the dependence of Benford distribution on NMR parameters such as signal to noise ratio, number of scans, pulse angles, and apodization. In this process we also find that, under certain circumstances, the Benford analysis can distinguish a genuine spectrum from a visually identical simulated spectrum. Further we find that chemical-sh...

  1. 13C Solution NMR Spectra of Poly(ether)urethanes

    Science.gov (United States)

    2002-11-01

    MDIO CH2 2019 14 DRDC Atlantic TM 2002-146 1 6 2 .9 8 1 5 4 .6 7 1 5 4 .5 8 1 3 8 .4 0 1 3 6 .6 2 1 2 9 .7 8 1...OCH2CH2 MDIO CH2CH2HN NH O C C O1 2 3 4 5 6 21 22 O CH2 OHCH2CH2O CH2CH2HN NH O C C O1 2 3 4 5 6 23 24 18 DRDC Atlantic TM 2002-146 1 6 2...DRDC Atlantic TM 2002-146 23 of the carbons arising from the diethylene glycol portion of DREA7. Comparison of the chemical environments

  2. NMR studies of the conformation and motion of tetrahydrofuran in graphite intercalation compounds

    Energy Technology Data Exchange (ETDEWEB)

    Caplan, D. F. [Lawrence Berkeley Lab., CA (United States); California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1991-11-01

    The behavior of tetrahydrofuran (THF) molecules intercalated in graphite layers in compounds Cs(THF){sub 1.3}C{sub 24} and K(THF){sub 2.5}C{sub 24} was studied by proton NMR. The graphite layers in these compounds impose a uniform ordering on the THF molecules, giving rise to sharp NMR spectra. Experimental and simulated proton NMR spectra were used to investigate geometry, orientation and conformation of intercalated THF, and to determine whether pseudorotation, a large amplitude low-frequency vibration observed in gaseous THF, can also occur in the constrained environment provided by the graphite intercalation compounds. Deuterium and multiple quantum proton NMR spectra were also simulated in order to determine if these techniques could further refine the proton NMR results.

  3. Search for 511 keV emission in satellite galaxies of the Milky Way with INTEGRAL/SPI

    Science.gov (United States)

    Siegert, Thomas; Diehl, Roland; Vincent, Aaron C.; Guglielmetti, Fabrizia; Krause, Martin G. H.; Boehm, Celine

    2016-10-01

    Context. The positron (e+) annihilation γ-ray signal in the Milky Way (MW) shows a puzzling morphology: a very bright bulge and a very low surface-brightness disk. A coherent explanation of the e+ origin, propagation through the Galaxy and subsequent annihilation in the interstellar medium has not yet been found. Tentative explanations involve e+s from radioactivity, X-ray binaries, and dark matter (DM). Aims: Dwarf satellite galaxies (DSGs) are believed to be dominated by DM and hence are promising candidates in the search for 511 keV emission as a result of DM annihilation into e+e--pairs. The goal of this study is to constrain possible 511 keV γ-ray signals from 39 DSGs of the MW and to test the annihilating DM scenario. Methods: We used the spectrometer SPI on INTEGRAL to extract individual spectra for the studied objects in the range 490-530 keV. As the diffuse galactic 511 keV emission dominates the overall signal, we modelled the large-scale morphology of the MW accordingly and included this in a maximum likelihood analysis. Alternatively, a distance-weighted stacked spectrum was determined, representing an average DSG seen in 511 keV. Results: Only Reticulum II (Ret II) shows a 3.1σ signal. Five other sources show tentative 2σ signals. The ratio of mass to 511 keV luminosity, Υ511, shows a marginal trend towards higher values for intrinsically brighter objects in contrast to the mass-to-light ratio, ΥV in the V band, which is generally used to uncover DM in DSGs. Conclusions: All derived 511 keV flux values or upper limits are above the flux level implied by a DM interpretation of the MW bulge signal. The signal detected from Ret II is unlikely to be related to a DM origin alone, otherwise, the MW bulge would be ~100 times brighter in 511 keV than what is seen with SPI. Ret II is exceptional considering the DSG sample and rather points to enhanced recent star formation activity if its origins are similar to processes in the MW. Understanding this

  4. E. coli chaperones DnaK, Hsp33 and Spy inhibit bacterial functional amyloid assembly.

    Science.gov (United States)

    Evans, Margery L; Schmidt, Jens C; Ilbert, Marianne; Doyle, Shannon M; Quan, Shu; Bardwell, James C A; Jakob, Ursula; Wickner, Sue; Chapman, Matthew R

    2011-01-01

    Amyloid formation is an ordered aggregation process, where β-sheet rich polymers are assembled from unstructured or partially folded monomers. We examined how two Escherichia coli cytosolic chaperones, DnaK and Hsp33, and a more recently characterized periplasmic chaperone, Spy, modulate the aggregation of a functional amyloid protein, CsgA. We found that DnaK, the Hsp70 homologue in E. coli, and Hsp33, a redox-regulated holdase, potently inhibited CsgA amyloidogenesis. The Hsp33 anti-amyloidogenesis activity was oxidation dependent, as oxidized Hsp33 was significantly more efficient than reduced Hsp33 at preventing CsgA aggregation. When soluble CsgA was seeded with preformed amyloid fibers, neither Hsp33 nor DnaK were able to efficiently prevent soluble CsgA from adopting the amyloid conformation. Moreover, both DnaK and Hsp33 increased the time that CsgA was reactive with the amyloid oligomer conformation-specific A11 antibody. Since CsgA must also pass through the periplasm during secretion, we assessed the ability of the periplasmic chaperone Spy to inhibit CsgA polymerization. Like DnaK and Hsp33, Spy also inhibited CsgA polymerization in vitro. Overexpression of Spy resulted in increased chaperone activity in periplasmic extracts and in reduced curli biogenesis in vivo. We propose that DnaK, Hsp33 and Spy exert their effects during the nucleation stages of CsgA fibrillation. Thus, both housekeeping and stress induced cytosolic and periplasmic chaperones may be involved in discouraging premature CsgA interactions during curli biogenesis.

  5. Monitoring oil displacement processes with k-t accelerated spin echo SPI.

    Science.gov (United States)

    Li, Ming; Xiao, Dan; Romero-Zerón, Laura; Balcom, Bruce J

    2016-03-01

    Magnetic resonance imaging (MRI) is a robust tool to monitor oil displacement processes in porous media. Conventional MRI measurement times can be lengthy, which hinders monitoring time-dependent displacements. Knowledge of the oil and water microscopic distribution is important because their pore scale behavior reflects the oil trapping mechanisms. The oil and water pore scale distribution is reflected in the magnetic resonance T2 signal lifetime distribution. In this work, a pure phase-encoding MRI technique, spin echo SPI (SE-SPI), was employed to monitor oil displacement during water flooding and polymer flooding. A k-t acceleration method, with low-rank matrix completion, was employed to improve the temporal resolution of the SE-SPI MRI measurements. Comparison to conventional SE-SPI T2 mapping measurements revealed that the k-t accelerated measurement was more sensitive and provided higher-quality results. It was demonstrated that the k-t acceleration decreased the average measurement time from 66.7 to 20.3 min in this work. A perfluorinated oil, containing no (1) H, and H2 O brine were employed to distinguish oil and water phases in model flooding experiments. High-quality 1D water saturation profiles were acquired from the k-t accelerated SE-SPI measurements. Spatially and temporally resolved T2 distributions were extracted from the profile data. The shift in the (1) H T2 distribution of water in the pore space to longer lifetimes during water flooding and polymer flooding is consistent with increased water content in the pore space. Copyright © 2015 John Wiley & Sons, Ltd.

  6. Genetic regulation of spy gene expression in Escherichia coli in the presence of protein unfolding agent ethanol.

    Science.gov (United States)

    Srivastava, Santosh Kumar; Lambadi, Paramesh Ramulu; Ghosh, Tamoghna; Pathania, Ranjana; Navani, Naveen Kumar

    2014-09-10

    In a living cell, folding of proteins is assisted by molecular chaperones and other folding helpers. In Escherichia coli (E. coli), recently an ATP independent chaperon 'Spy' was discovered which is highly up-regulated in the presence of protein unfolding agents like ethanol, butanol and tannic acid. Two response regulators; BaeR and CpxR have been recognized as transcriptional regulators of spy gene. However, the mechanism of genetic regulation of spy under protein denaturants like ethanol has not been studied in detail so far. Based on a combination of genetic, molecular biology and biochemical experimental data, we propose that BaeR protein is the primary regulator of spy gene in response to ethanol stress in E. coli. In addition, we expanded the experimental spectrum and validated that regulation of spy gene in the presence of zinc and copper metal stress is primarily via BaeR and CpxR regulators respectively. We also performed in-silico analysis to identify the homologs of Spy protein and their cognate regulatory elements in bacterial species belonging to enterobacteriaceae family. Based on the unique ATP-independent chaperone nature and genetic regulation of spy we also propose its importance in biosensor development and facilitated production of properly folded recombinant proteins.

  7. Spi-1/PU.1 oncogene accelerates DNA replication fork elongation and promotes genetic instability in the absence of DNA breakage.

    Science.gov (United States)

    Rimmelé, Pauline; Komatsu, Jun; Hupé, Philippe; Roulin, Christophe; Barillot, Emmanuel; Dutreix, Marie; Conseiller, Emmanuel; Bensimon, Aaron; Moreau-Gachelin, Françoise; Guillouf, Christel

    2010-09-01

    The multistage process of cancer formation is driven by the progressive acquisition of somatic mutations. Replication stress creates genomic instability in mammals. Using a well-defined multistep leukemia model driven by Spi-1/PU.1 overexpression in the mouse and Spi-1/PU.1-overexpressing human leukemic cells, we investigated the relationship between DNA replication and cancer progression. Here, using DNA molecular combing and flow cytometry methods, we show that Spi-1 increases the speed of replication by acting specifically on elongation rather than enhancing origin firing. This shortens the S-phase duration. Combining data from Spi-1 knockdown in murine cells with Spi-1 overexpression in human cells, we provide evidence that inappropriate Spi-1 expression is directly responsible for the replication alteration observed. Importantly, the acceleration of replication progression coincides with an increase in the frequency of genomic mutations without inducing DNA breakage. Thus, we propose that the hitherto unsuspected role for spi-1 oncogene in promoting replication elongation and genomic mutation promotes blastic progression during leukemic development.

  8. A possible long-term activity cycle for ι Horologii: First results from SPI-HKα project

    Science.gov (United States)

    Flores, Matías G.; Buccino, Andrea P.; Saffe, Carlos E.; Mauas, Pablo J. D.

    2017-02-01

    In order to detect stellar activity cycles and study possible star-planet interactions (SPIs), we have been developing the HKα and SPI-HKα projects since 1999 and 2012 respectively. In this work, we present preliminary results of possible SPIs from studies of chromospheric activity and look for possible correlations between stellar activity and stellar/planetary parameters. We find that for stars with a similar Teff, stellar activity increases with the mass of the planet, similar to results from previous works. However, stellar ages can also play a role, and a larger stellar sample is needed to verify these trends. We also note that some of these stars present a remarkably high level of chromospheric activity, comparable even with RSCvn or BY Dra active stars. In addition, we do not observe any correlation between stellar activity and semi-major axis. We present the first long-term activity study of the star ι Horologii, a young solar-type star that hosts a non-transiting Jovian planet and exhibits a high activity level. We analysed our own spectra, obtained between 2002 and 2015, in conjunction with public HARPS (High Accuracy Radial velocity Planet Searcher) observations. We calculated the Ca II indexes derived from the 987 Complejo Astronómico El Leoncito (CASLEO) and HARPS spectra and converted them to the Mt Wilson scale. We found a long-term activity cycle of ˜5 yr which fits the active sequence of Böhm-Vitense. The amplitude of this longer cycle is irregular, as was also observed for the shorter cycle. This phenomenon could be attributable to an antisymmetric distribution of active regions on the stellar surface.

  9. Correction: The role of coupled positive feedback in the expression of the SPI1 type three secretion system in Salmonella.

    Directory of Open Access Journals (Sweden)

    Supreet Saini

    2010-08-01

    Full Text Available Salmonella enterica serovar Typhimurium is a common food-borne pathogen that induces inflammatory diarrhea and invades intestinal epithelial cells using a type three secretion system (T3SS encoded within Salmonella pathogenicity island 1 (SPI1. The genes encoding the SPI1 T3SS are tightly regulated by a network of interacting transcriptional regulators involving three coupled positive feedback loops. While the core architecture of the SPI1 gene circuit has been determined, the relative roles of these interacting regulators and associated feedback loops are still unknown. To determine the function of this circuit, we measured gene expression dynamics at both population and single-cell resolution in a number of SPI1 regulatory mutants. Using these data, we constructed a mathematical model of the SPI1 gene circuit. Analysis of the model predicted that the circuit serves two functions. The first is to place a threshold on SPI1 activation, ensuring that the genes encoding the T3SS are expressed only in response to the appropriate combination of environmental and cellular cues. The second is to amplify SPI1 gene expression. To experimentally test these predictions, we rewired the SPI1 genetic circuit by changing its regulatory architecture. This enabled us to directly test our predictions regarding the function of the circuit by varying the strength and dynamics of the activating signal. Collectively, our experimental and computational results enable us to deconstruct this complex circuit and determine the role of its individual components in regulating SPI1 gene expression dynamics.

  10. Topology Engineering of Proteins in Vivo Using Genetically Encoded, Mechanically Interlocking SpyX Modules for Enhanced Stability

    Science.gov (United States)

    2017-01-01

    Recombinant proteins are traditionally limited to linear configuration. Herein, we report in vivo protein topology engineering using highly efficient, mechanically interlocking SpyX modules named AXB and BXA. SpyX modules are protein domains composed of p53dim (X), SpyTag (A), and SpyCatcher (B). The p53dim guides the intertwining of the two nascent protein chains followed by autocatalytic isopeptide bond formation between SpyTag and SpyCatcher to fulfill the interlocking, leading to a variety of backbone topologies. Direct expression of AXB or BXA produces protein catenanes with distinct ring sizes. Recombinant proteins containing SpyX modules are obtained either as mechanically interlocked obligate dimers if the protein of interest is fused to the N- or C-terminus of SpyX modules, or as star proteins if the protein is fused to both N- and C-termini. As examples, cellular syntheses of dimers of (GB1)2 (where GB1 stands for immunoglobulin-binding domain B1 of streptococcal protein G) and of four-arm elastin-like star proteins were demonstrated. Comparison of the catenation efficiencies in different constructs reveals that BXA is generally much more effective than AXB, which is rationalized by the arrangement of three domains in space. Mechanical interlocking induces considerable stability enhancement. Both AXB and BXA have a melting point ∼20 °C higher than the linear controls and the BXA catenane has a melting point ~2 °C higher than the cyclic control BX’A. Notably, four-arm elastin-like star proteins demonstrate remarkable tolerance against trypsin digestion. The SpyX modules provide a convenient and versatile approach to construct unconventional protein topologies via the “assembly-reaction” synergy, which opens a new horizon in protein science for stability enhancement and function reinforcement via topology engineering. PMID:28573210

  11. Development and applications of NMR (nuclear magnetic resonance) in low fields and zero field

    Energy Technology Data Exchange (ETDEWEB)

    Bielecki, A.

    1987-05-01

    This dissertation is about nuclear magnetic resonance (NMR) spectroscopy in the absence of applied magnetic fields. NMR is usually done in large magnetic fields, often as large as can be practically attained. The motivation for going the opposite way, toward zero field, is that for certain types of materials, particularly powdered or polycrystalline solids, the NMR spectra in zero field are easier to interpret than those obtained in high field. 92 refs., 60 figs., 1 tab.

  12. Ageing of Starch Based Systems as observed with FT-IR and Solid State NMR Spectroscopy

    NARCIS (Netherlands)

    Smits, A.L.M.; Ruhnau, F.C.; Vliegenthart, J.F.G.; Soest, van J.J.G.

    1998-01-01

    The retrogradation and physical ageing of model starch systems with respect to their glass transition temperatures Tg have been investigated by Fourier transform infrared spectroscopy and solid state NMR spectroscopy. Diffuse reflectance Fourier transform infrared (DRIFT) spectra demonstrate the com

  13. Ageing of starch based systems as observed with FT-IR and solid state NMR spectroscopy

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Smits, A.L.M.; Ruhnau, F.C.; Soest, J.J.G. van

    1998-01-01

    The retrogradation and physical ageing of model starch systems with respect to their glass transition temperatures Tg have been investigated by Fourier transform infrared Spectroscopy and solid state NMR spectroscopy. Diffuse reflectance Fourier transform infrared (DRIFT) spectra demonstrate the com

  14. The Application Based On SPI Software Calculation Module%基于SPI软件的计算应用

    Institute of Scientific and Technical Information of China (English)

    陆地

    2014-01-01

    This paper analyzes the basic functions of SPI software. The calculation module of SPI is introduced in detail. In view of the calculation module, application analyzes are made combined with actual project. This method helps designer to select instrument according to the SPI calculation report.%介绍了SPI软件的基本功能;对SPI的计算功能作了详细介绍,针对计算模块,结合实际项目进行了应用分析;有利于设计人员根据SPI计算模块进行仪表选型。

  15. PepsNMR for the 1H-NMR metabolomic data pre-processing

    OpenAIRE

    Martin, Manon; Legat, Benoît; Leenders, Justine; Vanwinsberghe, Julien; Rousseau, Réjane; Boulanger, Bruno; Eilers, Paul H. C.; De Tullio, Pascal; Govaerts, Bernadette

    2017-01-01

    In the analysis of complex biological samples, control over experimental design and data acquisition procedures cannot ensure alone well-conditioned 1H-NMR spectra with maximal information recovery for data analysis. A third major element affects the accuracy and robustness of the results: the data pre-processing/pre-treatment for which not enough attention is usually devoted, in particular in the metabolomic studies. The usual approach is to use proprietary software provided by the analytica...

  16. Spectroscopic approaches to resolving ambiguities of hyper-polarized NMR signals from different reaction cascades

    DEFF Research Database (Denmark)

    Jensen, Pernille Rose; Meier, Sebastian

    2016-01-01

    The influx of exogenous substrates into cellular reaction cascades on the seconds time scale is directly observable by NMR spectroscopy when using nuclear spin polarization enhancement. Conventional NMR assignment spectra for the identification of reaction intermediates are not applicable in thes...

  17. Structure elucidation of glycoprotein glycans and of polysaccharides by NMR spectroscopy

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Leeflang, B.R.; Faber, E.J.; Erbel, P.J.A.

    2000-01-01

    The applicability of 1H-NMR spectroscopy for the determination of the primary and tertiary structure of carbohydrate-containing molecules is demonstrated. For classes of known compounds the characterization can be based on chemical shifts observed in 1D NMR spectra with or without the aid of a compu

  18. Experimental Determination of pK[subscript a] Values by Use of NMR Chemical Shifts, Revisited

    Science.gov (United States)

    Gift, Alan D.; Stewart, Sarah M.; Bokashanga, Patrick Kwete

    2012-01-01

    This laboratory experiment, using proton NMR spectroscopy to determine the dissociation constant for heterocyclic bases, has been modified from a previously described experiment. A solution of a substituted pyridine is prepared using deuterium oxide (D[subscript 2]O) as the solvent. The pH of the solution is adjusted and proton NMR spectra are…

  19. Hypothesis: the sound of the individual metabolic phenotype? Acoustic detection of NMR experiments

    NARCIS (Netherlands)

    Cacciatore, S.; Saccenti, E.; Piccioli, M.

    2015-01-01

    We present here an innovative hypothesis and report preliminary evidence that the sound of NMR signals could provide an alternative to the current representation of the individual metabolic fingerprint and supply equally significant information. The NMR spectra of the urine samples provided by four

  20. BOOK REVIEW: NMR Imaging of Materials

    Science.gov (United States)

    Blümich, Bernhard

    2003-09-01

    spectroscopic methods to weight or filter the spin signals represents the core of the book. This is a subject where Blümich is deeply involved with substantial contributions. The chapter includes a lot of ideas to provide MR contrast between different regions based on their mobility, diffusion, spin couplings or NMR spectra. After describing NMR imaging methods for solids with broad lines, Blümich spends time on applications in the last two chapters of the book. This part is really fun to read. It underlines the effort to bring NMR into many kinds of manufacturing. Car tyres and high-voltage cables are just two such areas. Elastomeric materials, green-state ceramics and food science represent other interesting fields of applications. This part of the book represents a personal but nevertheless extensive compilation of modern applications. As a matter of course the MOUSE is presented, a portable permanent-magnet based NMR developed by Blümich and his co-workers. Thus the book is not only of interest to NMR spectroscopists but also to people in material science and chemical engineering. The bibliography and indexing are excellent and may serve as an attractive reference source for NMR spectroscopists. The book is the first on the subject and likely to become the standard text for NMR imaging of materials as the books by Abragam, Slicher and Ernst et al are for NMR spectroscopy. The purchase of this beautiful book for people dealing with NMR spectroscopy or medical MRI is highly recommended. Ralf Ludwig

  1. Assignments of 1H and 13C NMR Signals of Mogroside IVa

    Institute of Scientific and Technical Information of China (English)

    ZHANGJian-ye; YANGXiu-wei

    2003-01-01

    Aim To investigate the structure of mogroside IVa isolated from traditional Chinese medicine fructus momordicae [fruits of Siraitia grosvenori (Swingle) C. Jeffery] and summarize the NMR characteristics of the structure. Methods Cormnon extraction, separafion and purification methods were used. Various NMR techniques including 1H NMR,13C NMR, DEPT, 1H-1H COSY, HSQC, HMBC, NOESY and molecular model simulated by comtmter were used to elucidate the structure. Results 1H and 13C NMR signals of mogroside IVa were assigned, and spectroscopic basis was obtained for identification of such type of compounds. Conclusion 1D and 2D NMR techniques including 1H-1H COSY, HSQC, HMBC, NOESY spectra are powerful tools for structure analysis. The structure determined by NMR methods is identical with energy minimized conformation simulated by computer.

  2. A Spiking Neural Network Model of the Lateral Geniculate Nucleus on the SpiNNaker Machine

    Directory of Open Access Journals (Sweden)

    Basabdatta Sen-Bhattacharya

    2017-08-01

    Full Text Available We present a spiking neural network model of the thalamic Lateral Geniculate Nucleus (LGN developed on SpiNNaker, which is a state-of-the-art digital neuromorphic hardware built with very-low-power ARM processors. The parallel, event-based data processing in SpiNNaker makes it viable for building massively parallel neuro-computational frameworks. The LGN model has 140 neurons representing a “basic building block” for larger modular architectures. The motivation of this work is to simulate biologically plausible LGN dynamics on SpiNNaker. Synaptic layout of the model is consistent with biology. The model response is validated with existing literature reporting entrainment in steady state visually evoked potentials (SSVEP—brain oscillations corresponding to periodic visual stimuli recorded via electroencephalography (EEG. Periodic stimulus to the model is provided by: a synthetic spike-train with inter-spike-intervals in the range 10–50 Hz at a resolution of 1 Hz; and spike-train output from a state-of-the-art electronic retina subjected to a light emitting diode flashing at 10, 20, and 40 Hz, simulating real-world visual stimulus to the model. The resolution of simulation is 0.1 ms to ensure solution accuracy for the underlying differential equations defining Izhikevichs neuron model. Under this constraint, 1 s of model simulation time is executed in 10 s real time on SpiNNaker; this is because simulations on SpiNNaker work in real time for time-steps dt ⩾ 1 ms. The model output shows entrainment with both sets of input and contains harmonic components of the fundamental frequency. However, suppressing the feed-forward inhibition in the circuit produces subharmonics within the gamma band (>30 Hz implying a reduced information transmission fidelity. These model predictions agree with recent lumped-parameter computational model-based predictions, using conventional computers. Scalability of the framework is demonstrated by a multi

  3. Some nitrogen-14 NMR studies in solids

    Energy Technology Data Exchange (ETDEWEB)

    Pratum, T.K.

    1983-11-01

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

  4. NMR and the local structure of relaxors

    Directory of Open Access Journals (Sweden)

    Blinc R.

    2002-01-01

    Full Text Available The relaxor transition in cubic perovskite relaxors (PMN, PSN and PST and tungsten bronze relaxor (SBN has been studied by NMR. The observed spectra are composed of a narrow -1/2 « 1/2 central transition superimposed on a broad background due to satellite transitions. The chemical heterogeneity, responsible for relaxor properties, is reflected here in the structure of the central transition part. The latter is composed of two components, one due to ordered and the other due to disordered regions. Despite of the fact that the macroscopic symmetry does not change when relaxor transition occurs, a non-zero quadruple coupling constant determined from NMR clearly demonstrates the broken local symmetry.

  5. Teaching NMR Using Online Textbooks

    Directory of Open Access Journals (Sweden)

    Joseph P. Hornak

    1999-12-01

    Full Text Available Nuclear magnetic resonance (NMR spectroscopy has almost become an essential analytical tool for the chemist. High-resolution one- and multi-dimensional NMR, timedomain NMR, and NMR microscopy are but a few of the NMR techniques at a chemist's disposal to determine chemical structure and dynamics. Consequently, even small chemistry departments are finding it necessary to provide students with NMR training and experience in at least some of these techniques. The hands-on experience is readily provided with access to state-of-the-art commercial spectrometers. Instruction in the principles of NMR is more difficult to achieve as most instructors try to teach NMR using single organic or analytical chemistry book chapters with static figures. This paper describes an online textbook on NMR spectroscopy called The Basics of NMR (http://www.cis.rit.edu/htbooks/nmr/ suitable for use in teaching the principles of NMR spectroscopy. The book utilizes hypertext and animations to present the principles of NMR spectroscopy. The book can be used as a textbook associated with a lecture or as a stand-alone teaching tool. Conference participants are encouraged to review the textbook and evaluate its suitability for us in teaching NMR spectroscopy to undergraduate chemistry majors.

  6. The design and implementation of configurable SPI master interface based on FPGA%一种基于FPGA的可配置SPI Master接口设计实现

    Institute of Scientific and Technical Information of China (English)

    李大江; 崔建明

    2010-01-01

    介绍一种基于FPGA的SPI Master Interface设计.依据SPI同步串行接12的通信协议,设计一个可配置的、高度灵活的SPI Master模块,以满足正常、异常及强度测试要求.利用Verilog语言实现SPI接12的设计原理和编程思想.

  7. NMR observation of rotory conformers in flexible-chain polymers

    Energy Technology Data Exchange (ETDEWEB)

    Sadykov, R.K.; Makhiyanov, N.; Kurbatov, V.A.; Savel' ev, V.S.; Kirpichnikov, P.A.

    1987-08-01

    The authors conduct a comprehensive line analysis of the NMR spectra of a number of polymers, including cis-1,4-polyisoprenes, cis-1-4-polybutadiene, polyisobutylene, and polyethylene, in a deuterated benzene solvent. Data are given on hyperfine structure and spin-spin coupling constants along with conformational behavior and a negative Overhauser effect observed in the isomers.

  8. Extraction of alkaloids for NMR-based profiling

    DEFF Research Database (Denmark)

    Yilmaz, Ali; Nyberg, Nils; Jaroszewski, Jerzy W.

    2012-01-01

    A museum collection of Cinchona cortex samples (n = 117), from the period 1850–1950, were extracted with a mixture of chloroform-d1, methanol-d4, water-d2, and perchloric acid in the ratios 5:5:1:1. The extracts were directly analyzed using 1H NMR spectroscopy (600 MHz) and the spectra evaluated ...

  9. Non-uniform sampling of NMR relaxation data

    DEFF Research Database (Denmark)

    Schwarz-Linnet, Troels; Teilum, Kaare

    2016-01-01

    The use of non-uniform sampling of NMR spectra may give significant reductions in the data acquisition time. For quantitative experiments such as the measurement of spin relaxation rates, non-uniform sampling is however not widely used as inaccuracies in peak intensities may lead to errors...

  10. NMR and NQR study of the thermodynamically stable quasicrystals

    Energy Technology Data Exchange (ETDEWEB)

    Shastri, Ananda [Iowa State Univ., Ames, IA (United States)

    1995-02-10

    27Al and 61,65Cu NMR measurements are reported for powder samples of stable AlCuFe and AlCuRu icosahedral quasicrystals and their crystalline approximants, and for a AlPdMn single grain quasicrystal. Furthermore, 27Al NQR spectra at 4.2 K have been observed in the AlCuFe and AlCuRu samples. From the quadrupole perturbed NMR spectra at different magnetic fields, and from the zero field NQR spectra, a wide distribution of local electric field gradient (EFG) tensor components and principal axis system orientations was found at the Al site. A model EFG calculation based on a 1/1 AlCuFe approximant was successful in explaining the observed NQR spectra. It is concluded that the average local gradient is largely determined by the p-electron wave function at the Al site, while the width of the distribution is due to the lattice contribution to the EFG. Comparison of 63Cu NMR with 27Al NMR shows that the EFG distribution at the two sites is similar, but that the electronic contribution to the EFG is considerably smaller at the Cu site, in agreement with a more s-type wave function of the conduction electrons.

  11. Genetically Encoded Spy Peptide Fusion System to Detect Plasma Membrane-Localized Proteins In Vivo.

    Science.gov (United States)

    Bedbrook, Claire N; Kato, Mihoko; Ravindra Kumar, Sripriya; Lakshmanan, Anupama; Nath, Ravi D; Sun, Fei; Sternberg, Paul W; Arnold, Frances H; Gradinaru, Viviana

    2015-08-20

    Membrane proteins are the main gatekeepers of cellular state, especially in neurons, serving either to maintain homeostasis or instruct response to synaptic input or other external signals. Visualization of membrane protein localization and trafficking in live cells facilitates understanding the molecular basis of cellular dynamics. We describe here a method for specifically labeling the plasma membrane-localized fraction of heterologous membrane protein expression using channelrhodopsins as a case study. We show that the genetically encoded, covalent binding SpyTag and SpyCatcher pair from the Streptococcus pyogenes fibronectin-binding protein FbaB can selectively label membrane-localized proteins in living cells in culture and in vivo in Caenorhabditis elegans. The SpyTag/SpyCatcher covalent labeling method is highly specific, modular, and stable in living cells. We have used the binding pair to develop a channelrhodopsin membrane localization assay that is amenable to high-throughput screening for opsin discovery and engineering.

  12. The papain inhibitor (SPI) of Streptomyces mobaraensis inhibits bacterial cysteine proteases and is an antagonist of bacterial growth

    NARCIS (Netherlands)

    S. Zindel (Stephan); W.E. Kaman (Wendy); S. Fröls (Sabrina); F. Pfeifer (Felicitas); A. Peters (Annette); J.P. Hays (John); H.-L. Fuchsbauer (Hans-Lothar)

    2013-01-01

    textabstractA novel papain inhibitory protein (SPI) from Streptomyces mobaraensis was studied to measure its inhibitory effect on bacterial cysteine protease activity (Staphylococcus aureus SspB) and culture supernatants (Porphyromonas gingivalis, Bacillus anthracis). Further, growth of Bacillus ant

  13. Optical analogue of 2D heteronuclear double-quantum NMR

    CERN Document Server

    Tollerud, Jonathan

    2016-01-01

    Heteronuclear multi-quantum spectroscopy is a powerful part of the NMR toolbox, commonly used to identify specific sequences of atoms in complex pulse sequences designed to determine the structure of complex molecules, including proteins. Optical coherent multidimensional spectroscopy (CMDS) is analogous to multidimensional NMR and many of the techniques of NMR have been adapted for application in the optical regime. This has been highly successful, with CMDS being used to understand energy transfer in photosynthesis and many body effects in semiconductor nanostructures amongst many other scientific breakthroughs. Experimental challenges have, however, prevented the translation of heteronuclear multi-quantum NMR to the optical regime, where capabilities to isolate signals in otherwise congested spectra, reduce acquisition times and enable more incisive probes of multi-particle correlations and complex electronic systems would have great benefit. Here we utilise a diffraction based pulseshaper to impose the tw...

  14. Observation of $\\Lambda^+_{c}\\to nK^0_S\\pi^+$

    CERN Document Server

    Ablikim, M; Ahmed, S; Ai, X C; Albayrak, O; Albrecht, M; Ambrose, D J; Amoroso, A; An, F F; An, Q; Bai, J Z; Bakina, O; Ferroli, R Baldini; Ban, Y; Bennett, D W; Bennett, J V; Berger, N; Bertani, M; Bettoni, D; Bian, J M; Bianchi, F; Boger, E; Boyko, I; Briere, R A; Cai, H; Cai, X; Cakir, O; Calcaterra, A; Cao, G F; Cetin, S A; Chang, J F; Chelkov, G; Chen, G; Chen, H S; Chen, J C; Chen, M L; Chen, S; Chen, S J; Chen, X; Chen, X R; Chen, Y B; Chu, X K; Cibinetto, G; Dai, H L; Dai, J P; Dbeyssi, A; Dedovich, D; Deng, Z Y; Denig, A; Denysenko, I; Destefanis, M; De Mori, F; Ding, Y; Dong, C; Dong, J; Dong, L Y; Dong, M Y; Dou, Z L; Du, S X; Duan, P F; Fan, J Z; Fang, J; Fang, S S; Fang, X; Fang, Y; Farinelli, R; Fava, L; Feldbauer, F; Felici, G; Feng, C Q; Fioravanti, E; Fritsch, M; Fu, C D; Gao, Q; Gao, X L; Gao, Y; Gao, Z; Garzia, I; Goetzen, K; Gong, L; Gong, W X; Gradl, W; Greco, M; Gu, M H; Gu, Y T; Guan, Y H; Guo, A Q; Guo, L B; Guo, R P; Guo, Y; Guo, Y P; Haddadi, Z; Hafner, A; Han, S; Hao, X Q; Harris, F A; He, K L; Heinsius, F H; Held, T; Heng, Y K; Holtmann, T; Hou, Z L; Hu, C; Hu, H M; Hu, J F; Hu, T; Hu, Y; Huang, G S; Huang, J S; Huang, X T; Huang, X Z; Huang, Z L; Hussain, T; Andersson, W Ikegami; Ji, Q; Ji, Q P; Ji, X B; Ji, X L; Jiang, L W; Jiang, X S; Jiang, X Y; Jiao, J B; Jiao, Z; Jin, D P; Jin, S; Johansson, T; Julin, A; Kalantar-Nayestanaki, N; Kang, X L; Kang, X S; Kavatsyuk, M; Ke, B C; Kiese, P; Kliemt, R; Kloss, B; Kolcu, O B; Kopf, B; Kornicer, M; Kupsc, A; Kühn, W; Lange, J S; Lara, M; Larin, P; Lavezzi, L; Leithoff, H; Leng, C; Li, C; Li, Cheng; Li, D M; Li, F; Li, F Y; Li, G; Li, H B; Li, H J; Li, J C; Li, Jin; Li, K; Li, K; Li, Lei; Li, P R; Li, Q Y; Li, T; Li, W D; Li, W G; Li, X L; Li, X N; Li, X Q; Li, Y B; Li, Z B; Liang, H; Liang, Y F; Liang, Y T; Liao, G R; Lin, D X; Liu, B; Liu, B J; Liu, C X; Liu, D; Liu, F H; Liu, Fang; Liu, Feng; Liu, H B; Liu, H H; Liu, H H; Liu, H M; Liu, J; Liu, J B; Liu, J P; Liu, J Y; Liu, K; Liu, K Y; Liu, L D; Liu, P L; Liu, Q; Liu, Q J; Liu, S B; Liu, X; Liu, Y B; Liu, Y Y; Liu, Z A; Liu, Z Q; Loehner, H; Lou, X C; Lu, H J; Lu, J G; Lu, Y; Lu, Y P; Luo, C L; Luo, M X; Luo, T; Luo, X L; Lyu, X R; Ma, F C; Ma, H L; Ma, L L; Ma, M M; Ma, Q M; Ma, T; Ma, X N; Ma, X Y; Ma, Y M; Maas, F E; Maggiora, M; Malik, Q A; Mao, Y J; Mao, Z P; Marcello, S; Messchendorp, J G; Mezzadri, G; Min, J; Min, T J; Mitchell, R E; Mo, X H; Mo, Y J; Morales, C Morales; Muchnoi, N Yu; Muramatsu, H; Musiol, P; Nefedov, Y; Nerling, F; Nikolaev, I B; Ning, Z; Nisar, S; Niu, S L; Niu, X Y; Olsen, S L; Ouyang, Q; Pacetti, S; Pan, Y; Patteri, P; Pelizaeus, M; Peng, H P; Peters, K; Pettersson, J; Ping, J L; Ping, R G; Poling, R; Prasad, V; Qi, H R; Qi, M; Qian, S; Qiao, C F; Qin, L Q; Qin, N; Qin, X S; Qin, Z H; Qiu, J F; Rashid, K H; Redmer, C F; Ripka, M; Rong, G; Rosner, Ch; Ruan, X D; Sarantsev, A; Savrié, M; Schnier, C; Schoenning, K; Shan, W; Shao, M; Shen, C P; Shen, P X; Shen, X Y; Sheng, H Y; Song, W M; Song, X Y; Sosio, S; Spataro, S; Sun, G X; Sun, J F; Sun, S S; Sun, X H; Sun, Y J; Sun, Y Z; Sun, Z J; Sun, Z T; Tang, C J; Tang, X; Tapan, I; Thorndike, E H; Tiemens, M; Uman, I; Varner, G S; Wang, B; Wang, B L; Wang, D; Wang, D Y; Wang, K; Wang, L L; Wang, L S; Wang, M; Wang, P; Wang, P L; Wang, W; Wang, W P; Wang, X F; Wang, Y; Wang, Y D; Wang, Y F; Wang, Y Q; Wang, Z; Wang, Z G; Wang, Z H; Wang, Z Y; Weber, T; Wei, D H; Weidenkaff, P; Wen, S P; Wiedner, U; Wolke, M; Wu, L H; Wu, L J; Wu, Z; Xia, L; Xia, L G; Xia, Y; Xiao, D; Xiao, H; Xiao, Z J; Xie, Y G; Xie, Y H; Xiu, Q L; Xu, G F; Xu, J J; Xu, L; Xu, Q J; Xu, Q N; Xu, X P; Yan, L; Yan, W B; Yan, W C; Yan, Y H; Yang, H J; Yang, H X; Yang, L; Yang, Y X; Ye, M; Ye, M H; Yin, J H; You, Z Y; Yu, B X; Yu, C X; Yu, J S; Yuan, C Z; Yuan, Y; Yuncu, A; Zafar, A A; Zeng, Y; Zeng, Z; Zhang, B X; Zhang, B Y; Zhang, C C; Zhang, D H; Zhang, H H; Zhang, H Y; Zhang, J; Zhang, J J; Zhang, J L; Zhang, J Q; Zhang, J W; Zhang, J Y; Zhang, J Z; Zhang, K; Zhang, L; Zhang, S Q; Zhang, X Y; Zhang, Y; Zhang, Y H; Zhang, Y N; Zhang, Y T; Zhang, Yu; Zhang, Z H; Zhang, Z P; Zhang, Z Y; Zhao, G; Zhao, J W; Zhao, J Y; Zhao, J Z; Zhao, Lei; Zhao, Ling; Zhao, M G; Zhao, Q; Zhao, Q W; Zhao, S J; Zhao, T C; Zhao, Y B; Zhao, Z G; Zhemchugov, A; Zheng, B; Zheng, J P; Zheng, W J; Zheng, Y H; Zhong, B; Zhou, L; Zhou, X; Zhou, X K; Zhou, X R; Zhou, X Y; Zhu, K; Zhu, K J; Zhu, S; Zhu, S H; Zhu, X L; Zhu, Y C; Zhu, Y S; Zhu, Z A; Zhuang, J; Zotti, L; Zou, B S; Zou, J H

    2016-01-01

    We report the first direct measurement of decays of the $\\Lambda^+_c$ baryon involving the neutron. The analysis is performed using 567 pb$^{-1}$ of $e^+e^-$ collision data collected at $\\sqrt{s}=4.599$ GeV with the BESIII detector at the BEPCII collider. We observe the decay $\\Lambda^+_{c}\\rightarrow n K^0_S\\pi^+$ and measure the absolute branching fraction to be $\\mathcal{B}({\\Lambda^+_{c}\\rightarrow n K^0_S\\pi^+})=(1.82\\pm0.23({\\rm stat})\\pm0.11({\\rm syst}))\\%$. A comparison to $\\mathcal{B}({\\Lambda^+_{c}\\rightarrow p(\\bar{K}\\pi)^0})$ provides an important test of isospin symmetry and final state interactions.

  15. SPY: A new scission point model based on microscopic ingredients to predict fission fragments properties

    Science.gov (United States)

    Lemaître, J.-F.; Dubray, N.; Hilaire, S.; Panebianco, S.; Sida, J.-L.

    2013-12-01

    Our purpose is to determine fission fragments characteristics in a framework of a scission point model named SPY for Scission Point Yields. This approach can be considered as a theoretical laboratory to study fission mechanism since it gives access to the correlation between the fragments properties and their nuclear structure, such as shell correction, pairing, collective degrees of freedom, odd-even effects. Which ones are dominant in final state? What is the impact of compound nucleus structure? The SPY model consists in a statistical description of the fission process at the scission point where fragments are completely formed and well separated with fixed properties. The most important property of the model relies on the nuclear structure of the fragments which is derived from full quantum microscopic calculations. This approach allows computing the fission final state of extremely exotic nuclei which are inaccessible by most of the fission model available on the market.

  16. SPY: A new scission point model based on microscopic ingredients to predict fission fragments properties

    Directory of Open Access Journals (Sweden)

    Lemaître J.-F.

    2013-12-01

    Full Text Available Our purpose is to determine fission fragments characteristics in a framework of a scission point model named SPY for Scission Point Yields. This approach can be considered as a theoretical laboratory to study fission mechanism since it gives access to the correlation between the fragments properties and their nuclear structure, such as shell correction, pairing, collective degrees of freedom, odd-even effects. Which ones are dominant in final state? What is the impact of compound nucleus structure? The SPY model consists in a statistical description of the fission process at the scission point where fragments are completely formed and well separated with fixed properties. The most important property of the model relies on the nuclear structure of the fragments which is derived from full quantum microscopic calculations. This approach allows computing the fission final state of extremely exotic nuclei which are inaccessible by most of the fission model available on the market.

  17. Splitting parameter yield (SPY): A program for semiautomatic analysis of shear-wave splitting

    Science.gov (United States)

    Zaccarelli, Lucia; Bianco, Francesca; Zaccarelli, Riccardo

    2012-03-01

    SPY is a Matlab algorithm that analyzes seismic waveforms in a semiautomatic way, providing estimates of the two observables of the anisotropy: the shear-wave splitting parameters. We chose to exploit those computational processes that require less intervention by the user, gaining objectivity and reliability as a result. The algorithm joins the covariance matrix and the cross-correlation techniques, and all the computation steps are interspersed by several automatic checks intended to verify the reliability of the yields. The resulting semiautomation generates two new advantages in the field of anisotropy studies: handling a huge amount of data at the same time, and comparing different yields. From this perspective, SPY has been developed in the Matlab environment, which is widespread, versatile, and user-friendly. Our intention is to provide the scientific community with a new monitoring tool for tracking the temporal variations of the crustal stress field.

  18. INTEGRAL/SPI Observations of Electron-Positron Annihilation Radiation from our Galaxy

    Science.gov (United States)

    Teegarden, B. J.; Watanabe, K.; Knoedlseder, J.; Jean, P.; Lonjou, V.; Weidenspointner, G.; Skinner, G.; von Ballmoos, P.; Vedrenne, G.; Roques, J.-P.; Schanne, S.; Schoenfelder, V.

    2004-12-01

    The spectrometer on INTEGRAL (SPI) is a coded-aperture gamma-ray telescope with moderate angular resolution (3 deg) and superior energy resolution (2 keV at 511 keV). One of it's principal science goals is the detailed study of 511 keV electron-positron annihilation from our Galaxy. The origin of this radiation remains a mystery, however current morphological studies suggest an older stellar population. There has also been recent speculation on the possibility of the existence of light (< 100 MeV) dark matter particles whose annihilation or decay could produce the observed 511 keV emission. In this paper we summarize the current results from SPI, compare them with previous results and discuss their implication on possible models for the production of the annihilation radiation. INTEGRAL is a project of ESA. This work was supported by NASA and CNES.

  19. Observation of the decay $B_c^+ \\to \\psi(2S)\\pi^+$

    CERN Document Server

    Aaij, R; Adeva, B; Adinolfi, M; Adrover, C; Affolder, A; Ajaltouni, Z; Albrecht, J; Alessio, F; Alexander, M; Ali, S; Alkhazov, G; Alvarez Cartelle, P; Alves Jr, A A; Amato, S; Amerio, S; Amhis, Y; Anderlini, L; Anderson, J; Andreassen, R; Appleby, R B; Aquines Gutierrez, O; Archilli, F; Artamonov, A; Artuso, M; Aslanides, E; Auriemma, G; Bachmann, S; Back, J J; Baesso, C; Balagura, V; Baldini, W; Barlow, R J; Barschel, C; Barsuk, S; Barter, W; Bauer, Th; Bay, A; Beddow, J; Bedeschi, F; Bediaga, I; Belogurov, S; Belous, K; Belyaev, I; Ben-Haim, E; Benayoun, M; Bencivenni, G; Benson, S; Benton, J; Berezhnoy, A; Bernet, R; Bettler, M -O; van Beuzekom, M; Bien, A; Bifani, S; Bird, T; Bizzeti, A; Bjørnstad, P M; Blake, T; Blanc, F; Blouw, J; Blusk, S; Bocci, V; Bondar, A; Bondar, N; Bonivento, W; Borghi, S; Borgia, A; Bowcock, T J V; Bowen, E; Bozzi, C; Brambach, T; van den Brand, J; Bressieux, J; Brett, D; Britsch, M; Britton, T; Brook, N H; Brown, H; Burducea, I; Bursche, A; Busetto, G; Buytaert, J; Cadeddu, S; Callot, O; Calvi, M; Calvo Gomez, M; Camboni, A; Campana, P; Carbone, A; Carboni, G; Cardinale, R; Cardini, A; Carranza-Mejia, H; Carson, L; Carvalho Akiba, K; Casse, G; Cattaneo, M; Cauet, Ch; Charles, M; Charpentier, Ph; Chen, P; Chiapolini, N; Chrzaszcz, M; Ciba, K; Cid Vidal, X; Ciezarek, G; Clarke, P E L; Clemencic, M; Cliff, H V; Closier, J; Coca, C; Coco, V; Cogan, J; Cogneras, E; Collins, P; Comerma-Montells, A; Contu, A; Cook, A; Coombes, M; Coquereau, S; Corti, G; Couturier, B; Cowan, G A; Craik, D; Cunliffe, S; Currie, R; D'Ambrosio, C; David, P; David, P N Y; De Bonis, I; De Bruyn, K; De Capua, S; De Cian, M; De Miranda, J M; De Oyanguren Campos, M; De Paula, L; De Silva, W; De Simone, P; Decamp, D; Deckenhoff, M; Del Buono, L; Derkach, D; Deschamps, O; Dettori, F; Di Canto, A; Dijkstra, H; Dogaru, M; Donleavy, S; Dordei, F; Dosil Suárez, A; Dossett, D; Dovbnya, A; Dupertuis, F; Dzhelyadin, R; Dziurda, A; Dzyuba, A; Easo, S; Egede, U; Egorychev, V; Eidelman, S; van Eijk, D; Eisenhardt, S; Eitschberger, U; Ekelhof, R; Eklund, L; El Rifai, I; Elsasser, Ch; Elsby, D; Falabella, A; Färber, C; Fardell, G; Farinelli, C; Farry, S; Fave, V; Ferguson, D; Fernandez Albor, V; Ferreira Rodrigues, F; Ferro-Luzzi, M; Filippov, S; Fitzpatrick, C; Fontana, M; Fontanelli, F; Forty, R; Francisco, O; Frank, M; Frei, C; Frosini, M; Furcas, S; Furfaro, E; Gallas Torreira, A; Galli, D; Gandelman, M; Gandini, P; Gao, Y; Garofoli, J; Garosi, P; Garra Tico, J; Garrido, L; Gaspar, C; Gauld, R; Gersabeck, E; Gersabeck, M; Gershon, T; Ghez, Ph; Gibson, V; Gligorov, V V; Göbel, C; Golubkov, D; Golutvin, A; Gomes, A; Gordon, H; Grabalosa Gándara, M; Graciani Diaz, R; Granado Cardoso, L A; Graugés, E; Graziani, G; Grecu, A; Greening, E; Gregson, S; Grünberg, O; Gui, B; Gushchin, E; Guz, Yu; Gys, T; Hadjivasiliou, C; Haefeli, G; Haen, C; Haines, S C; Hall, S; Hampson, T; Hansmann-Menzemer, S; Harnew, N; Harnew, S T; Harrison, J; Hartmann, T; He, J; Heijne, V; Hennessy, K; Henrard, P; Hernando Morata, J A; van Herwijnen, E; Hicks, E; Hill, D; Hoballah, M; Hombach, C; Hopchev, P; Hulsbergen, W; Hunt, P; Huse, T; Hussain, N; Hutchcroft, D; Hynds, D; Iakovenko, V; Idzik, M; Ilten, P; Jacobsson, R; Jaeger, A; Jans, E; Jaton, P; Jing, F; John, M; Johnson, D; Jones, C R; Jost, B; Kaballo, M; Kandybei, S; Karacson, M; Karbach, T M; Kenyon, I R; Kerzel, U; Ketel, T; Keune, A; Khanji, B; Kochebina, O; Komarov, I; Koopman, R F; Koppenburg, P; Korolev, M; Kozlinskiy, A; Kravchuk, L; Kreplin, K; Kreps, M; Krocker, G; Krokovny, P; Kruse, F; Kucharczyk, M; Kudryavtsev, V; Kvaratskheliya, T; La Thi, V N; Lacarrere, D; Lafferty, G; Lai, A; Lambert, D; Lambert, R W; Lanciotti, E; Lanfranchi, G; Langenbruch, C; Latham, T; Lazzeroni, C; Le Gac, R; van Leerdam, J; Lees, J -P; Lefèvre, R; Leflat, A; Lefrançois, J; Leo, S; Leroy, O; Leverington, B; Li, Y; Li Gioi, L; Liles, M; Lindner, R; Linn, C; Liu, B; Liu, G; von Loeben, J; Lohn, S; Lopes, J H; Lopez Asamar, E; Lopez-March, N; Lu, H; Lucchesi, D; Luisier, J; Luo, H; Machefert, F; Machikhiliyan, I V; Maciuc, F; Maev, O; Malde, S; Manca, G; Mancinelli, G; Marconi, U; Märki, R; Marks, J; Martellotti, G; Martens, A; Martin, L; Martín Sánchez, A; Martinelli, M; Martinez Santos, D; Martins Tostes, D; Massafferri, A; Matev, R; Mathe, Z; Matteuzzi, C; Maurice, E; Mazurov, A; McCarthy, J; McNulty, R; Mcnab, A; Meadows, B; Meier, F; Meissner, M; Merk, M; Milanes, D A; Minard, M -N; Molina Rodriguez, J; Monteil, S; Moran, D; Morawski, P; Morello, M J; Mountain, R; Mous, I; Muheim, F; Müller, K; Muresan, R; Muryn, B; Muster, B; Naik, P; Nakada, T; Nandakumar, R; Nasteva, I; Needham, M; Neufeld, N; Nguyen, A D; Nguyen, T D; Nguyen-Mau, C; Nicol, M; Niess, V; Niet, R; Nikitin, N; Nikodem, T; Nomerotski, A; Novoselov, A; Oblakowska-Mucha, A; Obraztsov, V; Oggero, S; Ogilvy, S; Okhrimenko, O; Oldeman, R; Orlandea, M; Otalora Goicochea, J M; Owen, P; Pal, B K; Palano, A; Palutan, M; Panman, J; Papanestis, A; Pappagallo, M; Parkes, C; Parkinson, C J; Passaleva, G; Patel, G D; Patel, M; Patrick, G N; Patrignani, C; Pavel-Nicorescu, C; Pazos Alvarez, A; Pellegrino, A; Penso, G; Pepe Altarelli, M; Perazzini, S; Perego, D L; Perez Trigo, E; Pérez-Calero Yzquierdo, A; Perret, P; Perrin-Terrin, M; Pessina, G; Petridis, K; Petrolini, A; Phan, A; Picatoste Olloqui, E; Pietrzyk, B; Pilař, T; Pinci, D; Playfer, S; Plo Casasus, M; Polci, F; Polok, G; Poluektov, A; Polycarpo, E; Popov, D; Popovici, B; Potterat, C; Powell, A; Prisciandaro, J; Pugatch, V; Puig Navarro, A; Punzi, G; Qian, W; Rademacker, J H; Rakotomiaramanana, B; Rangel, M S; Raniuk, I; Rauschmayr, N; Raven, G; Redford, S; Reid, M M; dos Reis, A C; Ricciardi, S; Richards, A; Rinnert, K; Rives Molina, V; Roa Romero, D A; Robbe, P; Rodrigues, E; Rodriguez Perez, P; Roiser, S; Romanovsky, V; Romero Vidal, A; Rouvinet, J; Ruf, T; Ruffini, F; Ruiz, H; Ruiz Valls, P; Sabatino, G; Saborido Silva, J J; Sagidova, N; Sail, P; Saitta, B; Salzmann, C; Sanmartin Sedes, B; Sannino, M; Santacesaria, R; Santamarina Rios, C; Santovetti, E; Sapunov, M; Sarti, A; Satriano, C; Satta, A; Savrie, M; Savrina, D; Schaack, P; Schiller, M; Schindler, H; Schlupp, M; Schmelling, M; Schmidt, B; Schneider, O; Schopper, A; Schune, M -H; Schwemmer, R; Sciascia, B; Sciubba, A; Seco, M; Semennikov, A; Senderowska, K; Sepp, I; Serra, N; Serrano, J; Seyfert, P; Shapkin, M; Shapoval, I; Shatalov, P; Shcheglov, Y; Shears, T; Shekhtman, L; Shevchenko, O; Shevchenko, V; Shires, A; Silva Coutinho, R; Skwarnicki, T; Smith, N A; Smith, E; Smith, M; Sokoloff, M D; Soler, F J P; Soomro, F; Souza, D; Souza De Paula, B; Spaan, B; Sparkes, A; Spradlin, P; Stagni, F; Stahl, S; Steinkamp, O; Stoica, S; Stone, S; Storaci, B; Straticiuc, M; Straumann, U; Subbiah, V K; Swientek, S; Syropoulos, V; Szczekowski, M; Szczypka, P; Szumlak, T; T'Jampens, S; Teklishyn, M; Teodorescu, E; Teubert, F; Thomas, C; Thomas, E; van Tilburg, J; Tisserand, V; Tobin, M; Tolk, S; Tonelli, D; Topp-Joergensen, S; Torr, N; Tournefier, E; Tourneur, S; Tran, M T; Tresch, M; Tsaregorodtsev, A; Tsopelas, P; Tuning, N; Ubeda Garcia, M; Ukleja, A; Urner, D; Uwer, U; Vagnoni, V; Valenti, G; Vazquez Gomez, R; Vazquez Regueiro, P; Vecchi, S; Velthuis, J J; Veltri, M; Veneziano, G; Vesterinen, M; Viaud, B; Vieira, D; Vilasis-Cardona, X; Vollhardt, A; Volyanskyy, D; Voong, D; Vorobyev, A; Vorobyev, V; Voß, C; Voss, H; Waldi, R; Wallace, R; Wandernoth, S; Wang, J; Ward, D R; Watson, N K; Webber, A D; Websdale, D; Whitehead, M; Wicht, J; Wiechczynski, J; Wiedner, D; Wiggers, L; Wilkinson, G; Williams, M P; Williams, M; Wilson, F F; Wishahi, J; Witek, M; Wotton, S A; Wright, S; Wu, S; Wyllie, K; Xie, Y; Xing, F; Xing, Z; Yang, Z; Young, R; Yuan, X; Yushchenko, O; Zangoli, M; Zavertyaev, M; Zhang, F; Zhang, L; Zhang, W C; Zhang, Y; Zhelezov, A; Zhokhov, A; Zhong, L; Zvyagin, A

    2013-01-01

    The decay $B_c^+ \\to \\psi(2S)\\pi^+$ with $\\psi(2S) \\to \\mu^+\\mu^-$ is observed with a significance of $5.2\\,\\sigma$ using $pp$ collision data corresponding to an integrated luminosity of 1.0 $fb^{-1}$ collected by the LHCb experiment. The branching fraction of $B_c^+ \\to \\psi(2S)\\pi^+$ decays relative to that of the $B_c^+ \\to J/\\psi\\pi^+$ mode is measured to be \\begin{equation*} \\frac{\\mathcal{B}(B_c^+ \\to \\psi(2S)\\pi^+)}{\\mathcal{B}(B_c^+ \\to J/\\psi\\pi^+)} = 0.250 \\pm 0.068 \\,\\text{stat} \\pm 0.014 \\,\\text{\\syst} \\pm 0.006 \\,(\\mathcal{B}). \\end{equation*} The last term is the uncertainty on the ratio $\\mathcal{B}(\\psi(2S) \\to \\mu^+\\mu^-)/\\mathcal{B}(J/\\psi \\to \\mu^+\\mu^-)$.

  20. A high EMS daisy-chain SPI interface for battery monitor system

    Science.gov (United States)

    Zhang, Qidong; Yang, Yintang; Chai, Changchun

    2017-03-01

    A high EMS current-mode SPI interface for battery monitor IC (BMIC) is presented to form a daisychain bus configuration for the cascaded BMICs and the communication between the MCU and master BMIC. Based on analog and digital mixed filtering technique, the proposed daisy-chain can avoid the isolated communication issue in electromagnetic interference environment, and reduce the extensively required I/O ports of MCU, at the same time reduce the system cost. The proposed daisy-chain interface was introduced in a 6-ch battery monitor IC which was fabricated with 0.35 μm 30 V BCD process. The measurement result shows that the presented daisy-chain SPI interface achieves better EMS performance with different EMI injection while just consuming a total operation current up to 1 mA. Project supported by the National Natural Science Foundation of China (No. 61334003).

  1. Reactor Neutrino Spectra

    OpenAIRE

    Hayes, A. C.; Vogel, Petr

    2016-01-01

    We present a review of the antineutrino spectra emitted from reactors. Knowledge of these spectra and their associated uncertainties is crucial for neutrino oscillation studies. The spectra used to date have been determined either by converting measured electron spectra to antineutrino spectra or by summing over all of the thousands of transitions that make up the spectra, using modern databases as input. The uncertainties in the subdominant corrections to β-decay plague both methods, and we ...

  2. Amide-Exchange-Rate-Edited NMR (AERE-NMR) Experiment:A Novel Method for Resolving Overlapping Resonances

    Institute of Scientific and Technical Information of China (English)

    LIU Xue-Hui; LIN Dong-Hai

    2007-01-01

    This paper describes an amide-exchange-rate-edited (AERE) NMR method that can effectively alleviate the problem of resonance overlap for proteins and peptides. This method exploits the diversity of amide proton exchange rates and consists of two complementary experiments: (1) SEA (solvent exposed amide)-type NMR experiments to map exchangeable surface residues whose amides are not involved in hydrogen bonding, and (2) presat-type NMR experiments to map solvent inaccessibly buried residues or nonexchangeable residues located in hydrogen-bonded secondary structures with properly controlled saturation transfer via amide proton exchanges with the solvent. This method separates overlapping resonances in a spectrum into two complementary spectra. The AERE-NMR method was demonstrated with a sample of 15N/13C/2H(70%) labeled ribosome-inactivating protein trichosanthin of 247 residues.

  3. SPY: an innovative intra-operative imaging system to evaluate graft patency during off-pump coronary artery bypass grafting.

    Science.gov (United States)

    Takahashi, Masao; Ishikawa, Toshihiro; Higashidani, Koichi; Katoh, Hiroki

    2004-09-01

    Off-pump coronary artery bypass grafting (CABG) has been rapidly increased, because of its less invasiveness with low complications. However, graft patency rate highly depends on the operators' capability due to technical difficulties. The SPY system, based on the fluorescence of indocyanine green, is an innovative device that permits validation of graft patency intra-operatively. Real time images of grafts are obtained with no need for catheterization, X-rays or iodine contrast medium. High-quality images could be obtained in all 290 grafts of 72 off-pump CABG cases (mean 4.0 grafts per patient). Four anastomoses (1.4%), including two proximal and two distal, were revised because of defects detected by SPY images. In one case, the SPY system revealed no blood flow in a radial sequential graft, although transit-time flow meter measurements showed a diastolic dominant pattern. SPY images provide critical information to surgeons to detect non-patent grafts, allowing them to be revised while the patient is still on the operating table. Using the SPY system, technical failures could be completely resolved during surgery. The use of the SPY system for intra-operative graft validation during off-pump CABG may become the gold standard for surgical management in the near future.

  4. SPI总线接口扩展与应用%Extension and Application of SPI Bus Interface

    Institute of Scientific and Technical Information of China (English)

    郑毛祥

    2012-01-01

    In many kinds of the MCU, there are not SPI serial bus interface, thus limiting its use with SPI bus interface device. This paper introduces the SPI serial bus characteristics and timing, By using the MCU I/O port, through the program control method, simulating SPI serial bus interface, so that it can work with SPI bus interface device transfers data between, and in a serial E2PROM application as an example, introduces the simulation of SPI serial bus the use of the interface method.%在众多型号的单片机中,有许多不带SPI串行总线接口,从而限制了其对SPI总线接口器件的使用.本文介绍了SPI串行总线的特征和时序,对无SPI总线接口的单片机采用其I/O端口,通过程序控制的方法,模拟SPI串行总线接口,使其能与SPI总线接口的器件之间进行数据传送,并以串行E2PROM应用为例,介绍了模拟SPI串行总线接口的使用方法.

  5. Regulation of Salmonella enterica pathogenicity island 1 (SPI-1) by the LysR-type regulator LeuO.

    Science.gov (United States)

    Espinosa, Elena; Casadesús, Josep

    2014-03-01

    LeuO is a quiescent LysR-type regulator belonging to the H-NS regulon. Activation of leuO transcription represses expression of pathogenicity island 1 (SPI-1) in Salmonella enterica serovar Typhimurium and inhibits invasion of epithelial cells. Loss of HilE suppresses LeuO-mediated downregulation of SPI-1. Activation of leuO transcription reduces the level of HilD protein, and loss of HilE restores the wild type HilD level. Hence, LeuO-mediated downregulation of SPI-1 may involve inhibition of HilD activity by HilE, a view consistent with the fact that HilE is a HilD inhibitor. In vivo analyses using β-galactosidase fusions indicate that LeuO activates hilE transcription. In vitro analyses by slot blotting, electrophoretic mobility shift analysis and DNase I footprinting show that LeuO binds the hilE promoter region. Although residual SPI-1 repression by LeuO is observed in the absence of HilE, the LeuO-HilE-HilD 'pathway' appears to be the major mechanism. Because both leuO and SPI-1 are repressed by H-NS, activation of leuO transcription may provide a backup mechanism for SPI-1 repression under conditions that impair H-NS-mediated silencing.

  6. Transcription factor Spi-B-dependent and -independent pathways for the development of Peyer's patch M cells.

    Science.gov (United States)

    Sato, S; Kaneto, S; Shibata, N; Takahashi, Y; Okura, H; Yuki, Y; Kunisawa, J; Kiyono, H

    2013-07-01

    Although many of the biological features of microfold cells (M cells) have been known for many years, the molecular mechanisms of M-cell development and antigen recognition have remained unclear. Here, we report that Umod is a novel M-cell-specific gene, the translation products of which might contribute to the uptake function of M cells. Transcription factor Spi-B was also specifically expressed in M cells among non-hematopoietic lineages. Spi-B-deficient mice showed reduced expression of most, but not all, other M-cell-specific genes and M-cell surface markers. Whereas uptake of Salmonella Typhimurium via M cells was obviously reduced in Spi-B-deficient mice, the abundance of intratissue cohabiting bacteria was comparable between wild-type and Spi-B-deficient mice. These data indicate that there is a small M-cell population with developmental regulation that is Spi-B independent; however, Spi-B is probably a candidate master regulator of M-cell functional maturation and development by another pathway.

  7. SPY: a new scission-point model based on microscopic inputs to predict fission fragment properties

    Energy Technology Data Exchange (ETDEWEB)

    Panebianco, Stefano; Lemaître, Jean-Francois; Sida, Jean-Luc [CEA Centre de Saclay, Gif-sur-Ivette (France); Dubray, Noëel [CEA, DAM, DIF, Arpajon (France); Goriely, Stephane [Institut d' Astronomie et d' Astrophisique, Universite Libre de Bruxelles, Brussels (Belgium)

    2014-07-01

    Despite the difficulty in describing the whole fission dynamics, the main fragment characteristics can be determined in a static approach based on a so-called scission-point model. Within this framework, a new Scission-Point model for the calculations of fission fragment Yields (SPY) has been developed. This model, initially based on the approach developed by Wilkins in the late seventies, consists in performing a static energy balance at scission, where the two fragments are supposed to be completely separated so that their macroscopic properties (mass and charge) can be considered as fixed. Given the knowledge of the system state density, averaged quantities such as mass and charge yields, mean kinetic and excitation energy can then be extracted in the framework of a microcanonical statistical description. The main advantage of the SPY model is the introduction of one of the most up-to-date microscopic descriptions of the nucleus for the individual energy of each fragment and, in the future, for their state density. These quantities are obtained in the framework of HFB calculations using the Gogny nucleon-nucleon interaction, ensuring an overall coherence of the model. Starting from a description of the SPY model and its main features, a comparison between the SPY predictions and experimental data will be discussed for some specific cases, from light nuclei around mercury to major actinides. Moreover, extensive predictions over the whole chart of nuclides will be discussed, with particular attention to their implication in stellar nucleosynthesis. Finally, future developments, mainly concerning the introduction of microscopic state densities, will be briefly discussed. (author)

  8. Standardized Precipitation Index (SPI) over the Mediterranean region based on high resolution gridded data.

    Science.gov (United States)

    Polychroni, Iliana; Nastos, Panagiotis

    2017-04-01

    Mediterranean water resource system is heavily influenced by changes in climate conditions, which in turns affect significantly the socioeconomic development, specifically over coastal areas. Taking into consideration that the surface temperature is projected to rise over the 21st century and the mean precipitation is likely to decrease in mid-latitude dry regions, according to IPCC 2014, we confronted the challenge to study the drought over the Mediterranean region by means of the Standardized Precipitation Index (SPI), defined as the difference from the mean for a specified time period divided by the standard deviation, where the mean and standard deviation are determined from past records. Drought is a long-range phenomenon that affects the Mediterranean. The drought not only affects food production but also has severe environmental, economic and social impacts. The objective of this study is to assess and analyze the spatio-temporal evolution of the SPI for 3-, 6-, 9-, 12- month timescales, during the period 1950-2015. For this purpose, we processed high resolution gridded daily precipitation datasets (0.25° x 0.25°), based on the E-OBS dataset from ECA&D. Mean SPI patterns and trends for the whole examined period, as well as successive 30-year periods, were assessed by using R-project. Moreover, the influence of the well-known atmospheric circulation index of the wider region of Europe, namely the North Atlantic Oscillation Index (NAOI), on the SPI over the Mediterranean was considered necessary to evaluate, because NAOI strongly modulates precipitation over Europe and the Mediterranean.

  9. SPY: a new scission-point model based on microscopic inputs to predict fission fragment properties

    Science.gov (United States)

    Panebianco, Stefano; Dubray, Nöel; Goriely, Stéphane; Hilaire, Stéphane; Lemaître, Jean-François; Sida, Jean-Luc

    2014-04-01

    Despite the difficulty in describing the whole fission dynamics, the main fragment characteristics can be determined in a static approach based on a so-called scission-point model. Within this framework, a new Scission-Point model for the calculations of fission fragment Yields (SPY) has been developed. This model, initially based on the approach developed by Wilkins in the late seventies, consists in performing a static energy balance at scission, where the two fragments are supposed to be completely separated so that their macroscopic properties (mass and charge) can be considered as fixed. Given the knowledge of the system state density, averaged quantities such as mass and charge yields, mean kinetic and excitation energy can then be extracted in the framework of a microcanonical statistical description. The main advantage of the SPY model is the introduction of one of the most up-to-date microscopic descriptions of the nucleus for the individual energy of each fragment and, in the future, for their state density. These quantities are obtained in the framework of HFB calculations using the Gogny nucleon-nucleon interaction, ensuring an overall coherence of the model. Starting from a description of the SPY model and its main features, a comparison between the SPY predictions and experimental data will be discussed for some specific cases, from light nuclei around mercury to major actinides. Moreover, extensive predictions over the whole chart of nuclides will be discussed, with particular attention to their implication in stellar nucleosynthesis. Finally, future developments, mainly concerning the introduction of microscopic state densities, will be briefly discussed.

  10. SPY: a new scission-point model based on microscopic inputs to predict fission fragment properties

    Directory of Open Access Journals (Sweden)

    Panebianco Stefano

    2014-04-01

    Full Text Available Despite the difficulty in describing the whole fission dynamics, the main fragment characteristics can be determined in a static approach based on a so-called scission-point model. Within this framework, a new Scission-Point model for the calculations of fission fragment Yields (SPY has been developed. This model, initially based on the approach developed by Wilkins in the late seventies, consists in performing a static energy balance at scission, where the two fragments are supposed to be completely separated so that their macroscopic properties (mass and charge can be considered as fixed. Given the knowledge of the system state density, averaged quantities such as mass and charge yields, mean kinetic and excitation energy can then be extracted in the framework of a microcanonical statistical description. The main advantage of the SPY model is the introduction of one of the most up-to-date microscopic descriptions of the nucleus for the individual energy of each fragment and, in the future, for their state density. These quantities are obtained in the framework of HFB calculations using the Gogny nucleon-nucleon interaction, ensuring an overall coherence of the model. Starting from a description of the SPY model and its main features, a comparison between the SPY predictions and experimental data will be discussed for some specific cases, from light nuclei around mercury to major actinides. Moreover, extensive predictions over the whole chart of nuclides will be discussed, with particular attention to their implication in stellar nucleosynthesis. Finally, future developments, mainly concerning the introduction of microscopic state densities, will be briefly discussed.

  11. A framework for plasticity implementation on the SpiNNaker neural architecture

    Directory of Open Access Journals (Sweden)

    Francesco eGalluppi

    2015-01-01

    Full Text Available Many of the precise biological mechanisms of synaptic plasticity remain elusive, but simulations of neural networks have greatly enhanced our understanding of how specific global functions arise from the massively parallel computation of neurons and local Hebbian or spike-timing dependent plasticity rules. For simulating large portions of neural tissue, this has created an increasingly strong need for large scale simulations of plastic neural networks on special purpose hardware platforms, because synaptic transmissions and updates are badly matched to computing style supported by current architectures. Because of the great diversity of biological plasticity phenomena and the corresponding diversity of models, there is a great need for testing various hypotheses about plasticity before committing to one hardware implementation. Here we present a novel framework for investigating different plasticity approaches on the SpiNNaker distributed digital neural simulation platform.The key innovation of the proposed architecture is to exploit the reconfigurability of the ARM processors inside SpiNNaker, dedicating a subset of them exclusively to process synaptic plasticity updates, while the rest perform the usual neural and synaptic simulations. We demonstrate the flexibility of the proposed approach by showing the implementation of a variety of spike- and rate-based learning rules, including standard Spike-Timing dependent plasticity (STDP, voltage-dependent STDP, and the rate-based BCM rule.We analyze their performance and validate them by running classical learning experiments in real time on a 4-chip SpiNNaker board. The result is an efficient, modular, flexible and scalable framework, which provides a valuable tool for the fast and easy exploration of learning models of very different kinds on the parallel and reconfigurable SpiNNaker system.

  12. A framework for plasticity implementation on the SpiNNaker neural architecture.

    Science.gov (United States)

    Galluppi, Francesco; Lagorce, Xavier; Stromatias, Evangelos; Pfeiffer, Michael; Plana, Luis A; Furber, Steve B; Benosman, Ryad B

    2014-01-01

    Many of the precise biological mechanisms of synaptic plasticity remain elusive, but simulations of neural networks have greatly enhanced our understanding of how specific global functions arise from the massively parallel computation of neurons and local Hebbian or spike-timing dependent plasticity rules. For simulating large portions of neural tissue, this has created an increasingly strong need for large scale simulations of plastic neural networks on special purpose hardware platforms, because synaptic transmissions and updates are badly matched to computing style supported by current architectures. Because of the great diversity of biological plasticity phenomena and the corresponding diversity of models, there is a great need for testing various hypotheses about plasticity before committing to one hardware implementation. Here we present a novel framework for investigating different plasticity approaches on the SpiNNaker distributed digital neural simulation platform. The key innovation of the proposed architecture is to exploit the reconfigurability of the ARM processors inside SpiNNaker, dedicating a subset of them exclusively to process synaptic plasticity updates, while the rest perform the usual neural and synaptic simulations. We demonstrate the flexibility of the proposed approach by showing the implementation of a variety of spike- and rate-based learning rules, including standard Spike-Timing dependent plasticity (STDP), voltage-dependent STDP, and the rate-based BCM rule. We analyze their performance and validate them by running classical learning experiments in real time on a 4-chip SpiNNaker board. The result is an efficient, modular, flexible and scalable framework, which provides a valuable tool for the fast and easy exploration of learning models of very different kinds on the parallel and reconfigurable SpiNNaker system.

  13. The heavy metals content in wild growing mushrooms from burdened Spiš area

    OpenAIRE

    Marek Slávik; Tomáš Tóth; Július Árvay; Ľuboš Harangozo; Miriama Kopernická

    2016-01-01

    In this work, we evaluated the rate of entry of heavy metals into the edible parts of wild mushrooms, from central Spiš area. The area is characterized by extremely high content of heavy metals particularly mercury in abiotic and biotic components of ecosystems. The toxicity of heavy metals is well known and described. Known is also the ability of fungi to accumulate contaminants from substrates in which mushrooms grow. We have collected commonly consumed species of mushr...

  14. Development of SPIES (Space Intelligent Eyeing System) for smart vehicle tracing and tracking

    Science.gov (United States)

    Abdullah, Suzanah; Ariffin Osoman, Muhammad; Guan Liyong, Chua; Zulfadhli Mohd Noor, Mohd; Mohamed, Ikhwan

    2016-06-01

    SPIES or Space-based Intelligent Eyeing System is an intelligent technology which can be utilized for various applications such as gathering spatial information of features on Earth, tracking system for the movement of an object, tracing system to trace the history information, monitoring driving behavior, security and alarm system as an observer in real time and many more. SPIES as will be developed and supplied modularly will encourage the usage based on needs and affordability of users. SPIES are a complete system with camera, GSM, GPS/GNSS and G-Sensor modules with intelligent function and capabilities. Mainly the camera is used to capture pictures and video and sometimes with audio of an event. Its usage is not limited to normal use for nostalgic purpose but can be used as a reference for security and material of evidence when an undesirable event such as crime occurs. When integrated with space based technology of the Global Navigational Satellite System (GNSS), photos and videos can be recorded together with positioning information. A product of the integration of these technologies when integrated with Information, Communication and Technology (ICT) and Geographic Information System (GIS) will produce innovation in the form of information gathering methods in still picture or video with positioning information that can be conveyed in real time via the web to display location on the map hence creating an intelligent eyeing system based on space technology. The importance of providing global positioning information is a challenge but overcome by SPIES even in areas without GNSS signal reception for the purpose of continuous tracking and tracing capability

  15. The PAW/GIPAW approach for computing NMR parameters: a new dimension added to NMR study of solids.

    Science.gov (United States)

    Charpentier, Thibault

    2011-07-01

    In 2001, Mauri and Pickard introduced the gauge including projected augmented wave (GIPAW) method that enabled for the first time the calculation of all-electron NMR parameters in solids, i.e. accounting for periodic boundary conditions. The GIPAW method roots in the plane wave pseudopotential formalism of the density functional theory (DFT), and avoids the use of the cluster approximation. This method has undoubtedly revitalized the interest in quantum chemical calculations in the solid-state NMR community. It has quickly evolved and improved so that the calculation of the key components of NMR interactions, namely the shielding and electric field gradient tensors, has now become a routine for most of the common nuclei studied in NMR. Availability of reliable implementations in several software packages (CASTEP, Quantum Espresso, PARATEC) make its usage more and more increasingly popular, maybe indispensable in near future for all material NMR studies. The majority of nuclei of the periodic table have already been investigated by GIPAW, and because of its high accuracy it is quickly becoming an essential tool for interpreting and understanding experimental NMR spectra, providing reliable assignments of the observed resonances to crystallographic sites or enabling a priori prediction of NMR data. The continuous increase of computing power makes ever larger (and thus more realistic) systems amenable to first-principles analysis. In the near future perspectives, as the incorporation of dynamical effects and/or disorder are still at their early developments, these areas will certainly be the prime target.

  16. OPTIMIZING THE USE OF AN SPI FLASH PROM IN MICROBLAZE-BASED EMBEDDED SYSTEMS

    Directory of Open Access Journals (Sweden)

    Ahmed Hanafi

    2013-11-01

    Full Text Available This paper aims to simplify FPGA designs that incorporate Embedded Software Systems using a soft core Processor. It describes a simple solution to reduce the need of multiple non-volatile memory devices by using one SPI (Serial Peripheral Interface Flash PROM for FPGA configuration data, software code (Processor applications, and miscellaneous user data. We have thus developed a design based on a MicroBlaze soft processor implemented on a Xilinx Spartan-6 FPGA SP605 Evaluation Kit. The hardware architecture with SPI flash was designed using the Xilinx Platform Studio (XPS and the software applications, including the bootloader, was developed with Xilinx Software Development Kit (SDK. ISE Design Tools prepared by Xilinx Company, is employed to create the files used to program flash memory which are SREC (S-record file associated with software code, Hexadecimal file for user data, and bootloader file to configure the FPGA and allows software applications stored in flash memory to be executed when the system is powered on. Reading access to the SPI Flash memory is simplified by the use of Xilinx In-System Flash (ISF library.

  17. Application of the SPI (Saliva Precipitation Index) to the evaluation of red wine astringency.

    Science.gov (United States)

    Rinaldi, Alessandra; Gambuti, Angelita; Moio, Luigi

    2012-12-15

    The aim of this work was to evaluate the astringency of red wines by means of a SDS-PAGE based-method. The optimization of the in vitro assay, named SPI (Saliva Precipitation Index) that measured the reactivity of salivary proteins towards wine polyphenols, has been performed. Improvements included the choice of saliva:wine ratio, saliva typology (resting or stimulated saliva), and temperature of binding. The LOD (0.05 g/L of condensed tannin) and LOQ (0.1g/L of condensed tannin) for the binding reaction between salivary proteins and tannins added in white wine were also determined. Fifty-seven red wines were analysed by the optimised SPI, the Folin-Ciocalteu Index, the gelatine index, the content of total tannins and the sensory quantitative evaluation of astringency. A significant correlation between the SPI and the astringency of red wines was found (R(2)=0.969), thus indicating that this assay may be useful as estimator of astringency.

  18. Characterization of the SPI-1 and Rsp type three secretion systems in Pseudomonas fluorescens F113.

    Science.gov (United States)

    Barret, Matthieu; Egan, Frank; Moynihan, Jennifer; Morrissey, John P; Lesouhaitier, Olivier; O'Gara, Fergal

    2013-06-01

    Pseudomonas fluorescens F113 is a plant growth-promoting rhizobacterium (PGPR) isolated from the sugar beet rhizosphere. The recent annotation of the F113 genome sequence has revealed that this strain encodes a wide array of secretion systems, including two complete type three secretion systems (T3SSs) belonging to the Hrp1 and SPI-1 families. While Hrp1 T3SSs are frequently encoded in other P. fluorescens strains, the presence of a SPI-1 T3SS in a plant-beneficial bacterial strain was unexpected. In this work, the genetic organization and expression of these two T3SS loci have been analysed by a combination of transcriptional reporter fusions and transcriptome analyses. Overexpression of two transcriptional activators has shown a number of genes encoding putative T3 effectors. In addition, the influence of these two T3SSs during the interaction of P. fluorescens F113 with some bacterial predators was also assessed. Our data revealed that the transcriptional activator hilA is induced by amoeba and that the SPI-1 T3SS could potentially be involved in resistance to amoeboid grazing.

  19. NMR, Water and Plants

    NARCIS (Netherlands)

    As, van H.

    1982-01-01

    This Thesis describes the application of a non-destructive pulsed proton NMR method mainly to measure water transport in the xylem vessels of plant stems and in some model systems. The results are equally well applicable to liquid flow in other biological objects than plants, e.g. flow of blood and

  20. Single-sided NMR

    CERN Document Server

    Casanova, Federico; Blümich, Bernhard

    2011-01-01

    Single-Sided NMR describes the design of the first functioning single-sided tomograph, the related measurement methods, and a number of applications. One of the key advantages to this method is the speed at which the images are obtained.

  1. Autonomous driving in NMR.

    Science.gov (United States)

    Perez, Manuel

    2017-01-01

    The automatic analysis of NMR data has been a much-desired endeavour for the last six decades, as it is the case with any other analytical technique. This need for automation has only grown as advances in hardware; pulse sequences and automation have opened new research areas to NMR and increased the throughput of data. Full automatic analysis is a worthy, albeit hard, challenge, but in a world of artificial intelligence, instant communication and big data, it seems that this particular fight is happening with only one technique at a time (let this be NMR, MS, IR, UV or any other), when the reality of most laboratories is that there are several types of analytical instrumentation present. Data aggregation, verification and elucidation by using complementary techniques (e.g. MS and NMR) is a desirable outcome to pursue, although a time-consuming one if performed manually; hence, the use of automation to perform the heavy lifting for users is required to make the approach attractive for scientists. Many of the decisions and workflows that could be implemented under automation will depend on the two-way communication with databases that understand analytical data, because it is desirable not only to query these databases but also to grow them in as much of an automatic manner as possible. How these databases are designed, set up and the data inside classified will determine what workflows can be implemented. Copyright © 2016 John Wiley & Sons, Ltd.

  2. Soils, Pores, and NMR

    Science.gov (United States)

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

    2010-05-01

    Within Cluster A, Partial Project A1, the pore space exploration by means of Nuclear Magnetic Resonance (NMR) plays a central role. NMR is especially convenient since it probes directly the state and dynamics of the substance of interest: water. First, NMR is applied as relaxometry, where the degree of saturation but also the pore geometry controls the NMR signature of natural porous systems. Examples are presented where soil samples from the Selhausen, Merzenhausen (silt loams), and Kaldenkirchen (sandy loam) test sites are investigated by means of Fast Field Cycling Relaxometry at different degrees of saturation. From the change of the relaxation time distributions with decreasing water content and by comparison with conventional water retention curves we conclude that the fraction of immobile water is characterized by T1 samples (Haber-Pohlmeier et al. 2010). Third, relaxometric information forms the basis of understanding magnetic resonance imaging (MRI) results. The general difficulty of imaging in soils are the inherent fast T2 relaxation times due to i) the small pore sizes, ii) presence of paramagnetic ions in the solid matrix, and iii) diffusion in internal gradients. The last point is important, since echo times can not set shorter than about 1ms for imaging purposes. The way out is either the usage of low fields for imaging in soils or special ultra-short pulse sequences, which do not create echoes. In this presentation we will give examples on conventional imaging of macropore fluxes in soil cores (Haber-Pohlmeier et al. 2010), and the combination with relaxometric imaging, as well as the advantages and drawbacks of low-field and ultra-fast pulse imaging. Also first results on the imaging of soil columns measured by SIP in Project A3 are given. Haber-Pohlmeier, S., S. Stapf, et al. (2010). "Waterflow Monitored by Tracer Transport in Natural Porous Media Using MRI." Vadose Zone J.: submitted. Haber-Pohlmeier, S., S. Stapf, et al. (2010). "Relaxation in a

  3. A new method for multi-exponential inversion of NMR relaxation measurements

    Institute of Scientific and Technical Information of China (English)

    WANG; Zhongdong; XIAO; Lizhi; LIU; Tangyan

    2004-01-01

    A new method for multi-exponential inversion to NMR T1 and T2 relaxation time distributions is suggested and tested. Inversion results are compared with MAP-II which is based on SVD algorithm and widely accepted in the industry. Inversed NMR relaxation spectra that have different pre-assigned relaxation times from echo trains with different SNR confirm that the new method with 16 to 64 equally spaced time constants in logarithm scale will ensure the relaxation distribution. Testing results show that the new inversion algorithm is a valuable tool for rock core NMR experimental analysis and NMR logging data process and interpretation.

  4. Enhancing NMR of insensitive nuclei by transfer of SABRE spin hyperpolarization

    Science.gov (United States)

    Pravdivtsev, Andrey N.; Yurkovskaya, Alexandra V.; Zimmermann, Herbert; Vieth, Hans-Martin; Ivanov, Konstantin L.

    2016-09-01

    We describe the performance of methods for enhancing NMR (Nuclear Magnetic Resonance) signals of "insensitive", but important NMR nuclei, which are based on the SABRE (Signal Amplification By Reversible Exchange) technique, i.e., on spin order transfer from parahydrogen (H2 molecule in its nuclear singlet spin state) to a substrate in a transient organometallic complex. Here such transfer is performed at high magnetic fields by INEPT-type NMR pulse sequences, modified for SABRE. Signal enhancements up to three orders of magnitude are obtained for 15N nuclei; the possibility of sensitive detection of 2D-NMR 1H-15N spectra of SABRE complexes and substrates is demonstrated.

  5. Dynamic NMR under nonstationary conditions: Theoretical model, numerical calculation, and potential of application.

    Science.gov (United States)

    Babailov, S P; Purtov, P A; Fomin, E S

    2016-08-01

    An expression has been derived for the time dependence of the NMR line shape for systems with multi-site chemical exchange in the absence of spin-spin coupling, in a zero saturation limit. The dynamics of variation of the NMR line shape with time is considered in detail for the case of two-site chemical exchange. Mathematical programs have been designed for numerical simulation of the NMR spectra of chemical exchange systems. The analytical expressions obtained are useful for NMR line shape simulations for systems with photoinduced chemical exchange.

  6. Nanogram-scale preparation and NMR analysis for mass-limited small volatile compounds.

    Directory of Open Access Journals (Sweden)

    Satoshi Nojima

    Full Text Available Semiochemicals are often produced in infinitesimally small quantities, so their isolation requires large amounts of starting material, not only requiring significant effort in sample preparation, but also resulting in a complex mixture of compounds from which the bioactive compound needs to be purified and identified. Often, compounds cannot be unambiguously identified by their mass spectra alone, and NMR analysis is required for absolute chemical identification, further exacerbating the situation because NMR is relatively insensitive and requires large amounts of pure analyte, generally more than several micrograms. We developed an integrated approach for purification and NMR analysis of <1 µg of material. Collections from high performance preparative gas-chromatography are directly eluted with minimal NMR solvent into capillary NMR tubes. With this technique, (1H-NMR spectra were obtained on 50 ng of geranyl acetate, which served as a model compound, and reasonable H-H COSY NMR spectra were obtained from 250 ng of geranyl acetate. This simple off-line integration of preparative GC and NMR will facilitate the purification and chemical identification of novel volatile compounds, such as insect pheromones and other semiochemicals, which occur in minute (sub-nanogram, and often limited, quantities.

  7. NMR for chemists and biologists

    CERN Document Server

    Carbajo, Rodrigo J

    2013-01-01

    This book offers a concise introduction to the field of nuclear magnetic resonance or NMR. It presents the basic foundations of NMR in a non-mathematical way and provides an overview of both recent and important biological applications of NMR.

  8. NMR magnet technology at MIT

    Energy Technology Data Exchange (ETDEWEB)

    Williams, J.E.C.; Bobrov, E.S.; Iwasa, Y.; Punchard, W.F.B.; Wrenn, J.; Zhukovsky, A. (Massachusetts Inst. of Tech., Cambridge, MA (United States). Francis Bitter National Magnet Lab.)

    1992-01-01

    The design and construction of high field superconducting NMR magnets has much in common with other types of adiabatic superconducting magnets. However, two issues have a particular relevance to NMR magnets. They are field drift and homogeneity. In this paper the control of these factors in the particular context of high field NMR spectrometer magnets is examined.

  9. Diverging trends between meteorological drought indices (SPI and SPEI) in Europe

    Science.gov (United States)

    Stagge, James; Kingston, Daniel; Tallaksen, Lena; Hannah, David

    2016-04-01

    Severe European droughts over the last decade and climate change projections of increased regional drought severity for the Mediterranean and eastern Europe make understanding drought events in a non-stationary climate a major scientific and practical concern for Europe. Additionally, the existence of numerous differing drought metrics is a challenge for the robust detection of drought occurrence trends. This research addresses these issues by testing the hypotheses that (a) there have been recent trends in meteorological drought severity across Europe, and (b) that the choice of drought index significantly affects these observed trends. Meteorological drought is quantified in this study using the 6-month Standardized Precipitation Index (SPI-6) and Standardized Precipitation-Evapotranspiration Index (SPEI-6), which are commonly recommended drought metrics that measure accumulated precipitation and climatic water balance (precipitation minus reference potential evapotranspiration), respectively. Climate data are based on the WATCH Forcing Data (WFD) and WFD ERA-Interim (WFDEI) datasets, which together cover the period 1958-2014. Trends in percentage of European land area in drought were calculated for this 56 year period by defining drought as occurring below the 20th index percentile (SPI/SPEI SPEI-6 drought area have been moderate, with a slight decrease in precipitation-only drought (SPI) area and a slight increase in climatic water balance drought (SPEI) area. The observed spatial trends in drought frequency are consistent with climate model output, with increases in drought frequency for southern Europe and decreases across northern Europe. However, the difference between percentage drought area measured using these two indices has steadily increased. Investigating the constituent climate variables shows that the increasing divergence between drought measured by SPI and SPEI is driven by an increase in temperature and thus PET, which is only accounted for in

  10. 29Si and 27AI MAS NMR Study of Alkali Feldspars

    Institute of Scientific and Technical Information of China (English)

    周玲棣; 郭九皋; 袁汉珍; 李丽云

    1994-01-01

    12 natural alkali feldspars have been studied by(29)~Si and(27)~Al MAS NMR as well as XRD,IR,EPMA and chemical analysis.Three kinds of(29)~Si NMR spectra,i.e.the spectra of microcline,perthiteand perthite with minor plagioclase,have been obtained.There are two types of(27)~Al NMR spectra.The(27)~Alspectrum of microcline is the same as that of perthite,but is different from the spectrum for perthite contain-ing plagioclase.Through this study,we found that the results of NMR and IR are inconsistent with that ofXRD,which shows that the transition of alkali feldspar from monoclinic to triclinic system might be a rathercomplicated process.

  11. 1H and 13C HR-MAS NMR investigations on native and enzymatically digested bovine nasal cartilage.

    Science.gov (United States)

    Schiller, J; Naji, L; Huster, D; Kaufmann, J; Arnold, K

    2001-08-01

    Rheumatic diseases are accompanied by a progressive destruction of the cartilage layer of the joints. Despite the frequency of the disease, degradation mechanisms are not yet understood and methods for early diagnosis are not available. Although some information on pathogenesis could be obtained from the analysis of degradation products of cartilage supernatants, the most direct information on degradation processes would come from the native cartilage as such. We have used 1H as well as 13C HR-MAS (high resolution magic angle spinning) NMR spectroscopy to obtain suitable line-widths of NMR resonances of native cartilage. 1D and 2D NMR spectra of native cartilage were compared with those of enzymatically-treated (collagenase and papain) samples. In the 1H NMR spectra of native cartilage, resonances of polysaccharides, lipids and a few amino acids of collagen were detectable, whereas the 13C NMR spectra primarily indicated the presence of chondroitin sulfate. Treatment with papain resulted only in small changes in the 1H NMR spectrum, whereas a clear diminution of all resonances was detectable in the 13C NMR spectra. On the other hand, treatment with collagenase caused the formation of peptides with an amino acid composition typical for collagen (glycine, proline, hydroxyproline and lysine). It is concluded that the HR-MAS NMR spectra of cartilage may be of significance for the investigation of cartilage degradation since they allow the fast evaluation of cartilage composition and only very small amounts of sample are required.

  12. Improved Mobility Control for Carbon Dioxide (CO{sub 2}) Enhanced Oil Recovery Using Silica-Polymer-Initiator (SPI) Gels

    Energy Technology Data Exchange (ETDEWEB)

    Oglesby, Kenneth

    2014-01-31

    SPI gels are multi-component silicate based gels for improving (areal and vertical) conformance in oilfield enhanced recovery operations, including water-floods and carbon dioxide (CO{sub 2}) floods, as well as other applications. SPI mixtures are like-water when pumped, but form light up to very thick, paste-like gels in contact with CO{sub 2}. When formed they are 3 to 10 times stronger than any gelled polyacrylamide gel now available, however, they are not as strong as cement or epoxy, allowing them to be washed / jetted out of the wellbore without drilling. This DOE funded project allowed 8 SPI field treatments to be performed in 6 wells (5 injection wells and 1 production well) in 2 different fields with different operators, in 2 different basins (Gulf Coast and Permian) and in 2 different rock types (sandstone and dolomite). Field A was in a central Mississippi sandstone that injected CO{sub 2} as an immiscible process. Field B was in the west Texas San Andres dolomite formation with a mature water-alternating-gas miscible CO{sub 2} flood. Field A treatments are now over 1 year old while Field B treatments have only 4 months data available under variable WAG conditions. Both fields had other operational events and well work occurring before/ during / after the treatments making definitive evaluation difficult. Laboratory static beaker and dynamic sand pack tests were performed with Ottawa sand and both fields’ core material, brines and crude oils to improve SPI chemistry, optimize SPI formulations, ensure SPI mix compatibility with field rocks and fluids, optimize SPI treatment field treatment volumes and methods, and ensure that strong gels set in the reservoir. Field quality control procedures were designed and utilized. Pre-treatment well (surface) injectivities ranged from 0.39 to 7.9 MMCF/psi. The SPI treatment volumes ranged from 20.7 cubic meters (m{sup 3}, 5460 gallons/ 130 bbls) to 691 m{sup 3} (182,658 gallons/ 4349 bbls). Various size and types

  13. Subtle distinct regulations of late erythroid molecular events by PI3K/AKT-mediated activation of Spi-1/PU.1 oncogene autoregulation loop.

    Science.gov (United States)

    Breig, O; Théoleyre, O; Douablin, A; Baklouti, F

    2010-05-13

    Spi-1/PU.1 oncogene is downregulated as proerythroblasts undergo terminal differentiation. Insertion of the Friend virus upstream of the Spi-1/PU.1 locus leads to the constitutive upregulation of Spi-1/PU.1, and a subsequent block in the differentiation of the affected erythroblasts. We have shown that sustained overexpression of Spi-1/PU.1 also inhibits the erythroid splicing of protein 4.1R exon 16, irrespective of chemical induction of differentiation. Here, we show a positive feedback loop that couples constitutive phosphatidylinositol 3-kinase (PI3K)/protein kinase B (AKT) signaling to high expression of Spi-1/PU.1 in Friend erythroleukemia cells. Inhibition of PI3K/AKT results in Spi-1/PU.1 downregulation in a stepwise manner and induces cell differentiation. Chromatin immunoprecipitation assays further supported the positive autoregulatory effect of Spi-1/PU.1. Mutational analysis indicated that Ser41, but not Ser148, is necessary for Spi-1/PU.1-mediated repression of hemoglobin expression, whereas both Ser residues are required for Spi-1/PU.1 inhibition of the erythroid splicing event. We further show that inhibition of the erythroid transcriptional and splicing events are strictly dependent on distinct Spi-1/PU.1 phosphorylation modifications rather than Spi-1/PU.1 expression level per se. Our data further support the fact that Spi-1/PU.1 inhibits 4.1R erythroid splicing through two different pathways, and bring new insights into the extracellular signal impact triggered by erythropoietin on late erythroid regulatory program, including pre-mRNA splicing.

  14. Synthesis of fluorinated maltose derivatives for monitoring protein interaction by 19F NMR

    Directory of Open Access Journals (Sweden)

    Michaela Braitsch

    2012-03-01

    Full Text Available A novel reporter system, which is applicable to the 19F NMR investigation of protein interactions, is presented. This approach uses 2-F-labeled maltose as a spy ligand to indirectly probe protein–ligand or protein–protein interactions of proteins fused or tagged to the maltose-binding protein (MBP. The key feature is the simultaneous NMR observation of both 19F NMR signals of gluco/manno-type-2-F-maltose-isomers; one isomer (α-gluco-type binds to MBP and senses the protein interaction, and the nonbinding isomers (β-gluco- and/or α/β-manno-type are utilized as internal references. Moreover, this reporter system was used for relative affinity studies of fluorinated and nonfluorinated carbohydrates to the maltose-binding protein, which were found to be in perfect agreement with published X-ray data. The results of the NMR competition experiments together with the established correlation between 19F chemical shift data and molecular interaction patterns, suggest valuable applications for studies of protein–ligand interaction interfaces.

  15. Principles of high resolution NMR in solids

    CERN Document Server

    Mehring, Michael

    1983-01-01

    The field of Nuclear Magnetic Resonance (NMR) has developed at a fascinating pace during the last decade. It always has been an extremely valuable tool to the organic chemist by supplying molecular "finger print" spectra at the atomic level. Unfortunately the high resolution achievable in liquid solutions could not be obtained in solids and physicists and physical chemists had to live with unresolved lines open to a wealth of curve fitting procedures and a vast amount of speculations. High resolution NMR in solids seemed to be a paradoxon. Broad structure­ less lines are usually encountered when dealing with NMR in solids. Only with the recent advent of mUltiple pulse, magic angle, cross-polarization, two-dimen­ sional and multiple-quantum spectroscopy and other techniques during the last decade it became possible to resolve finer details of nuclear spin interactions in solids. I have felt that graduate students, researchers and others beginning to get involved with these techniques needed a book which trea...

  16. Cutoff-Free Traveling Wave NMR

    CERN Document Server

    Tang, Joel A; Sodickson, Daniel K; Jerschow, Alexej

    2011-01-01

    Recently, the concept of traveling-wave NMR/MRI was introduced by Brunner et al. (Nature 457, 994-992 (2009)), who demonstrated MR images acquired using radio frequency (RF) waves propagating down the bore of an MR scanner. One of the significant limitations of this approach is that each bore has a specific cutoff frequency, which can be higher than most Larmor frequencies of at the magnetic field strengths commonly in use for MR imaging and spectroscopy today. We overcome this limitation by using a central conductor in the waveguide and thereby converting it to a transmission line (TL), which has no cutoff frequency. Broadband propagation of waves through the sample thus becomes possible. NMR spectra and images with such an arrangement are presented and genuine traveling wave behavior is demonstrated. In addition to facilitating NMR spectroscopy and imaging in smaller bores via traveling waves, this approach also allows one to perform multinuclear traveling wave experiments (an example of which is shown), an...

  17. NMR Studies of Cartilage Dynamics, Diffusion, Degradation

    Science.gov (United States)

    Huster, Daniel; Schiller, Jurgen; Naji, Lama; Kaufmann Jorn; Arnold, Klaus

    An increasing number of people is suffering from rheumatic diseases, and, therefore, methods of early diagnosis of joint degeneration are urgently required. For their establishment, however, an improved knowledge about the molecular organisation of cartilage would be helpful. Cartilage consists of three main components: Water, collagen and chondroitin sulfate (CS) that is (together with further polysaccharides and proteins) a major constituent of the proteoglycans of cartilage. 1H and 13C MAS (magic-angle spinning) NMR (nuclear magnetic resonance) opened new perspectives for the study of the macromolecular components in cartilage. We have primarily studied the mobilities of CS and collagen in bovine nasal and pig articular cartilage (that differ significantly in their collagen/polysaccharide content) by measuring 13C NMR relaxation times as well as the corresponding 13C CP (cross polarisation) MAS NMR spectra. These data clearly indicate that the mobility of cartilage macromolecules is broadly distributed from almost completely rigid (collagen) to highly mobile (polysaccharides), which lends cartilage its mechanical strength and shock-absorbing properties.

  18. The role of SPY and its TPR domain in the regulation of gibberellin action throughout the life cycle of Petunia hybrida plants.

    Science.gov (United States)

    Izhaki, A; Swain, S M; Tseng, T S; Borochov, A; Olszewski, N E; Weiss, D

    2001-10-01

    SPY acts as a negative regulator of gibberellin (GA) action in Arabidopsis, but its mode of action and regulation are still unknown. SPY over-expression in transgenic petunia plants affected various GA-regulated processes, including seed germination, shoot elongation, flower initiation, flower development and the expression of a GA-induced gene, GIP. A similar phenotype was obtained when wild-type petunia plants were treated with the GA-biosynthesis inhibitor, paclobutrazol. The N-terminus of SPY contains tetratricopeptide repeats (TPR). TPR motifs participate in protein-protein interactions, suggesting that SPY is part of a multiprotein complex. To test this hypothesis, we over-expressed the SPY's TPR region without the catalytic domain in transgenic petunia and generated a dominant-negative SPY mutant. The transgenic seeds were able to germinate on paclobutrazol, suggesting an enhanced GA signal. We cloned the petunia SPY homologue, PhSPY, and showed that its mRNA level is not affected by GA or ABA. The results of this study support the role of SPY as a negative regulator of GA action, suggest that the TPR domain is required for the interaction with other proteins to form an active complex and indicate that different plants use similar mechanisms to transduce the GA signal.

  19. SPI-1-encoded type III secretion system of Salmonella enterica is required for the suppression of porcine alveolar macrophage cytokine expression

    Directory of Open Access Journals (Sweden)

    Pavlova Barbora

    2011-01-01

    Full Text Available Abstract Genes localized at Salmonella pathogenicity island-1 (SPI-1 are involved in Salmonella enterica invasion of host non-professional phagocytes. Interestingly, in macrophages, SPI-1-encoded proteins, in addition to invasion, induce cell death via activation of caspase-1 which also cleaves proIL-1β and proIL-18, precursors of 2 proinflammatory cytokines. In this study we were therefore interested in whether SPI-1-encoded type III secretion system (T3SS may influence proinflammatory response of macrophages. To test this hypothesis, we infected primary porcine alveolar macrophages with wild-type S. Typhimurium and S. Enteritidis and their isogenic SPI-1 deletion mutants. ΔSPI1 mutants of both serovars invaded approx. 5 times less efficiently than the wild-type strains and despite this, macrophages responded to the infection with ΔSPI1 mutants by increased expression of proinflammatory cytokines IL-1β, IL-8, TNFα, IL-23α and GM-CSF. Identical macrophage responses to that induced by the ΔSPI1 mutants were also observed to the infection with sipB but not the sipA mutant. The hilA mutant exhibited an intermediate phenotype between the ΔSPI1 mutant and the wild-type S. Enteritidis. Our results showed that the SPI-1-encoded T3SS is required not only for cell invasion but in macrophages also for the suppression of early proinflammatory cytokine expression.

  20. NMR of unfolded proteins

    Indian Academy of Sciences (India)

    Amarnath Chtterjee; Ashutosh Kumar; Jeetender Chugh; Sudha Srivastava; Neel S Bhavesh; Ramakrishna V Hosur

    2005-01-01

    In the post-genomic era, as more and more genome sequences are becoming known and hectic efforts are underway to decode the information content in them, it is becoming increasingly evident that flexibility in proteins plays a crucial role in many of the biological functions. Many proteins have intrinsic disorder either wholly or in specific regions. It appears that this disorder may be important for regulatory functions of the proteins, on the one hand, and may help in directing the folding process to reach the compact native state, on the other. Nuclear magnetic resonance (NMR) has over the last two decades emerged as the sole, most powerful technique to help characterize these disordered protein systems. In this review, we first discuss the significance of disorder in proteins and then describe the recent developments in NMR methods for their characterization. A brief description of the results obtained on several disordered proteins is presented at the end.