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Sample records for nmr correlation experiments

  1. A discrete Fourier-encoded, diagonal-free experiment to simplify homonuclear 2D NMR correlations

    Science.gov (United States)

    Huang, Zebin; Guan, Quanshuai; Chen, Zhong; Frydman, Lucio; Lin, Yulan

    2017-07-01

    Nuclear magnetic resonance (NMR) spectroscopy has long served as an irreplaceable, versatile tool in physics, chemistry, biology, and materials sciences, owing to its ability to study molecular structure and dynamics in detail. In particular, the connectivity of chemical sites within molecules, and thereby molecular structure, becomes visible by multi-dimensional NMR. Homonuclear correlation experiments are a powerful tool for identifying coupled spins. Generally, diagonal peaks in these correlation spectra display the strongest intensities and do not offer any new information beyond the standard one-dimensional spectrum, whereas weaker, symmetrically placed cross peaks contain most of the coupling information. The cross peaks near the diagonal are often affected by the tails of strong diagonal peaks or even obscured entirely by the diagonal. In this paper, we demonstrate a homonuclear encoding approach based on imparting a discrete phase modulation of the targeted cross peaks and combine it with a site-selective sculpting scheme, capable of simplifying the patterns arising in these 2D correlation spectra. The theoretical principles of the new methods are laid out, and experimental observations are rationalized on the basis of theoretical analyses. The ensuing techniques provide a new way to retrieve 2D coupling information within homonuclear spin systems, with enhanced sensitivity, speed, and clarity.

  2. A NMR experiment for simultaneous correlations of valine and leucine/isoleucine methyls with carbonyl chemical shifts in proteins.

    Science.gov (United States)

    Tugarinov, Vitali; Venditti, Vincenzo; Marius Clore, G

    2014-01-01

    A methyl-detected 'out-and-back' NMR experiment for obtaining simultaneous correlations of methyl resonances of valine and isoleucine/leucine residues with backbone carbonyl chemical shifts, SIM-HMCM(CGCBCA)CO, is described. The developed pulse-scheme serves the purpose of convenience in recording a single data set for all Ile(δ1), Leu(δ) and Val(γ) (ILV) methyl positions instead of acquiring two separate spectra selective for valine or leucine/isoleucine residues. The SIM-HMCM(CGCBCA)CO experiment can be used for ILV methyl assignments in moderately sized protein systems (up to ~100 kDa) where the backbone chemical shifts of (13)C(α), (13)Cβ and (13)CO are known from prior NMR studies and where some losses in sensitivity can be tolerated for the sake of an overall reduction in NMR acquisition time.

  3. Theoretical NMR correlations based Structure Discussion

    Directory of Open Access Journals (Sweden)

    Junker Jochen

    2011-07-01

    Full Text Available Abstract The constitutional assignment of natural products by NMR spectroscopy is usually based on 2D NMR experiments like COSY, HSQC, and HMBC. The actual difficulty of the structure elucidation problem depends more on the type of the investigated molecule than on its size. The moment HMBC data is involved in the process or a large number of heteroatoms is present, a possibility of multiple solutions fitting the same data set exists. A structure elucidation software can be used to find such alternative constitutional assignments and help in the discussion in order to find the correct solution. But this is rarely done. This article describes the use of theoretical NMR correlation data in the structure elucidation process with WEBCOCON, not for the initial constitutional assignments, but to define how well a suggested molecule could have been described by NMR correlation data. The results of this analysis can be used to decide on further steps needed to assure the correctness of the structural assignment. As first step the analysis of the deviation of carbon chemical shifts is performed, comparing chemical shifts predicted for each possible solution with the experimental data. The application of this technique to three well known compounds is shown. Using NMR correlation data alone for the description of the constitutions is not always enough, even when including 13C chemical shift prediction.

  4. Solid‐state NMR H‐N‐(C)‐H and H‐N‐C‐C 3D/4D correlation experiments for resonance assignment of large proteins

    OpenAIRE

    Fraga, Hugo; Arnaud, Charles-Adrien; Gauto, Diego; Audin, Maxime; Kurauskas, Vilius; Macek, Pavel,; Krichel, Carsten; Guan, Jia-Ying; Boisbouvier, Jérôme; Sprangers, Remco; Breyton, Cecile,; Schanda, Paul

    2017-01-01

    International audience; Solid-state NMR can provide insight into protein structure and dynamics at the atomic level without inherent protein size limitations. However, a major hurdle to studying large proteins by solid-state NMR spectroscopy is related to spectral complexity and resonance overlap, which increase with molecular weight and severely hamper the assignment process. Here we show the use of two sets of experiments that expand the tool kit of 1H-detected assignment approaches, and wh...

  5. An Inversion Recovery NMR Kinetics Experiment

    Science.gov (United States)

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

    2011-01-01

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

  6. Effective rotational correlation times of proteins from NMR relaxation interference

    Science.gov (United States)

    Lee, Donghan; Hilty, Christian; Wider, Gerhard; Wüthrich, Kurt

    2006-01-01

    Knowledge of the effective rotational correlation times, τc, for the modulation of anisotropic spin-spin interactions in macromolecules subject to Brownian motion in solution is of key interest for the practice of NMR spectroscopy in structural biology. The value of τc enables an estimate of the NMR spin relaxation rates, and indicates possible aggregation of the macromolecular species. This paper reports a novel NMR pulse scheme, [ 15N, 1H]-TRACT, which is based on transverse relaxation-optimized spectroscopy and permits to determine τc for 15N- 1H bonds without interference from dipole-dipole coupling of the amide proton with remote protons. [ 15N, 1H]-TRACT is highly efficient since only a series of one-dimensional NMR spectra need to be recorded. Its use is suggested for a quick estimate of the rotational correlation time, to monitor sample quality and to determine optimal parameters for complex multidimensional NMR experiments. Practical applications are illustrated with the 110 kDa 7,8-dihydroneopterin aldolase from Staphylococcus aureus, the uniformly 15N-labeled Escherichia coli outer membrane protein X (OmpX) in 60 kDa mixed OmpX/DHPC micelles with approximately 90 molecules of unlabeled 1,2-dihexanoyl- sn-glycero-3-phosphocholine (DHPC), and the 16 kDa pheromone-binding protein from Bombyx mori, which cover a wide range of correlation times.

  7. Relaxation-optimised Hartmann-Hahn transfer using a specifically Tailored MOCCA-XY16 mixing sequence for carbonyl-carbonyl correlation spectroscopy in {sup 13}C direct detection NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

    Felli, Isabella C.; Pierattelli, Roberta [University of Florence, Department of Chemistry and Magnetic Resonance Center (CERM) (Italy); Glaser, Steffen J.; Luy, Burkhard [Technische Universitaet Muenchen, Department of Chemistry (Germany)], E-mail: Burkhard.Luy@ch.tum.de

    2009-03-15

    Isotropic mixing sequences are one of the key methods to achieve efficient coherence transfer. Among them, the MOCCA-XY16, which keeps the magnetization longitudinal for a significant amount of time, is characterised by favourable relaxation properties. We show here that its adapted version is particularly suited for carbonyl-carbonyl correlations in {sup 13}C direct detection NMR experiments.

  8. 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...

  9. 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)

  10. 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.

  11. 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)

  12. Benchmarking NMR experiments: a relational database of protein pulse sequences.

    Science.gov (United States)

    Senthamarai, Russell R P; Kuprov, Ilya; Pervushin, Konstantin

    2010-03-01

    Systematic benchmarking of multi-dimensional protein NMR experiments is a critical prerequisite for optimal allocation of NMR resources for structural analysis of challenging proteins, e.g. large proteins with limited solubility or proteins prone to aggregation. We propose a set of benchmarking parameters for essential protein NMR experiments organized into a lightweight (single XML file) relational database (RDB), which includes all the necessary auxiliaries (waveforms, decoupling sequences, calibration tables, setup algorithms and an RDB management system). The database is interfaced to the Spinach library (http://spindynamics.org), which enables accurate simulation and benchmarking of NMR experiments on large spin systems. A key feature is the ability to use a single user-specified spin system to simulate the majority of deposited solution state NMR experiments, thus providing the (hitherto unavailable) unified framework for pulse sequence evaluation. This development enables predicting relative sensitivity of deposited implementations of NMR experiments, thus providing a basis for comparison, optimization and, eventually, automation of NMR analysis. The benchmarking is demonstrated with two proteins, of 170 amino acids I domain of alphaXbeta2 Integrin and 440 amino acids NS3 helicase.

  13. Integration of spin-state-selective excitation into 2D NMR correlation experiments with heteronuclear ZQ/2Q {pi} rotations for{sup 1} J{sub XH}

    Energy Technology Data Exchange (ETDEWEB)

    Meissner, Axel; Duus, Jens O.; Sorensen, Ole Winneche [Department of Chemistry, Carlsberg Laboratory (Denmark)

    1997-07-15

    Spin-State-Selective Excitation (S{sup 3}E), which for example selectively excites amide proton resonances corresponding to exclusively either the {alpha} or the {beta} spin state of the covalently bound {sup 15}N atom is employed for E.COSY-type extraction of heteronuclear J coupling constants. Instead of having one spectrum with two peaks (corresponding to the {alpha} or {beta} spin state of{sup 15}N), S{sup 3}E generates two spectra, each with only one peak for each {sup 15}N nucleus. These two spectra are generated from the same data set, so that there is no reduction in sensitivity compared to conventional {sup 1}J{sub NH}-resolved methods.Another interesting feature in comparison with conventional methods is that{sup 1}J{sub NH} can be suppressed during the evolution period, meaning that no heteronuclear multiplet structure is visible in the{omega}{sub 1} frequency dimension. The S{sup 3}E pulse sequence element is combined with NOESY for measurement of{sup 3}J{sub N-H{beta}} and J{sub N-H{alpha}}coupling constants in either a hetero- or a homonuclear correlated version.Experimental confirmation is obtained using the protein RAP 17-;97(N-terminal domain of {alpha}{sub 2}-macroglobulin Receptor Associated Protein)

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

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Richard [Huazhong University of Science and Technology, School of Software Engineering (China); Wang, Yan [Huazhong University of Science and Technology, School of Life Science and Technology (China); Xue, Zhidong, E-mail: zdxue@hust.edu.cn [Huazhong University of Science and Technology, School of Software Engineering (China); Zhang, Yang, E-mail: zhng@umich.edu [University of Michigan, Department of Computational Medicine and Bioinformatics (United States)

    2015-08-15

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

  15. Structure-Correlation NMR Spectroscopy for Macromolecules Using Repeated Bidirectional Photoisomerization of Azobenzene.

    Science.gov (United States)

    Nagashima, Toshio; Ueda, Keisuke; Nishimura, Chiaki; Yamazaki, Toshio

    2015-11-17

    Control over macromolecular structure offers bright potentials for manipulation of macromolecular functions. We here present structure-correlation NMR spectroscopy to analyze the correlation between polymorphic macromolecular structures driven by photoisomerization of azobenzene. The structural conversion of azobenzene was induced within the mixing time of a NOESY experiment using a colored light source, and the reverse structural conversion was induced during the relaxation delay using a light source of another color. The correlation spectrum between trans- and cis-azobenzene was then obtained. To maximize the efficiency of the bidirectional photoisomerization of azobenzene-containing macromolecules, we developed a novel light-irradiation NMR sample tube and method for irradiating target molecules in an NMR radio frequency (rf) coil. When this sample tube was used for photoisomerization of an azobenzene derivative at a concentration of 0.2 mM, data collection with reasonable sensitivity applicable to macromolecules was achieved. We performed isomerization of an azobenzene-cross-linked peptide within the mixing time of a NOESY experiment that produced cross-peaks between helix and random-coil forms of the peptide. Thus, these results indicate that macromolecular structure manipulation can be incorporated into an NMR pulse sequence using an azobenzene derivative and irradiation with light of two types of wavelengths, providing a new method for structural analysis of metastable states of macromolecules.

  16. Direct correlation of diffusion and pore size distributions with low field NMR

    Science.gov (United States)

    Zhang, Yan; Xiao, Lizhi; Liao, Guangzhi; Song, Yi-Qiao

    2016-08-01

    The time-dependent diffusion coefficient (D) is a powerful tool to probe microstructure in porous media, and can be obtained by the NMR method. In a real porous sample, molecular diffusion is very complex. Here we present a new method which directly measures the relationship between effective diffusion coefficients and pore size distributions without knowing surface relaxivity. This method is used to extract structural information and explore the relationship between D and a in porous media having broad pore size distributions. The diffusion information is encoded by the Pulsed Field Gradient (PFG) method and the pore size distributions are acquired by the Decay due to Diffusion in the Internal Field (DDIF) method. Two model samples were measured to verify this method. Restricted diffusion was analyzed, and shows that most fluid molecules experience pore wall. The D(a) curves obtained from correlation maps were fitted to the Padé approximant equation and a good agreement was found between the fitting lines and the measured data. Then a sandstone sample with unknown structure was measured. The state of confined fluids was analyzed and structural information, such as pore size distributions, were extracted. The D - T1 correlation maps were also obtained using the same method, which yielded surface relaxivities for different samples. All the experiments were conducted on 2 MHz NMR equipment to obtain accurate diffusion information, where internal gradients can be neglected. This method is expected to have useful applications in the oil industry, particularly for NMR logging in the future.

  17. Cation Hydration Constants by Proton NMR: A Physical Chemistry Experiment.

    Science.gov (United States)

    Smith, Robert L.; And Others

    1988-01-01

    Studies the polarization effect on water by cations and anions. Describes an experiment to illustrate the polarization effect of sodium, lithium, calcium, and strontium ions on the water molecule in the hydration spheres of the ions. Analysis is performed by proton NMR. (MVL)

  18. NMR cross-correlated relaxation rates reveal ion coordination sites in DNA

    NARCIS (Netherlands)

    Fiala, R.; Spackova, N.; Foldynová-Trantírková, S.; Sponer, J.; Sklenár, V.; Trantirek, L.

    2011-01-01

    In this work, a novel NMR method for the identification of preferential coordination sites between physiologically relevant counterions and nucleic acid bases is demonstrated. In this approach, the NMR cross-correlated relaxation rates between the aromatic carbon chemical shift anisotropy and the pr

  19. Motions and entropies in proteins as seen in NMR relaxation experiments and molecular dynamics simulations.

    Science.gov (United States)

    Allnér, Olof; Foloppe, Nicolas; Nilsson, Lennart

    2015-01-22

    Molecular dynamics simulations of E. coli glutaredoxin1 in water have been performed to relate the dynamical parameters and entropy obtained in NMR relaxation experiments, with results extracted from simulated trajectory data. NMR relaxation is the most widely used experimental method to obtain data on dynamics of proteins, but it is limited to relatively short timescales and to motions of backbone amides or in some cases (13)C-H vectors. By relating the experimental data to the all-atom picture obtained in molecular dynamics simulations, valuable insights on the interpretation of the experiment can be gained. We have estimated the internal dynamics and their timescales by calculating the generalized order parameters (O) for different time windows. We then calculate the quasiharmonic entropy (S) and compare it to the entropy calculated from the NMR-derived generalized order parameter of the amide vectors. Special emphasis is put on characterizing dynamics that are not expressed through the motions of the amide group. The NMR and MD methods suffer from complementary limitations, with NMR being restricted to local vectors and dynamics on a timescale determined by the rotational diffusion of the solute, while in simulations, it may be difficult to obtain sufficient sampling to ensure convergence of the results. We also evaluate the amount of sampling obtained with molecular dynamics simulations and how it is affected by the length of individual simulations, by clustering of the sampled conformations. We find that two structural turns act as hinges, allowing the α helix between them to undergo large, long timescale motions that cannot be detected in the time window of the NMR dipolar relaxation experiments. We also show that the entropy obtained from the amide vector does not account for correlated motions of adjacent residues. Finally, we show that the sampling in a total of 100 ns molecular dynamics simulation can be increased by around 50%, by dividing the

  20. 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.

  1. Robust, integrated computational control of NMR experiments to achieve optimal assignment by ADAPT-NMR.

    Science.gov (United States)

    Bahrami, Arash; Tonelli, Marco; Sahu, Sarata C; Singarapu, Kiran K; Eghbalnia, Hamid R; Markley, John L

    2012-01-01

    ADAPT-NMR (Assignment-directed Data collection Algorithm utilizing a Probabilistic Toolkit in NMR) represents a groundbreaking prototype for automated protein structure determination by nuclear magnetic resonance (NMR) spectroscopy. With a [(13)C,(15)N]-labeled protein sample loaded into the NMR spectrometer, ADAPT-NMR delivers complete backbone resonance assignments and secondary structure in an optimal fashion without human intervention. ADAPT-NMR achieves this by implementing a strategy in which the goal of optimal assignment in each step determines the subsequent step by analyzing the current sum of available data. ADAPT-NMR is the first iterative and fully automated approach designed specifically for the optimal assignment of proteins with fast data collection as a byproduct of this goal. ADAPT-NMR evaluates the current spectral information, and uses a goal-directed objective function to select the optimal next data collection step(s) and then directs the NMR spectrometer to collect the selected data set. ADAPT-NMR extracts peak positions from the newly collected data and uses this information in updating the analysis resonance assignments and secondary structure. The goal-directed objective function then defines the next data collection step. The procedure continues until the collected data support comprehensive peak identification, resonance assignments at the desired level of completeness, and protein secondary structure. We present test cases in which ADAPT-NMR achieved results in two days or less that would have taken two months or more by manual approaches.

  2. Robust, integrated computational control of NMR experiments to achieve optimal assignment by ADAPT-NMR.

    Directory of Open Access Journals (Sweden)

    Arash Bahrami

    Full Text Available ADAPT-NMR (Assignment-directed Data collection Algorithm utilizing a Probabilistic Toolkit in NMR represents a groundbreaking prototype for automated protein structure determination by nuclear magnetic resonance (NMR spectroscopy. With a [(13C,(15N]-labeled protein sample loaded into the NMR spectrometer, ADAPT-NMR delivers complete backbone resonance assignments and secondary structure in an optimal fashion without human intervention. ADAPT-NMR achieves this by implementing a strategy in which the goal of optimal assignment in each step determines the subsequent step by analyzing the current sum of available data. ADAPT-NMR is the first iterative and fully automated approach designed specifically for the optimal assignment of proteins with fast data collection as a byproduct of this goal. ADAPT-NMR evaluates the current spectral information, and uses a goal-directed objective function to select the optimal next data collection step(s and then directs the NMR spectrometer to collect the selected data set. ADAPT-NMR extracts peak positions from the newly collected data and uses this information in updating the analysis resonance assignments and secondary structure. The goal-directed objective function then defines the next data collection step. The procedure continues until the collected data support comprehensive peak identification, resonance assignments at the desired level of completeness, and protein secondary structure. We present test cases in which ADAPT-NMR achieved results in two days or less that would have taken two months or more by manual approaches.

  3. Chemical-shift-resolved ¹⁹F NMR spectroscopy between 13.5 and 135 MHz: Overhauser-DNP-enhanced diagonal suppressed correlation spectroscopy.

    Science.gov (United States)

    George, Christy; Chandrakumar, Narayanan

    2014-08-01

    Overhauser-DNP-enhanced homonuclear 2D (19)F correlation spectroscopy with diagonal suppression is presented for small molecules in the solution state at moderate fields. Multi-frequency, multi-radical studies demonstrate that these relatively low-field experiments may be operated with sensitivity rivalling that of standard 200-1000 MHz NMR spectroscopy. Structural information is accessible without a sensitivity penalty, and diagonal suppressed 2D NMR correlations emerge despite the general lack of multiplet resolution in the 1D ODNP spectra. This powerful general approach avoids the rather stiff excitation, detection, and other special requirements of high-field (19)F NMR spectroscopy.

  4. Multidimensional J-driven NMR correlations by single-scan offset-encoded recoupling

    Science.gov (United States)

    Lin, Yulan; Lupulescu, Adonis; Frydman, Lucio

    2016-04-01

    Two-dimensional (2D) correlations between bonded heteroatoms, lie at the cornerstone of many uses given to contemporary nuclear magnetic resonance (NMR). Improving the efficiency with which these correlations are established is an important topic in modern NMR, with potential applications in rapid chemical analysis and dynamic biophysical studies. Alternatives have been developed over the last decade to speed up these experiments, based among others on reducing the number of data points that need to be sampled, and/or shortening the inter-scan delays. Approaches have also been proposed to forfeit multi-scan schemes altogether, and complete full 2D correlations in a single shot. Here we explore and discuss a new alternative enabling the collection of such very fast - in principle, single-scan - acquisitions of 2D heteronuclear correlations among bonded species, which operates on the basis of a partial reintroduction of J couplings. Similar approaches had been proposed in the past based on collecting coupled spectra for arrays of off-resonance decoupling values; the proposal that is here introduced operates on the basis of suitably incorporating frequency-swept pulses, into spin-echo sequences. Thanks to the offset-dependent amplitude modulations of the in- and anti-phase components that such sequences impart, chemical shifts of coupled but otherwise unobserved nuclear species, can be extracted from the relative intensities and phases of J-coupled multiplets observed in one-dimensional acquisitions. A description of the steps needed to implement this rapid acquisition approach in a quantitative fashion, as well as applications of the ensuing sequences, are presented.

  5. 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.

  6. Spectroscopic correlation analysis of NMR-based metabonomics in exercise science.

    Science.gov (United States)

    Kirwan, Gemma M; Coffey, Vernon G; Niere, Julie O; Hawley, John A; Adams, Michael J

    2009-10-12

    Spectroscopic studies of complex clinical fluids have led to the application of a more holistic approach to their chemical analysis becoming more popular and widely employed. The efficient and effective interpretation of multidimensional spectroscopic data relies on many chemometric techniques and one such group of tools is represented by so-called correlation analysis methods. Typical of these techniques are two-dimensional correlation analysis and statistical total correlation spectroscopy (STOCSY). Whilst the former has largely been applied to optical spectroscopic analysis, STOCSY was developed and has been applied almost exclusively to NMR metabonomic studies. Using a (1)H NMR study of human blood plasma, from subjects recovering from exhaustive exercise trials, the basic concepts and applications of these techniques are examined. Typical information from their application to NMR-based metabonomics is presented and their value in aiding interpretation of NMR data obtained from biological systems is illustrated. Major energy metabolites are identified in the NMR spectra and the dynamics of their appearance and removal from plasma during exercise recovery are illustrated and discussed. The complementary nature of two-dimensional correlation analysis and statistical total correlation spectroscopy are highlighted.

  7. Generalised 2D-correlation NMR analysis of a wine fermentation.

    Science.gov (United States)

    Kirwan, Gemma M; Clark, Shona; Barnett, Neil W; Niere, Julie O; Adams, Michael J

    2008-11-23

    A wine fermentation has been monitored on a daily basis by (1)H NMR spectroscopy. Following data pre-processing that includes synthesis of the spectra to ensure all peaks are of constant half-width, the series of spectra were examined using generalised two-dimensional correlation techniques. Synchronous and asynchronous data maps have been generated and employed to interpret the changes in the fermentation process as a function of time. The results illustrate the potential of high resolution NMR with multivariate data analysis as a tool for process monitoring and the manner in which two-dimensional correlation mapping can aid in data interpretation.

  8. Correlating nuclear frequencies by two-dimensional ELDOR-detected NMR spectroscopy.

    Science.gov (United States)

    Kaminker, Ilia; Wilson, Tiffany D; Savelieff, Masha G; Hovav, Yonatan; Zimmermann, Herbert; Lu, Yi; Goldfarb, Daniella

    2014-03-01

    ELDOR (Electron Double Resonance)-detected NMR (EDNMR) is a pulse EPR experiment that is used to measure the transition frequencies of nuclear spins coupled to electron spins. These frequencies are further used to determine hyperfine and quadrupolar couplings, which are signatures of the electronic and spatial structures of paramagnetic centers. In recent years, EDNMR has been shown to be particularly useful at high fields/high frequencies, such as W-band (∼95 GHz, ∼3.5 T), for low γ quadrupolar nuclei. Although at high fields the nuclear Larmor frequencies are usually well resolved, the limited resolution of EDNMR still remains a major concern. In this work we introduce a two dimensional, triple resonance, correlation experiment based on the EDNMR pulse sequence, which we term 2D-EDNMR. This experiment allows circumventing the resolution limitation by spreading the signals in two dimensions and the observed correlations help in the assignment of the signals. First we demonstrate the utility of the 2D-EDNMR experiment on a nitroxide spin label, where we observe correlations between (14)N nuclear frequencies. Negative cross-peaks appear between lines belonging to different MS electron spin manifolds. We resolved two independent correlation patterns for nuclear frequencies arising from the EPR transitions corresponding to the (14)N mI=0 and mI=-1 nuclear spin states, which severely overlap in the one dimensional EDNMR spectrum. The observed correlations could be accounted for by considering changes in the populations of energy levels that S=1/2, I=1 spin systems undergo during the pulse sequence. In addition to these negative cross-peaks, positive cross-peaks appear as well. We present a theoretical model based on the Liouville equation and use it to calculate the time evolution of populations of the various energy levels during the 2D-EDNMR experiment and generated simulated 2D-EDMR spectra. These calculations show that the positive cross-peaks appear due to

  9. Correlating nuclear frequencies by two-dimensional ELDOR-detected NMR spectroscopy

    Science.gov (United States)

    Kaminker, Ilia; Wilson, Tiffany D.; Savelieff, Masha G.; Hovav, Yonatan; Zimmermann, Herbert; Lu, Yi; Goldfarb, Daniella

    2014-03-01

    ELDOR (Electron Double Resonance)-detected NMR (EDNMR) is a pulse EPR experiment that is used to measure the transition frequencies of nuclear spins coupled to electron spins. These frequencies are further used to determine hyperfine and quadrupolar couplings, which are signatures of the electronic and spatial structures of paramagnetic centers. In recent years, EDNMR has been shown to be particularly useful at high fields/high frequencies, such as W-band (∼95 GHz, ∼3.5 T), for low γ quadrupolar nuclei. Although at high fields the nuclear Larmor frequencies are usually well resolved, the limited resolution of EDNMR still remains a major concern. In this work we introduce a two dimensional, triple resonance, correlation experiment based on the EDNMR pulse sequence, which we term 2D-EDNMR. This experiment allows circumventing the resolution limitation by spreading the signals in two dimensions and the observed correlations help in the assignment of the signals. First we demonstrate the utility of the 2D-EDNMR experiment on a nitroxide spin label, where we observe correlations between 14N nuclear frequencies. Negative cross-peaks appear between lines belonging to different MS electron spin manifolds. We resolved two independent correlation patterns for nuclear frequencies arising from the EPR transitions corresponding to the 14N mI = 0 and mI = -1 nuclear spin states, which severely overlap in the one dimensional EDNMR spectrum. The observed correlations could be accounted for by considering changes in the populations of energy levels that S = 1/2, I = 1 spin systems undergo during the pulse sequence. In addition to these negative cross-peaks, positive cross-peaks appear as well. We present a theoretical model based on the Liouville equation and use it to calculate the time evolution of populations of the various energy levels during the 2D-EDNMR experiment and generated simulated 2D-EDMR spectra. These calculations show that the positive cross-peaks appear due

  10. NMR spectroscopy study of local correlations in water

    Science.gov (United States)

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Stanley, H. Eugene

    2016-12-01

    Using nuclear magnetic resonance we study the dynamics of the hydrogen bond (HB) sub-domains in bulk and emulsified water across a wide temperature range that includes the supercooled regime. We measure the proton spin-lattice T1 and spin-spin T2 relaxation times to understand the hydrophilic interactions that determine the properties of water. We use (i) the Bloembergen, Purcell, and Pound approach that focuses on a single characteristic correlation time τc, and (ii) the Powles and Hubbard approach that measures the proton rotational time τθ. We find that when the temperature is low both relaxation times are strongly correlated when the HB lifetime is long, and that when the temperature is high a decrease in the HB lifetime destroys the water clusters and decouples the dynamic modes of the system.

  11. Indirectly detected chemical shift correlation NMR spectroscopy in solids under fast magic angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Kanmi [Iowa State Univ., Ames, IA (United States)

    2011-01-01

    The development of fast magic angle spinning (MAS) opened up an opportunity for the indirect detection of insensitive low-γ nuclei (e.g., 13C and 15N) via the sensitive high-{gamma} nuclei (e.g., 1H and 19F) in solid-state NMR, with advanced sensitivity and resolution. In this thesis, new methodology utilizing fast MAS is presented, including through-bond indirectly detected heteronuclear correlation (HETCOR) spectroscopy, which is assisted by multiple RF pulse sequences for 1H-1H homonuclear decoupling. Also presented is a simple new strategy for optimization of 1H-1H homonuclear decoupling. As applications, various classes of materials, such as catalytic nanoscale materials, biomolecules, and organic complexes, are studied by combining indirect detection and other one-dimensional (1D) and two-dimensional (2D) NMR techniques. Indirectly detected through-bond HETCOR spectroscopy utilizing refocused INEPT (INEPTR) mixing was developed under fast MAS (Chapter 2). The time performance of this approach in 1H detected 2D 1H{l_brace}13C{r_brace} spectra was significantly improved, by a factor of almost 10, compared to the traditional 13C detected experiments, as demonstrated by measuring naturally abundant organic-inorganic mesoporous hybrid materials. The through-bond scheme was demonstrated as a new analytical tool, which provides complementary structural information in solid-state systems in addition to through-space correlation. To further benefit the sensitivity of the INEPT transfer in rigid solids, the combined rotation and multiple-pulse spectroscopy (CRAMPS) was implemented for homonuclear 1H decoupling under fast MAS (Chapter 3). Several decoupling schemes (PMLG5m$\\bar{x}$, PMLG5mm$\\bar{x}$x and SAM3) were analyzed to maximize the performance of through-bond transfer based

  12. A general framework to quantify the effect of restricted diffusion on the NMR signal with applications to double pulsed field gradient NMR experiments.

    Science.gov (United States)

    Ozarslan, Evren; Shemesh, Noam; Basser, Peter J

    2009-03-14

    Based on a description introduced by Robertson, Grebenkov recently introduced a powerful formalism to represent the diffusion-attenuated NMR signal for simple pore geometries such as slabs, cylinders, and spheres analytically. In this work, we extend this multiple correlation function formalism by allowing for possible variations in the direction of the magnetic field gradient waveform. This extension is necessary, for example, to incorporate the effects of imaging gradients in diffusion-weighted NMR imaging scans and in characterizing anisotropy at different length scales via double pulsed field gradient (PFG) experiments. In cylindrical and spherical pores, respectively, two- and three-dimensional vector operators are employed whose form is deduced from Grebenkov's results via elementary operator algebra for the case of cylinders and the Wigner-Eckart theorem for the case of spheres. The theory was validated by comparison with known findings and with experimental double-PFG data obtained from water-filled microcapillaries.

  13. 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.

  14. Metabolic response to exogenous ethanol in yeast: An in vivo statistical total correlation NMR spectroscopy approach

    Indian Academy of Sciences (India)

    Maso Ricci; Marianna Aggravi; Claudia Bonechi; Silvia Martini; Anna Maria; Claudio Rossi

    2012-09-01

    In vivo NMR spectroscopy, together with selectively 13C-labelled substrates and ‘statistical total correlation spectroscopy’ analysis (STOCSY), are valuable tools to collect and interpret the metabolic responses of a living organism to external stimuli. In this study, we applied this approach to evaluate the effects of increasing concentration of exogenous ethanol on the Saccharomyces cerevisiae fermentative metabolism. We show that the STOCSY analysis correctly identifies the different types of correlations among the enriched metabolites involved in the fermentation, and that these correlations are quite stable even in presence of a stressing factor such as the exogenous ethanol.

  15. Metabolic response to exogenous ethanol in yeast: an in vivo statistical total correlation NMR spectroscopy approach.

    Science.gov (United States)

    Ricci, Maso; Aggravi, Marianna; Bonechi, Claudia; Martini, Silvia; Aloisi, Anna Maria; Rossi, Claudio

    2012-09-01

    In vivo NMR spectroscopy, together with selectively 13C-labelled substrates and 'statistical total correlation spectroscopy' analysis (STOCSY), are valuable tools to collect and interpret the metabolic responses of a living organism to external stimuli. In this study, we applied this approach to evaluate the effects of increasing concentration of exogenous ethanol on the Saccharomyces cerevisiae fermentative metabolism. We show that the STOCSY analysis correctly identifies the different types of correlations among the enriched metabolites involved in the fermentation, and that these correlations are quite stable even in presence of a stressing factor such as the exogenous ethanol.

  16. Because the Light is Better Here: Correlation-Time Analysis by NMR Spectroscopy.

    Science.gov (United States)

    Smith, Albert A; Ernst, Matthias; Meier, Beat H

    2017-08-30

    Relaxation data in NMR spectra are often used for dynamics analysis, by modeling motion in the sample with a correlation function consisting of one or more decaying exponential terms, each described by an order parameter, and a correlation time. This method has its origins in the Lipari-Szabo model-free approach, which originally considered overall tumbling plus one internal motion and was later expanded to several internal motions. Considering several of these cases in the solid state it is found that if the real motion is more complex than the assumed model, model fitting is biased towards correlation times where the relaxation data are most sensitive. This leads to unexpected distortions in the resulting dynamics description. Therefore dynamics detectors should be used, which characterize different ranges of correlation times and can help in the analysis of protein motion without assuming a specific model of the correlation function. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Spatial reorientation experiments for NMR of solids and partially oriented liquids.

    Science.gov (United States)

    Martin, Rachel W; Kelly, John E; Collier, Kelsey A

    2015-11-01

    Motional reorientation experiments are extensions of Magic Angle Spinning (MAS) where the rotor axis is changed in order to average out, reintroduce, or scale anisotropic interactions (e.g. dipolar couplings, quadrupolar interactions or chemical shift anisotropies). This review focuses on Variable Angle Spinning (VAS), Switched Angle Spinning (SAS), and Dynamic Angle Spinning (DAS), all of which involve spinning at two or more different angles sequentially, either in successive experiments or during a multidimensional experiment. In all of these experiments, anisotropic terms in the Hamiltonian are scaled by changing the orientation of the spinning sample relative to the static magnetic field. These experiments vary in experimental complexity and instrumentation requirements. In VAS, many one-dimensional spectra are collected as a function of spinning angle. In SAS, dipolar couplings and/or chemical shift anisotropies are reintroduced by switching the sample between two different angles, often 0° or 90° and the magic angle, yielding a two-dimensional isotropic-anisotropic correlation spectrum. Dynamic Angle Spinning (DAS) is a related experiment that is used to simultaneously average out the first- and second-order quadrupolar interactions, which cannot be accomplished by spinning at any unique rotor angle in physical space. Although motional reorientation experiments generally require specialized instrumentation and data analysis schemes, some are accessible with only minor modification of standard MAS probes. In this review, the mechanics of each type of experiment are described, with representative examples. Current and historical probe and coil designs are discussed from the standpoint of how each one accomplishes the particular objectives of the experiment(s) it was designed to perform. Finally, applications to inorganic materials and liquid crystals, which present very different experimental challenges, are discussed. The review concludes with perspectives

  18. Citrus Quality Control: An NMR/MRI Problem-Based Experiment

    Science.gov (United States)

    Erhart, Sarah E.; McCarrick, Robert M.; Lorigan, Gary A.; Yezierski, Ellen J.

    2016-01-01

    An experiment seated in an industrial context can provide an engaging framework and unique learning opportunity for an upper-division physical chemistry laboratory. An experiment that teaches NMR/MRI through a problem-based quality control of citrus products was developed. In this experiment, using a problem-based learning (PBL) approach, students…

  19. Direct correlation of internal gradients and pore size distributions with low field NMR

    Science.gov (United States)

    Zhang, Yan; Xiao, Lizhi; Liao, Guangzhi; Blümich, Bernhard

    2016-06-01

    Internal magnetic field gradients Gint, which arise from the magnetic susceptibility difference Δχ between solid matrix and fluid in porous media relate to the pore geometry. However, this relationship is complex and not well understood. Here we correlate internal-gradient distributions to pore-size distributions directly to examine internal gradients in detail at low field NMR. The pore-size distributions were obtained by the method of Decay due to Diffusion in the Internal Field (DDIF), and the internal-gradient distributions were measured with the Carr-Purcell-Meiboom-Gill (CPMG) method. The internal-gradient-pore-size distributions correlation maps were obtained for water in packs of glass beads with different diameter and in a sandstone sample. The relationship between internal gradients and pore structure is analyzed in detail by considering the restricted diffusion of fluids in porous samples. For each case diffusion regimes are assigned by plotting normalized CPMG data and comparing the diffusion lengths, the dephasing lengths and pore diameters. In the free-diffusion limit, the correlation maps reveal the true relationship between pore structure and internal gradients so that Δχ can be approximated from the correlation maps. This limit is met most easily at low field. It provides information about porous media, which is expected to benefit the oil industry, in particular NMR well logging.

  20. Correlation of tryptophan fluorescence intensity decay parameters with sup 1 H NMR-determined rotamer conformations: (tryptophan sup 2 )oxytocin

    Energy Technology Data Exchange (ETDEWEB)

    Ross, J.B.A.; Schwartz, G.P.; Laws, W.R. (Mount Sinai, New York, NY (United States)); Wyssbrod, H.R.; Porter, R.A. (Univ. of Louisville, KY (United States)); Michaels, C.A. (Swarthmore Coll., PA (United States))

    1992-02-18

    While the fluorescence decay kinetics of tyrosine model compounds can be explained in terms of heterogeneity derived from the three ground-state {chi}{sup 1} rotamers, a similar correlation has yet to be directly observed for a tryptophan residue. In addition, the asymmetric indole ring might also lead to heterogeneity from {chi}{sup 2} rotations. In this paper, the time-resolved and steady-state fluorescence properties of (tryptophan{sup 2})oxytocin at pH 3 are presented and compared with {sup 1}H NMR results. According to the unrestricted analyses of individual fluorescence decay curves taken as a function of emission wavelength-independent decay constants, only three exponential terms are required. In addition, the preexponential weighting factors (amplitudes) have the same relative relationship (weights) as the {sup 1}H NMR-determined {chi}{sup 1} rotamer populations of the indole side chain. {sup 15}N was used in heteronuclear coupling experiments to confirm the rotamer assignments. Inclusion of a linked function restricting the decay amplitudes to the {chi}{sup 1} rotamer populations in the individual decay curve analyses and in the global analysis confirms this correlation. According to qualitative nuclear Overhauser data, there are two {chi}{sup 2} populations.

  1. Report for in-situ 7Li NMR experiment in PNNL Phase -1

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Jian Zhi [Pacific Northwest National Laboratory

    2014-08-19

    To understand the detailed local structural evolution, an in-situ 7Li NMR study was performed. An operando identification of the lithium germanide phases under various cycling regimens permitted understanding of the kinetics of phase transition between different structural phases, including the amorphous phases, and how these correlated with capacity retention. Combining data from TEM and in-situ 7Li NMR, we discovered that the phase inter-conversion during cycling was mediated by co-existing amorphous and crystalline phases, and that the high capacity observed was correlated with an over-lithiated lithium germanide phase.

  2. Determination of protein rotational correlation time from NMR relaxation data at various solvent viscosities

    Energy Technology Data Exchange (ETDEWEB)

    Korchuganov, Denis S.; Gagnidze, Ivan E.; Tkach, Elena N.; Schulga, Alexey A.; Kirpichnikov, Mikhail P.; Arseniev, Alexander S. [Russian Academy of Sciences, Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry (Russian Federation)], E-mail: aars@nmr.ru

    2004-12-15

    An accurate determination of the overall rotation of a protein plays a crucial role in the investigation of its internal motions by NMR. In the present work, an innovative approach to the determination of the protein rotational correlation time {tau}{sub R} from the heteronuclear relaxation data is proposed. The approach is based on a joint fit of relaxation data acquired at several viscosities of a protein solution. The method has been tested on computer simulated relaxation data as compared to the traditional {tau}{sub R} determination method from T{sub 1}/T{sub 2} ratio. The approach has been applied to ribonuclease barnase from Bacillus amyloliquefaciens dissolved in an aqueous solution and deuterated glycerol as a viscous component. The resulting rotational correlation time of 5.56 {+-} 0.01 ns and other rotational diffusion tensor parameters are in good agreement with those determined from T{sub 1}/T{sub 2} ratio.

  3. The Heteronuclear Single-Quantum Correlation (HSQC) Experiment: Vectors versus Product Operators

    Science.gov (United States)

    de la Vega-Herna´ndez, Karen; Antuch, Manuel

    2015-01-01

    A vectorial representation of the full sequence of events occurring during the 2D-NMR heteronuclear single-quantum correlation (HSQC) experiment is presented. The proposed vectorial representation conveys an understanding of the magnetization evolution during the HSQC pulse sequence for those who have little or no quantum mechanical background.…

  4. Effects of radiation damping for biomolecular NMR experiments in solution: a hemisphere concept for water suppression.

    Science.gov (United States)

    Ishima, Rieko

    2015-09-01

    Abundant solvent nuclear spins, such as water protons in aqueous solution, cause radiation damping in NMR experiments. It is important to know how the effect of radiation damping appears in high-resolution protein NMR because macromolecular studies always require very high magnetic field strengths with a highly sensitive NMR probe that can easily cause radiation damping. Here, we show the behavior of water magnetization after a pulsed-field gradient (PFG) using nutation experiments at 900 MHz with a cryogenic probe: when water magnetization is located in the upper hemisphere (having +Z component, parallel to the external magnetic field), dephasing of the magnetization by a PFG effectively suppresses residual water magnetization in the transverse plane. In contrast, when magnetization is located in the lower hemisphere (having -Z component), the small residual transverse component remaining after a PFG is still sufficient to induce radiation damping. Based on this observation, we designed (1)H-(15)N HSQC experiments in which water magnetization is maintained in the upper hemisphere, but not necessarily along Z, and compared them with the conventional experiments, in which water magnetization is inverted during the t1 period. The result demonstrates moderate gain of signal-to-noise ratio, 0-28%. Designing the experiments such that water magnetization is maintained in the upper hemisphere allows shorter pulses to be used compared to the complete water flip-back and, thereby, is useful as a building block of protein NMR pulse programs in solution.

  5. NMR Determination of Hydrogen Bond Thermodynamics in a Simple Diamide: A Physical Chemistry Experiment

    Science.gov (United States)

    Morton, Janine G.; Joe, Candice L.; Stolla, Massiel C.; Koshland, Sophia R.; Londergan, Casey H.; Schofield, Mark H.

    2015-01-01

    Variable temperature NMR spectroscopy is used to determine the ?H° and ?S° of hydrogen bond formation in a simple diamide. In this two- or three-day experiment, students synthesize N,N'-dimethylmalonamide, dimethylsuccinamide, dimethylglutaramide, or dimethyladipamide from methylamine and the corresponding diester (typically in 50% recrystallized…

  6. NMR Determination of Hydrogen Bond Thermodynamics in a Simple Diamide: A Physical Chemistry Experiment

    Science.gov (United States)

    Morton, Janine G.; Joe, Candice L.; Stolla, Massiel C.; Koshland, Sophia R.; Londergan, Casey H.; Schofield, Mark H.

    2015-01-01

    Variable temperature NMR spectroscopy is used to determine the ?H° and ?S° of hydrogen bond formation in a simple diamide. In this two- or three-day experiment, students synthesize N,N'-dimethylmalonamide, dimethylsuccinamide, dimethylglutaramide, or dimethyladipamide from methylamine and the corresponding diester (typically in 50% recrystallized…

  7. Intermediate length scale organisation in tin borophosphate glasses: new insights from high field correlation NMR.

    Science.gov (United States)

    Tricot, G; Saitoh, A; Takebe, H

    2015-11-28

    The structure of tin borophosphate glasses, considered for the development of low temperature sealing glasses or anode materials for Li-batteries, has been analysed at the intermediate length scale by a combination of high field standard and advanced 1D/2D nuclear magnetic resonance techniques. The nature and extent of B/P mixing were analysed using the (11)B((31)P) dipolar heteronuclear multiple quantum coherence NMR sequence and the data interpretation allowed (i) detecting the presence and analysing the nature of the B-O-P linkages, (ii) re-interpreting the 1D (31)P spectra and (iii) extracting the proportion of P connected to borate species. Interaction between the different borate species was analysed using the (11)B double quantum-simple quantum experiment to (i) investigate the presence and nature of the B-O-B linkage, (ii) assign the different borate species observed all along the composition line and (iii) monitor the borate network formation. In addition, (119)Sn static NMR was used to investigate the evolution of the chemical environment of the tin polyhedra. Altogether, the set of data allowed determining the structural units constituting the glass network and quantifying the extent of B/P mixing. The structural data were then used to explain the non-linear and unusual evolution of the glass transition temperature.

  8. Perturbed Angular Correlation (PAC)/NMR spectroscopic properties and dynamics of compounds containing metal ions

    DEFF Research Database (Denmark)

    Arcisauskaité, Vaida

    steps towards understanding how Zn(II) reaches its target position in biological systems in vivo and in vitro experiments in aqueous solution, is the detailed investigation of water exchange reactions for Zn(II)(aq). A very advanced (albeit not complete) picture of structure and dynamics of solvated Zn......199mHg PAC and 199Hg NMR spectroscopic properties, nuclear quadrupole coupling constants, Q, asymmetry parameters, , and chemical shifts, , respectively, are the fingerprint of the local molecular and electronic structure, at the probed Hg nuclei. For this reason, these spectroscopic techniques...... compounds in terms of the atomic constituents. The analysis provided a chemophysical interpretation of changes in Vzz upon structural distortions and ligand exchange. The gained insights can be useful when predicting and understanding changes in Q values for Hg binding sites in proteins. One of the first...

  9. Correlative and quantitative 1H NMR-based metabolomics reveals specific metabolic pathway disturbances in diabetic rats.

    Science.gov (United States)

    Zhang, Shucha; Nagana Gowda, G A; Asiago, Vincent; Shanaiah, Narasimhamurthy; Barbas, Coral; Raftery, Daniel

    2008-12-01

    Type 1 diabetes was induced in Sprague-Dawley rats using streptozotocin. Rat urine samples (8 diabetic and 10 control) were analyzed by 1H nuclear magnetic resonance (NMR) spectroscopy. The derived metabolites using univariate and multivariate statistical analysis were subjected to correlative analysis. Plasma metabolites were measured by a series of bioassays. A total of 17 urinary metabolites were identified in the 1H NMR spectra and the loadings plots after principal components analysis. Diabetic rats showed significantly increased levels of glucose (P cycle and a contribution from gut microbial metabolism. Specific perturbed metabolic pathways include the glucose-alanine and Cori cycles, the acetate switch, and choline metabolism. Detection of the altered metabolic pathways and bacterial metabolites using this correlative and quantitative NMR-based metabolomics approach should help to further the understanding of diabetes-related mechanisms.

  10. Reduced Dimensionality (4,3)D-hnCOCANH Experiment: An Efficient Backbone Assignment tool for NMR studies of Proteins

    CERN Document Server

    Kumar, Dinesh

    2013-01-01

    Sequence specific resonance assignment and secondary structure determination of proteins form the basis for variety of structural and functional proteomics studies by NMR. In this context, an efficient standalone method for rapid assignment of backbone (1H, 15N, 13Ca and 13C') resonances and secondary structure determination of proteins has been presented here. Compared to currently available strategies used for the purpose, the method employs only a single reduced dimensionality (RD) experiment -(4,3)D-hnCOCANH and exploits the linear combinations of backbone (13Ca and 13C') chemical shifts to achieve a dispersion relatively better compared to those of individual chemical shifts (see the text) for efficient and rapid data analysis. Further, the experiment leads to the spectrum with direct distinction of self (intra-residue) and sequential (inter-residue) carbon correlation peaks; these appear opposite in signs and therefore can easily be discriminated without using an additional complementary experiment. On ...

  11. Correlation of 1H NMR Chemical Shift for Aqueous Solutions by Statistical Associating Fluid Theory Association Model

    Institute of Scientific and Technical Information of China (English)

    许波; 李浩然; 王从敏; 许映杰; 韩世钧

    2005-01-01

    1H NMR chemical shifts of binary aqueous mixtures of acylamide, alcohol, dimethyl sulphoxide (DMSO), and acetone are correlated by statistical associating fluid theory (SAFT) association model. The comparison between SAFT association model and Wilson equation shows that the former is better for dealing with aqueous solutions. Finally, the specialties of both models are discussed.

  12. The theoretic design of NMR pulses program of arbitrary N-qubit Grover's algorithm and the NMR experiment proof

    Institute of Scientific and Technical Information of China (English)

    杨晓冬; 缪希茄

    2002-01-01

    Grover's quantum searching algorithm is most widely studied in the current quantum computation research, and has been implemented experimentally by NMR (Nuclear Magnetic Resonance) technique. In this article, we design arbitrary N-qubit NMR pulses program of Grover's algorithm based on the multiple-quantum operator algebra theory and demonstrate 2-qubit pulses program experimentally. The result also proves the validity of the multiple-quantum operator algebra theory.

  13. Hydrolysis Studies and Quantitative Determination of Aluminum Ions Using [superscript 27]Al NMR: An Undergraduate Analytical Chemistry Experiment

    Science.gov (United States)

    Curtin, Maria A.; Ingalls, Laura R.; Campbell, Andrew; James-Pederson, Magdalena

    2008-01-01

    This article describes a novel experiment focused on metal ion hydrolysis and the equilibria related to metal ions in aqueous systems. Using [superscript 27]Al NMR, the students become familiar with NMR spectroscopy as a quantitative analytical tool for the determination of aluminum by preparing a standard calibration curve using standard aluminum…

  14. Director tumbling of nematic wormlike micelles under shear: time-resolved rheo-NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

    Sinyavsky, N. [Dept. of Physics, Baltic State Academy, Kaliningrad (Russian Federation); Quijada-Garrido, I. [Inst. de Ciencia y Tecnologia de Polimeros, Consejo Superior de Investigaciones Cientificas, Madrid (Spain); Schmidt, C. [Dept. Chemie, Univ. Paderborn (Germany)

    2007-07-01

    Nematic liquid crystals show a complex flow behavior due to the coupling between orientation and flow. Some materials show a stable director orientation in steady shear flow (flow aligning), while for others no stable director orientation exists (tumbling). Director tumbling gives rise to oscillations of shear and normal stresses in rheological experiments and can be detected by optical methods, for example by microscopy or birefringence measurements. We have used deuterium NMR spectroscopy to observe shear-induced director orientations. In the lyotropic system cetylpyridinium chloride/hexanol/brine, which forms a nematic phase of wormlike micelles, time-resolved observations of the director orientation by means of deuterium NMR spectroscopy of D{sub 2}O have been possible for the first time. The time-dependence of the director orientations in both shear start-up and flow-reversal experiments will be presented. (orig.)

  15. NMR artifacts caused by decoupling of multiple-spin coherences: improved SLAP experiment.

    Science.gov (United States)

    Blechta, Vratislav; Schraml, Jan

    2015-06-01

    Contrary to common expectations, multiple-spin coherences containing products of proton and heteronucleus operators (e.g. Hu Cx , u = x, y, z) can produce not only sidebands but also noticeable centerband NMR signals of the heteronucleus during acquisition under 1H broadband decoupling. Such centerband signals of low abundant heteronuclei can be sources of relatively strong unexpected artifacts in NMR experiments that aim to detect very weak signals from much less-abundant isotopomers, e.g. 13C-13C ones. These findings lead to a new design of Sign Labeled Polarization Transfer (SLAP) pulse sequence (MSS-SLAP) with improved suppression of centerband peaks that are because of singly, e.g. 13C, labeled molecules (parent peaks). The MSS-SLAP experiment and its MSS-BIRD-SLAP variant are compared with a few older SLAP versions.

  16. Psychophysiological Correlations with Gameplay Experience Dimensions

    CERN Document Server

    Drachen, Anders; Yannakakis, Georgios; Pedersen, Anja Lee

    2010-01-01

    In this paper, we report a case study using two easy-to-deploy psychophysiological measures - electrodermal activity (EDA) and heart rate (HR) - and correlating them with a gameplay experience questionnaire (GEQ) in an attempt to establish this mixed-methods approach for rapid application in a commercial game development context. Results indicate that there is a statistically significant correlation (p < 0.01) between measures of psychophysiological arousal (HR, EDA) and self-reported UX in games (GEQ), with some variation between the EDA and HR measures. Results are consistent across three major commercial First-Person Shooter (FPS) games.

  17. Hypothesis: the sound of the individual metabolic phenotype? Acoustic detection of NMR experiments.

    Science.gov (United States)

    Cacciatore, Stefano; Saccenti, Edoardo; Piccioli, Mario

    2015-03-01

    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 healthy donors were converted into audio signals that were analyzed in two audio experiments by listeners with both musical and non-musical training. The listeners were first asked to cluster the audio signals of two donors on the basis of perceived similarity and then to classify unknown samples after having listened to a set of reference signals. In the clustering experiment, the probability of obtaining the same results by pure chance was 7.04% and 0.05% for non-musicians and musicians, respectively. In the classification experiment, musicians scored 84% accuracy which compared favorably with the 100% accuracy attained by sophisticated pattern recognition methods. The results were further validated and confirmed by analyzing the NMR metabolic profiles belonging to two other different donors. These findings support our hypothesis that the uniqueness of the metabolic phenotype is preserved even when reproduced as audio signal and warrants further consideration and testing in larger study samples.

  18. Optimization of identity operation in NMR spectroscopy via genetic algorithm: Application to the TEDOR experiment

    Science.gov (United States)

    Manu, V. S.; Veglia, Gianluigi

    2016-12-01

    Identity operation in the form of π pulses is widely used in NMR spectroscopy. For an isolated single spin system, a sequence of even number of π pulses performs an identity operation, leaving the spin state essentially unaltered. For multi-spin systems, trains of π pulses with appropriate phases and time delays modulate the spin Hamiltonian to perform operations such as decoupling and recoupling. However, experimental imperfections often jeopardize the outcome, leading to severe losses in sensitivity. Here, we demonstrate that a newly designed Genetic Algorithm (GA) is able to optimize a train of π pulses, resulting in a robust identity operation. As proof-of-concept, we optimized the recoupling sequence in the transferred-echo double-resonance (TEDOR) pulse sequence, a key experiment in biological magic angle spinning (MAS) solid-state NMR for measuring multiple carbon-nitrogen distances. The GA modified TEDOR (GMO-TEDOR) experiment with improved recoupling efficiency results in a net gain of sensitivity up to 28% as tested on a uniformly 13C, 15N labeled microcrystalline ubiquitin sample. The robust identity operation achieved via GA paves the way for the optimization of several other pulse sequences used for both solid- and liquid-state NMR used for decoupling, recoupling, and relaxation experiments.

  19. General order parameter based correlation analysis of protein backbone motions between experimental NMR relaxation measurements and molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Qing; Shi, Chaowei [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Yu, Lu [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); High Magnetic Field Laboratory, Chinese Academy of Science, Hefei, Anhui, 230031 (China); Zhang, Longhua [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Xiong, Ying, E-mail: yxiong73@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Tian, Changlin, E-mail: cltian@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); High Magnetic Field Laboratory, Chinese Academy of Science, Hefei, Anhui, 230031 (China)

    2015-02-13

    Internal backbone dynamic motions are essential for different protein functions and occur on a wide range of time scales, from femtoseconds to seconds. Molecular dynamic (MD) simulations and nuclear magnetic resonance (NMR) spin relaxation measurements are valuable tools to gain access to fast (nanosecond) internal motions. However, there exist few reports on correlation analysis between MD and NMR relaxation data. Here, backbone relaxation measurements of {sup 15}N-labeled SH3 (Src homology 3) domain proteins in aqueous buffer were used to generate general order parameters (S{sup 2}) using a model-free approach. Simultaneously, 80 ns MD simulations of SH3 domain proteins in a defined hydrated box at neutral pH were conducted and the general order parameters (S{sup 2}) were derived from the MD trajectory. Correlation analysis using the Gromos force field indicated that S{sup 2} values from NMR relaxation measurements and MD simulations were significantly different. MD simulations were performed on models with different charge states for three histidine residues, and with different water models, which were SPC (simple point charge) water model and SPC/E (extended simple point charge) water model. S{sup 2} parameters from MD simulations with charges for all three histidines and with the SPC/E water model correlated well with S{sup 2} calculated from the experimental NMR relaxation measurements, in a site-specific manner. - Highlights: • Correlation analysis between NMR relaxation measurements and MD simulations. • General order parameter (S{sup 2}) as common reference between the two methods. • Different protein dynamics with different Histidine charge states in neutral pH. • Different protein dynamics with different water models.

  20. Two-dimensional MAS NMR correlation protocols involving double-quantum filtering of quadrupolar spin-pairs.

    Science.gov (United States)

    Edén, Mattias

    2010-05-01

    Three two-dimensional (2D) NMR homonuclear correlation techniques invoking double-quantum (2Q) filtration of the central transitions of half-integer spins are evaluated numerically and experimentally. They correlate directly detected single-quantum (1Q) coherences in the t(2) domain with either of 1Q, two-spin 2Q or single-spin multiple-quantum coherence-evolutions in the indirect (t(1)) dimension. We employ experimental (23)Na and (27)Al NMR on sodium sulfite and the natural mineral sillimanite (SiAl(2)O(5)), in conjunction with simulated 2D spectra from pairs of dipolar-recoupled spins-3/2 and 5/2 at different external magnetic fields, to compare the correlation strategies from the viewpoints of 2D spectral resolution, signal sensitivity, implementational aspects and their relative merits for establishing internuclear proximities and quadrupolar tensor orientations.

  1. Computer-intensive simulation of solid-state NMR experiments using SIMPSON

    Science.gov (United States)

    Tošner, Zdeněk; Andersen, Rasmus; Stevensson, Baltzar; Edén, Mattias; Nielsen, Niels Chr.; Vosegaard, Thomas

    2014-09-01

    Conducting large-scale solid-state NMR simulations requires fast computer software potentially in combination with efficient computational resources to complete within a reasonable time frame. Such simulations may involve large spin systems, multiple-parameter fitting of experimental spectra, or multiple-pulse experiment design using parameter scan, non-linear optimization, or optimal control procedures. To efficiently accommodate such simulations, we here present an improved version of the widely distributed open-source SIMPSON NMR simulation software package adapted to contemporary high performance hardware setups. The software is optimized for fast performance on standard stand-alone computers, multi-core processors, and large clusters of identical nodes. We describe the novel features for fast computation including internal matrix manipulations, propagator setups and acquisition strategies. For efficient calculation of powder averages, we implemented interpolation method of Alderman, Solum, and Grant, as well as recently introduced fast Wigner transform interpolation technique. The potential of the optimal control toolbox is greatly enhanced by higher precision gradients in combination with the efficient optimization algorithm known as limited memory Broyden-Fletcher-Goldfarb-Shanno. In addition, advanced parallelization can be used in all types of calculations, providing significant time reductions. SIMPSON is thus reflecting current knowledge in the field of numerical simulations of solid-state NMR experiments. The efficiency and novel features are demonstrated on the representative simulations.

  2. Computer-intensive simulation of solid-state NMR experiments using SIMPSON.

    Science.gov (United States)

    Tošner, Zdeněk; Andersen, Rasmus; Stevensson, Baltzar; Edén, Mattias; Nielsen, Niels Chr; Vosegaard, Thomas

    2014-09-01

    Conducting large-scale solid-state NMR simulations requires fast computer software potentially in combination with efficient computational resources to complete within a reasonable time frame. Such simulations may involve large spin systems, multiple-parameter fitting of experimental spectra, or multiple-pulse experiment design using parameter scan, non-linear optimization, or optimal control procedures. To efficiently accommodate such simulations, we here present an improved version of the widely distributed open-source SIMPSON NMR simulation software package adapted to contemporary high performance hardware setups. The software is optimized for fast performance on standard stand-alone computers, multi-core processors, and large clusters of identical nodes. We describe the novel features for fast computation including internal matrix manipulations, propagator setups and acquisition strategies. For efficient calculation of powder averages, we implemented interpolation method of Alderman, Solum, and Grant, as well as recently introduced fast Wigner transform interpolation technique. The potential of the optimal control toolbox is greatly enhanced by higher precision gradients in combination with the efficient optimization algorithm known as limited memory Broyden-Fletcher-Goldfarb-Shanno. In addition, advanced parallelization can be used in all types of calculations, providing significant time reductions. SIMPSON is thus reflecting current knowledge in the field of numerical simulations of solid-state NMR experiments. The efficiency and novel features are demonstrated on the representative simulations.

  3. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu [Biophysics and Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109-1055 (United States)

    2016-01-21

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D {sup 1}H/{sup 13}C/{sup 1}H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t{sub 1} and t{sub 3} periods, respectively. In addition to through-space and through-bond {sup 13}C/{sup 1}H and {sup 13}C/{sup 13}C chemical shift correlations, the 3D {sup 1}H/{sup 13}C/{sup 1}H experiment also provides a COSY-type {sup 1}H/{sup 1}H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices ({sup 1}H/{sup 1}H chemical shift correlation spectrum) at different {sup 13}C chemical shift frequencies from the 3D {sup 1}H/{sup 13}C/{sup 1}H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the

  4. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS.

    Science.gov (United States)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-21

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D (1)H/(13)C/(1)H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond (13)C/(1)H and (13)C/(13)C chemical shift correlations, the 3D (1)H/(13)C/(1)H experiment also provides a COSY-type (1)H/(1)H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices ((1)H/(1)H chemical shift correlation spectrum) at different (13)C chemical shift frequencies from the 3D (1)H/(13)C/(1)H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D (1)H/(13)C/(1)H experiment would be useful to study the structure and dynamics of

  5. /sup 3/H-/sup 1/H shift correlation NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Funke, C.W.; Wagenaars, G.N.; Kaspersen, F.M.

    1986-05-01

    Three two-dimensional /sup 3/H-/sup 1/H chemical shift correlation experiments are described, all using familiar pulse sequences. The experiments reveal the chemical shifts of the /sup 1/H spins which are coupled scalarly to a /sup 3/H spin and, thus, assist in the unambiguous location of this /sup 3/H spin within the molecule. The limitations for molecules involving a /sup 3/H spin which is coupled differently to various /sup 1/H spins are indicated. In practice, the detection limit is of the order of 100 MBq per /sup 3/H-labelling site.

  6. Si-29 NMR spectroscopy of naturally-shocked quartz from Meteor Crater, Arizona: Correlation to Kieffer's classification scheme

    Science.gov (United States)

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

    1993-01-01

    We have applied solid state Si-29 nuclear magnetic resonance (NMR) spectroscopy to five naturally-shocked Coconino Sandstone samples from Meteor Crater, Arizona, with the goal of examining possible correlations between NMR spectral characteristics and shock level. This work follows our observation of a strong correlation between the width of a Si-29 resonance and peak shock pressure for experimentally shocked quartz powders. The peak width increase is due to the shock-induced formation of amorphous silica, which increases as a function of shock pressure over the range that we studied (7.5 to 22 GPa). The Coconino Sandstone spectra are in excellent agreement with the classification scheme of Kieffer in terms of presence and approximate abundances of quartz, coesite, stishovite, and glass. We also observe a new resonance in two moderately shocked samples that we have tentatively identified with silicon in tetrahedra with one hydroxyl group in a densified form of amorphous silica.

  7. A PFG NMR experiment for translational diffusion measurements in low-viscosity solvents containing multiple resonances

    Science.gov (United States)

    Simorellis, Alana K.; Flynn, Peter F.

    2004-10-01

    Pulsed gradient simulated-echo (PGSE) NMR diffusion measurements provide a facile and accurate means for determining the self-diffusion coefficients for molecules over a wide range of sizes and conditions. The measurement of diffusion in solvents of low intrinsic viscosity is particularly challenging, due to the persistent presence of convection. Although convection can occur in most solvent systems at elevated temperatures, in lower viscosity solvents (e.g., short chain alkanes), convection may manifest itself even at ambient laboratory temperatures. In most circumstances, solvent suppression will also be required, and for solvents that have multiple resonances, effective suppression can likewise represent a substantial challenge. In this article, we report an NMR experiment that combines a double-stimulated echo PFG approach with a WET-based solvent suppression scheme that effectively and simultaneously address the issues of dynamic range and the deleterious effects of convection. The experiment described will be of general benefit to studies aimed at the characterization of diffusion of single molecules directly dissolved in low-viscosity solvents, and should also be of substantial utility in studies of supramolecular assemblies such as reverse-micelles dissolved in apolar solvents.

  8. Sequential backbone assignment based on dipolar amide-to-amide correlation experiments.

    Science.gov (United States)

    Xiang, ShengQi; Grohe, Kristof; Rovó, Petra; Vasa, Suresh Kumar; Giller, Karin; Becker, Stefan; Linser, Rasmus

    2015-07-01

    Proton detection in solid-state NMR has seen a tremendous increase in popularity in the last years. New experimental techniques allow to exploit protons as an additional source of information on structure, dynamics, and protein interactions with their surroundings. In addition, sensitivity is mostly improved and ambiguity in assignment experiments reduced. We show here that, in the solid state, sequential amide-to-amide correlations turn out to be an excellent, complementary way to exploit amide shifts for unambiguous backbone assignment. For a general assessment, we compare amide-to-amide experiments with the more common (13)C-shift-based methods. Exploiting efficient CP magnetization transfers rather than less efficient INEPT periods, our results suggest that the approach is very feasible for solid-state NMR.

  9. Sequential backbone assignment based on dipolar amide-to-amide correlation experiments

    Energy Technology Data Exchange (ETDEWEB)

    Xiang, ShengQi; Grohe, Kristof; Rovó, Petra; Vasa, Suresh Kumar; Giller, Karin; Becker, Stefan; Linser, Rasmus, E-mail: rali@nmr.mpibpc.mpg.de [Max Planck Institute for Biophysical Chemistry, Department for NMR-Based Structural Biology (Germany)

    2015-07-15

    Proton detection in solid-state NMR has seen a tremendous increase in popularity in the last years. New experimental techniques allow to exploit protons as an additional source of information on structure, dynamics, and protein interactions with their surroundings. In addition, sensitivity is mostly improved and ambiguity in assignment experiments reduced. We show here that, in the solid state, sequential amide-to-amide correlations turn out to be an excellent, complementary way to exploit amide shifts for unambiguous backbone assignment. For a general assessment, we compare amide-to-amide experiments with the more common {sup 13}C-shift-based methods. Exploiting efficient CP magnetization transfers rather than less efficient INEPT periods, our results suggest that the approach is very feasible for solid-state NMR.

  10. Accurate determination of order parameters from 1H,15N dipolar couplings in MAS solid-state NMR experiments.

    Science.gov (United States)

    Chevelkov, Veniamin; Fink, Uwe; Reif, Bernd

    2009-10-01

    A reliable site-specific estimate of the individual N-H bond lengths in the protein backbone is the fundamental basis of any relaxation experiment in solution and in the solid-state NMR. The N-H bond length can in principle be influenced by hydrogen bonding, which would result in an increased N-H distance. At the same time, dynamics in the backbone induces a reduction of the experimental dipolar coupling due to motional averaging. We present a 3D dipolar recoupling experiment in which the (1)H,(15)N dipolar coupling is reintroduced in the indirect dimension using phase-inverted CP to eliminate effects from rf inhomogeneity. We find no variation of the N-H dipolar coupling as a function of hydrogen bonding. Instead, variations in the (1)H,(15)N dipolar coupling seem to be due to dynamics of the protein backbone. This is supported by the observed correlation between the H(N)-N dipolar coupling and the amide proton chemical shift. The experiment is demonstrated for a perdeuterated sample of the alpha-spectrin SH3 domain. Perdeuteration is a prerequisite to achieve high accuracy. The average error in the analysis of the H-N dipolar couplings is on the order of +/-370 Hz (+/-0.012 A) and can be as small as 150 Hz, corresponding to a variation of the bond length of +/-0.005 A.

  11. Nitrogen-detected CAN and CON experiments as alternative experiments for main chain NMR resonance assignments.

    Science.gov (United States)

    Takeuchi, Koh; Heffron, Gregory; Sun, Zhen-Yu J; Frueh, Dominique P; Wagner, Gerhard

    2010-08-01

    Heteronuclear direct-detection experiments, which utilize the slower relaxation properties of low gamma nuclei, such as (13)C have recently been proposed for sequence-specific assignment and structural analyses of large, unstructured, and/or paramagnetic proteins. Here we present two novel (15)N direct-detection experiments. The CAN experiment sequentially connects amide (15)N resonances using (13)C(alpha) chemical shift matching, and the CON experiment connects the preceding (13)C' nuclei. When starting from the same carbon polarization, the intensities of nitrogen signals detected in the CAN or CON experiments would be expected four times lower than those of carbon resonances observed in the corresponding (13)C-detecting experiment, NCA-DIPAP or NCO-IPAP (Bermel et al. 2006b; Takeuchi et al. 2008). However, the disadvantage due to the lower gamma is counteracted by the slower (15)N transverse relaxation during detection, the possibility for more efficient decoupling in both dimensions, and relaxation optimized properties of the pulse sequences. As a result, the median S/N in the (15)N observe CAN experiment is 16% higher than in the (13)C observe NCA-DIPAP experiment. In addition, significantly higher sensitivity was observed for those residues that are hard to detect in the NCA-DIPAP experiment, such as Gly, Ser and residues with high-field C(alpha) resonances. Both CAN and CON experiments are able to detect Pro resonances that would not be observed in conventional proton-detected experiments. In addition, those experiments are free from problems of incomplete deuterium-to-proton back exchange in amide positions of perdeuterated proteins expressed in D(2)O. Thus, these features and the superior resolution of (15)N-detected experiments provide an attractive alternative for main chain assignments. The experiments are demonstrated with the small model protein GB1 at conditions simulating a 150 kDa protein, and the 52 kDa glutathione S-transferase dimer, GST.

  12. Heating and temperature gradients of lipid bilayer samples induced by RF irradiation in MAS solid-state NMR experiments.

    Science.gov (United States)

    Wang, Jing; Zhang, Zhengfeng; Zhao, Weijing; Wang, Liying; Yang, Jun

    2016-05-09

    The MAS solid-state NMR has been a powerful technique for studying membrane proteins within the native-like lipid bilayer environment. In general, RF irradiation in MAS NMR experiments can heat and potentially destroy expensive membrane protein samples. However, under practical MAS NMR experimental conditions, detailed characterization of RF heating effect of lipid bilayer samples is still lacking. Herein, using (1) H chemical shift of water for temperature calibration, we systematically study the dependence of RF heating on hydration levels and salt concentrations of three lipids in MAS NMR experiments. Under practical (1) H decoupling conditions used in biological MAS NMR experiments, three lipids show different dependence of RF heating on hydration levels as well as salt concentrations, which are closely associated with the properties of lipids. The maximum temperature elevation of about 10 °C is similar for the three lipids containing 200% hydration, which is much lower than that in static solid-state NMR experiments. The RF heating due to salt is observed to be less than that due to hydration, with a maximum temperature elevation of less than 4 °C in the hydrated samples containing 120 mmol l(-1) of salt. Upon RF irradiation, the temperature gradient across the sample is observed to be greatly increased up to 20 °C, as demonstrated by the remarkable broadening of (1) H signal of water. Based on detailed characterization of RF heating effect, we demonstrate that RF heating and temperature gradient can be significantly reduced by decreasing the hydration levels of lipid bilayer samples from 200% to 30%. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  13. Nonuniform sampling of hypercomplex multidimensional NMR experiments: Dimensionality, quadrature phase and randomization

    Science.gov (United States)

    Schuyler, Adam D; Maciejewski, Mark W; Stern, Alan S; Hoch, Jeffrey C

    2015-01-01

    Nonuniform sampling (NUS) in multidimensional NMR permits the exploration of higher dimensional experiments and longer evolution times than the Nyquist Theorem practically allows for uniformly sampled experiments. However, the spectra of NUS data include sampling-induced artifacts and may be subject to distortions imposed by sparse data reconstruction techniques, issues not encountered with the discrete Fourier transform (DFT) applied to uniformly sampled data. The characterization of these NUS-induced artifacts allows for more informed sample schedule design and improved spectral quality. The DFT–Convolution Theorem, via the point-spread function (PSF) for a given sampling scheme, provides a useful framework for exploring the nature of NUS sampling artifacts. In this work, we analyze the PSFs for a set of specially constructed NUS schemes to quantify the interplay between randomization and dimensionality for reducing artifacts relative to uniformly undersampled controls. In particular, we find a synergistic relationship between the indirect time dimensions and the “quadrature phase dimension” (i.e. the hypercomplex components collected for quadrature detection). The quadrature phase dimension provides additional degrees of freedom that enable partial-component NUS (collecting a subset of quadrature components) to further reduce sampling-induced aliases relative to traditional full-component NUS (collecting all quadrature components). The efficacy of artifact reduction is exponentially related to the dimensionality of the sample space. Our results quantify the utility of partial-component NUS as an additional means for introducing decoherence into sampling schemes and reducing sampling artifacts in high dimensional experiments. PMID:25899289

  14. Correlations for a new Bell's inequality experiment

    CERN Document Server

    Sica, L

    2002-01-01

    Proofs of Bell's theorem and the data analysis used to show its violation have commonly assumed a spatially stationary underlying process. However, it has been shown recently that the appropriate Bell's inequality holds identically for cross correlations of three or four lists of + or - 1's, independently of statistical assumptions. When data consistent with its derivation are analyzed without imposition of the stationarity assumption, the resulting correlations satisfy the Bell inequality.

  15. Extraction and [superscript 1]H NMR Analysis of Fats from Convenience Foods: A Laboratory Experiment for Organic Chemistry

    Science.gov (United States)

    Hartel, Aaron M.; Moore, Amy C.

    2014-01-01

    The extraction and analysis of fats from convenience foods (crackers, cookies, chips, candies) has been developed as an experiment for a second-year undergraduate organic chemistry laboratory course. Students gravimetrically determine the fat content per serving and then perform a [superscript 1]H NMR analysis of the recovered fat to determine the…

  16. Analysis of Bromination of Ethylbenzene Using a 45 MHz NMR Spectrometer: An Undergraduate Organic Chemistry Laboratory Experiment

    Science.gov (United States)

    Isaac-Lam, Meden F.

    2014-01-01

    A 45 MHz benchtop NMR spectrometer is used to identify the structures and determine the amount of 1-bromoethylbenzene and 1,1-dibromoethylbenzene produced from free-radical bromination of ethylbenzene. The experiment is designed for nonchemistry majors, specifically B.S. Biology students, in a predominantly undergraduate institution with…

  17. Extraction and [superscript 1]H NMR Analysis of Fats from Convenience Foods: A Laboratory Experiment for Organic Chemistry

    Science.gov (United States)

    Hartel, Aaron M.; Moore, Amy C.

    2014-01-01

    The extraction and analysis of fats from convenience foods (crackers, cookies, chips, candies) has been developed as an experiment for a second-year undergraduate organic chemistry laboratory course. Students gravimetrically determine the fat content per serving and then perform a [superscript 1]H NMR analysis of the recovered fat to determine the…

  18. Synthesis and Resolution of the Atropisomeric 1,1'-Bi-2-Naphthol: An Experiment in Organic Synthesis and 2-D NMR Spectroscopy

    Science.gov (United States)

    Mak, Kendrew K. W.

    2004-01-01

    NMR spectroscopy is presented. It is seen that the experiment regarding the synthesis and resolution of 1,1'-Bi-2-naphtol presents a good experiment for teaching organic synthesis and NMR spectroscopy and provides a strategy for obtaining enantiopure compounds from achiral starting materials.

  19. Synthesis and Resolution of the Atropisomeric 1,1'-Bi-2-Naphthol: An Experiment in Organic Synthesis and 2-D NMR Spectroscopy

    Science.gov (United States)

    Mak, Kendrew K. W.

    2004-01-01

    NMR spectroscopy is presented. It is seen that the experiment regarding the synthesis and resolution of 1,1'-Bi-2-naphtol presents a good experiment for teaching organic synthesis and NMR spectroscopy and provides a strategy for obtaining enantiopure compounds from achiral starting materials.

  20. Jet and particle correlations with ATLAS experiment

    CERN Document Server

    Kepka, Oldrich; The ATLAS collaboration

    2017-01-01

    Two new ATLAS measurements are discussed. The jet energy-energy correlations was measured using 8TeV data and the observables were used to extract the strong coupling constant. The observables are constructed in such a way to reduce both experimental and theoretical uncertainties. The second measurement deals with the study of two-particle correlations using three-hadron particle chains. It is observed that particle pairs with small momentum difference are entirely produced by low mass chain. This observation is compatible with helix-light fragmentation and is not described by the existing MC generators.

  1. An NMR Experiment Based on Off-the-Shelf Digital Data-Acquisition Equipment

    Science.gov (United States)

    Hilty, Christian; Bowen, Sean

    2010-01-01

    Nuclear magnetic resonance (NMR) poses significant challenges for teaching in the context of an undergraduate laboratory, foremost because of high equipment cost. Current off-the-shelf data-acquisition hardware, however, is sufficiently powerful to constitute the core of a fully digital NMR spectrometer operating at the earth's field. We present…

  2. 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

  3. Psychophysical correlates of phantom limb experience.

    OpenAIRE

    Katz, J

    1992-01-01

    Phantom limb phenomena were correlated with psychophysiological measures of peripheral sympathetic nervous system activity measured at the amputation stump and contralateral limb. Amputees were assigned to one of three groups depending on whether they reported phantom limb pain, non-painful phantom limb sensations, or no phantom limb at all. Skin conductance and skin temperature were recorded continuously during two 30 minute sessions while subjects continuously monitored and rated the intens...

  4. Determination of ¹J(⁵⁹Co-⁵⁹Co) scalar coupling constants in the tetrahedral mixed-metal cluster HFeCo₃(CO)₁₀(PCyH₂)(PPh₂[CH₂C(O)Ph]) using COSY-type NMR experiments.

    Science.gov (United States)

    Kempgens, Pierre; Rosé, Jacky

    2011-03-01

    Two-dimensional ⁵⁹Co correlation spectroscopy (COSY) and double-quantum-filtered (DQF) COSY NMR experiments are reported for the tetrahedral mixed-metal cluster HFeCo₃(CO)₁₀(PCyH₂)(PPh₂[CH₂C(O)Ph]), which consists from the point of view of ⁵⁹Co NMR spectroscopy, of an AMX system of three-spin S=7/2. Both 2D NMR spectra prove the existence of a J scalar coupling constant between non-equivalent ⁵⁹Co nuclei. By contrast to what happens with the conventional 2D ⁵⁹Co COSY NMR spectrum, it was possible to simulate the 2D ⁵⁹Co DQF-COSY NMR spectrum by density matrix calculations in order to extract the values of the ¹J(⁵⁹Co-⁵⁹Co) coupling constants. The comparison between experimental and theoretical 2D NMR spectra gives spin-couplings constants of several hundreds Hertz for this cluster. Copyright © 2010 Elsevier Inc. All rights reserved.

  5. Correlations of the chemical shift on fasly rotating biological solids by means of NMR spectroscopy; Korrelationen der chemischen Verschiebung an schnell rotierenden biologischen Festkoerpern mittels NMR-Spektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Herbst, Christian

    2010-04-27

    The basic aim of the thesis was the development and improvement of homo- and heteronuclear feedback sequences for the generation of correlation spectra of the chemical shift. In a first step the possibility of the acquisition of {sup 13}C-{sup 13} correlation spectra of the chemical shift by means of inversion pulses with low RF power factor was studied. Furthermore it was shown that broad-band phase-modulated inversion and universal rotational pulses can be constructed by means of global optimization procedures like the genetic algorithms under regardment of the available RF field strength. By inversion, universal rotational, and 360 pulses as starting values of the optimization efficient homonuclear CN{sub n}{sup {nu}} and RN{sub n}{sup {nu}} mixing sequences as well as heteronuclear RN{sub n}{sup {nu}{sub s},{nu}{sub k}} feedback sequences were generated. The satisfactory power of the numerically optimized sequences was shown by means of the simulation as well by means of correlation experiments of the chemical shift of L-histidine, L-arginine, and the (CUG){sub 97}-RNA. This thesis deals furthermore with the possibility to acquire simultaneously different signals with several receivers. By means of numerically optimized RN{sub n}{sup {nu}{sub s},{nu}{sub k}} pulse sequences both {sup 15}N-{sup 13}C and {sup 13}C-{sup 15}N correlation spectra were simultaneously generated. Furthermore it could be shown that the simultaneous acquisition of 3D-{sup 15}N-{sup 13}C-{sup 13}C and {sup 13}C-{sup 15}N-({sup 1}H)-{sup 1}H correlation spectra is possible. By this in only one measurement process resonance assignments can be met and studies of the global folding performed. A further application of several receivers is the simultaneous acquisition of CHHC, NHHN, NHHC, as well as CHHN spectra. By such experiments it is possible to characterize the hydrogen-bonding pattern and the glycosidic torsion angle {sup {chi}} in RNA. This was demonstrated by means of the (CUG){sub 97

  6. Neural correlates of aesthetic experience in art

    OpenAIRE

    Di Dio, Cinzia

    2012-01-01

    The present thesis discusses the results of studies on neuroesthetics, which were aimed at unfolding the basic mechanisms and processes underpinning the aesthetic experience for art and, in particular, its hedonic dimension. The type of art we considered is visual using, as main stimulus, the human body. Two studies were conducted using the functional magnetic resonance (fMRI) technique and two studies using the eye-tracking technique. The main results of our neuroimaging studies suggest that...

  7. Magic-Angle-Spinning Solid-State NMR of Membrane Proteins

    NARCIS (Netherlands)

    Baker, Lindsay A.; Folkers, Gert E.; Sinnige, Tessa; Houben, Klaartje; Kaplan, M.; van der Cruijsen, Elwin A W; Baldus, Marc

    2015-01-01

    Solid-state NMR spectroscopy (ssNMR) provides increasing possibilities to examine membrane proteins in different molecular settings, ranging from synthetic bilayers to whole cells. This flexibility often enables ssNMR experiments to be directly correlated with membrane protein function. In this

  8. Shale characteristics impact on Nuclear Magnetic Resonance (NMR fluid typing methods and correlations

    Directory of Open Access Journals (Sweden)

    Mohamed Mehana

    2016-06-01

    Full Text Available The development of shale reservoirs has brought a paradigm shift in the worldwide energy equation. This entails developing robust techniques to properly evaluate and unlock the potential of those reservoirs. The application of Nuclear Magnetic Resonance techniques in fluid typing and properties estimation is well-developed in conventional reservoirs. However, Shale reservoirs characteristics like pore size, organic matter, clay content, wettability, adsorption, and mineralogy would limit the applicability of the used interpretation methods and correlation. Some of these limitations include the inapplicability of the controlling equations that were derived assuming fast relaxation regime, the overlap of different fluids peaks and the lack of robust correlation to estimate fluid properties in shale. This study presents a state-of-the-art review of the main contributions presented on fluid typing methods and correlations in both experimental and theoretical side. The study involves Dual Tw, Dual Te, and doping agent's application, T1-T2, D-T2 and T2sec vs. T1/T2 methods. In addition, fluid properties estimation such as density, viscosity and the gas-oil ratio is discussed. This study investigates the applicability of these methods along with a study of the current fluid properties correlations and their limitations. Moreover, it recommends the appropriate method and correlation which are capable of tackling shale heterogeneity.

  9. Psychophysical correlates of phantom limb experience.

    Science.gov (United States)

    Katz, J

    1992-09-01

    Phantom limb phenomena were correlated with psychophysiological measures of peripheral sympathetic nervous system activity measured at the amputation stump and contralateral limb. Amputees were assigned to one of three groups depending on whether they reported phantom limb pain, non-painful phantom limb sensations, or no phantom limb at all. Skin conductance and skin temperature were recorded continuously during two 30 minute sessions while subjects continuously monitored and rated the intensity of any phantom limb sensation or pain they experienced. The results from both sessions showed that mean skin temperature was significantly lower at the stump than the contralateral limb in the groups with phantom limb pain and non-painful phantom limb sensations, but not among subjects with no phantom limb at all. In addition, stump skin conductance responses correlated significantly with the intensity of non-painful phantom limb paresthesiae but not other qualities of sensation or pain. Between-limb measures of pressure sensitivity were not significantly different in any group. The results suggest that the presence of a phantom limb, whether painful or painless, is related to the sympathetic-efferent outflow of cutaneous vasoconstrictor fibres in the stump and stump neuromas. The hypothesis of a sympathetic-efferent somatic-afferent mechanism involving both sudomotor and vasoconstrictor fibres is proposed to explain the relationship between stump skin conductance responses and non-painful phantom limb paresthesiae. It is suggested that increases in the intensity of phantom limb paresthesiae follow bursts of sympathetic activity due to neurotransmitter release onto apposing sprouts of large diameter primary afferents located in stump neuromas, and decreases correspond to periods of relative sympathetic inactivity. The results of the study agree with recent suggestions that phantom limb pain is not a unitary syndrome, but a symptom class with each class subserved by

  10. A Toolbox of Solid-State NMR Experiments for the Characterization of Soft Organic Nanomaterials

    KAUST Repository

    Straasø, Lasse Arnt

    2016-02-02

    Determining how organic molecules self-assemble into a solid material is a challenging and demanding task if a single crystal of the material cannot be produced. Solid-state NMR spectroscopy offers access to such molecular details via an appropriate selection of techniques. This report gives a selected overview of 1D and 2D solid-state NMR techniques for elucidating the structure of soft organic solids. We focus on how the solid-state NMR techniques are designed from the perspective of the different nuclear interactions, using average Hamiltonian theory and product operators. We also introduce recent methods for quantification and reduction of experimental artifacts. Finally, we highlight how the solid-state NMR techniques can be applied to soft organic materials by reviewing recent applications to semicrystalline polymers, π-conjugated polymers, natural silk, and graphene-related materials.

  11. Disclosing traumatic experiences: Correlates, context, and consequences.

    Science.gov (United States)

    Marriott, Brigid R; Lewis, Cara C; Gobin, Robyn L

    2016-03-01

    The type and severity of traumatic events differentially predict negative posttraumatic outcomes, with betrayal traumas (in which the victim is perpetrated by someone s/he trusts) touted as the most harmful. Although disclosure is considered an important component of the "healing process," nondisclosure and delayed disclosure persist. This study explored factors predicting and the context surrounding disclosure as well as the link between disclosure timing and a trauma survivor's experience with depression. Participants (N = 124) were attendees of a Mental Health Awareness event who had experienced a traumatic event. Participant report of traumatic experiences revealed that 28.2%, 36.3%, and 35.5% of participants had experienced a low betrayal (LB), medium betrayal (MB), and high betrayal (HB) trauma, respectively. Almost half (43.5%) disclosed immediately after the trauma, 32.3% disclosed within a month, and 24.2% disclosed after 1 month or more. Betrayal trauma level significantly predicted disclosure timing with individuals who had experienced HB traumas significantly more likely to delay disclosure (HB:LB, odds ratio [OR] = 21.79; MB:LB, OR = 4.57). Trauma survivors predominantly first disclosed to informal support sources (e.g., friends, family), typically citing that they thought it would allow them to feel better or they perceived the other person to be concerned about their well-being as their reason for disclosing. Experiencing a HB trauma predicted subsequent depression severity, but disclosure status was not predictive of subsequent depression. Results will be discussed with respect to implications for assessment and interventions for trauma survivors.

  12. The Heteronuclear Multiple-Quantum Correlation Experiment: Perspective from Classical Vectors, Nonclassical Vectors, and Product Operators

    Directory of Open Access Journals (Sweden)

    Karen de la Vega-Hernández

    2016-01-01

    Full Text Available It is usually accepted that most 2D-NMR experiments cannot be approached using classical models. Instructors argue that Product Operators (PO or density matrix formalisms are the only alternative to get insights into complex spin evolution for experiments involving Multiple-Quantum Coherence, such as the Heteronuclear Multiple-Quantum Correlation (HMQC technique. Nevertheless, in recent years, several contributions have been published to provide vectorial descriptions for the HMQC taking PO formalism as the starting point. In this work we provide a graphical representation of the HMQC experiment, taking the basic elements of Bloch’s vector model as building blocks. This description bears an intuitive and comfortable understanding of spin evolution during the pulse sequence, for those who are novice in 2D-NMR. Finally, this classical vectorial depiction is tested against the PO formalism and nonclassical vectors, conveying the didactic advantage of shedding light on a single phenomenon from different perspectives. This comparative approach could be useful to introduce PO and nonclassical vectors for advanced upper-division undergraduate and graduate education.

  13. NMR measurement of the magnetic field correlation function in porous media.

    Science.gov (United States)

    Cho, H; Song, Yi-Qiao

    2008-01-18

    The structure factor provides a fundamental characterization of porous and granular materials as it is the key for solid crystals via measurements of x-ray and neutron scattering. Here, we demonstrate that the structure factor of the granular and porous media can be approximated by the pair correlation function of the inhomogeneous internal magnetic field, which arises from the susceptibility difference between the pore filling liquid and the solid matrix. In-depth understanding of the internal field is likely to contribute to further development of techniques to study porous and granular media.

  14. Suppression of electron correlations in the collapsed tetragonal phase of CaFe2As2 under ambient pressure demonstrated by As75 NMR/NQR measurements

    Energy Technology Data Exchange (ETDEWEB)

    Furukawa, Yuji [Ames Laboratory; Roy, Beas [Ames Laboratory; Ran, Sheng [Ames Laboratory; Budko, Sergey L. [Ames Laboratory; Canfield, Paul C. [Ames Laboratory

    2014-03-20

    The static and the dynamic spin correlations in the low-temperature collapsed tetragonal and the high-temperature tetragonal phase in CaFe2As2 have been investigated by As75 nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements. Through the temperature (T) dependence of the nuclear spin lattice relaxation rates (1/T1) and the Knight shifts, although stripe-type antiferromagnetic (AFM) spin correlations are realized in the high-temperature tetragonal phase, no trace of the AFM spin correlations can be found in the nonsuperconducting, low-temperature, collapsed tetragonal (cT) phase. Given that there is no magnetic broadening in As75 NMR spectra, together with the T-independent behavior of magnetic susceptibility χ and the T dependence of 1/T1Tχ, we conclude that Fe spin correlations are completely quenched statically and dynamically in the nonsuperconducting cT phase in CaFe2As2.

  15. Suppression of electron correlations in the collapsed tetragonal phase of CaFe2As2 under ambient pressure demonstrated by As75 NMR/NQR measurements

    Science.gov (United States)

    Furukawa, Y.; Roy, B.; Ran, S.; Bud'ko, S. L.; Canfield, P. C.

    2014-03-01

    The static and the dynamic spin correlations in the low-temperature collapsed tetragonal and the high-temperature tetragonal phase in CaFe2As2 have been investigated by As75 nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements. Through the temperature (T) dependence of the nuclear spin lattice relaxation rates (1/T1) and the Knight shifts, although stripe-type antiferromagnetic (AFM) spin correlations are realized in the high-temperature tetragonal phase, no trace of the AFM spin correlations can be found in the nonsuperconducting, low-temperature, collapsed tetragonal (cT) phase. Given that there is no magnetic broadening in As75 NMR spectra, together with the T-independent behavior of magnetic susceptibility χ and the T dependence of 1/T1Tχ, we conclude that Fe spin correlations are completely quenched statically and dynamically in the nonsuperconducting cT phase in CaFe2As2.

  16. Bond length-bond angle correlation in densified silica—Results from 17O NMR spectroscopy

    Science.gov (United States)

    Trease, Nicole M.; Clark, Ted M.; Grandinetti, Philip J.; Stebbins, Jonathan F.; Sen, Sabyasachi

    2017-05-01

    Pressure induced correlated evolution of the distributions of the Si-O distance and Si-O-Si inter-tetrahedral bond angle in vitreous silica quenched from pressures of up to ˜14 GPa at ambient temperature is measured in unprecedented detail using two-dimensional dynamic-angle-spinning 17O nuclear magnetic resonance spectroscopy. The results demonstrate that, in contrast to the conventional wisdom, vitreous silica undergoes irreversible structural changes even at pressures as low as ˜8 GPa. These structural changes at the short range involve a progressive reduction in the mean Si-O-Si angle and a broadening of the corresponding distribution, with increasing pressure. This bond angle reduction is accompanied by a concomitant monotonic increase in the mean Si-O distance. The mean values of the Si-O-Si angle and Si-O distance at various pressures closely follow the minimum in the corresponding potential energy surface calculated for the H6Si2O7 dimer molecule.

  17. Study of multi-site chemical exchange in solution state by NMR: 1D experiments with multiply selective excitation

    Indian Academy of Sciences (India)

    Samanwita Pal

    2010-07-01

    Chemical exchange in solution state has been investigated traditionally by both 1D and 2D NMR, permitting the extraction of kinetic parameters (e.g. the spin-lattice relaxation time 1, the exchange rate constant and the activation parameters). This work demonstrates a simple 1D NMR approach employing multiply selective excitation to study multi-site exchange processes in solution, applying it to systems that exhibit three-site exchange. This approach involves simultaneous excitation of all - or a chosen subset of - the exchanging sites by using an appropriately modulated shaped radiofrequency pulse. The pulse sequence, as well as analysis is summarized. Significant features of the experiment, which relies on sign labelling of the exchanging sites, include considerably shorter experiment time compared to standard 2D exchange work, clear definition of the exchange time window and uniform pulse non-ideality effects for all the exchanging sites. Complete kinetic information is reported in the study of dynamic processes in superacid solutions of two weak bases, studied by 1H NMR. An analytical solution, leading to the determination of four rate parameters, is presented for proton exchange studies on these systems, which involve a mixture of two weak bases in arbitrary concentration ratio, and stoichiometric excess of the superacid.

  18. Denoising EMG and EEG for Monitoring Small Animal Models During NMR Experiments

    Science.gov (United States)

    2007-11-02

    electrodes. EEG and EMG signals were analogue band-pass filtered at 1-500 Hz, and sampled at 2 kHz. NMR signals were provided using a surface coil...et traitement des signaux physiologiques en vue de l’identification automatique des états de vigilance chez le petit animal », Systèmes et

  19. Chain Length Effects of Linear Alkanes in Zeolite Ferrierite. 1. Sorption and 13C NMR Experiments

    NARCIS (Netherlands)

    Well, van Willy J.M.; Cottin, Xavier; Haan, vde Jan W.; Smit, Berend; Nivarthy, Gautam; Lercher, Johannes A.; Hooff, van Jan H.C.; Santen, van Rutger A.

    1998-01-01

    Temperature-programmed desorption, heat of adsorption, adsorption isotherm, and 13C NMR measurements are used to study the sorption properties of linear alkanes in ferrierite. Some remarkable chain length effects are found in these properties. While propane, n-butane, and n-pentane fill the ferrieri

  20. chain length effects of linear alkanes in zeolite ferrierite.1. sorption and 13C NMR experiments

    NARCIS (Netherlands)

    van Well, Willy J.M.; Cottin, Xavier; vde Haan, Jan W.; Smit, Berend; Nivarthy, G.S.; Lercher, J.A.; van Hooff, Jan H.C.; van Santen, Rutger A.

    1998-01-01

    Temperature-programmed desorption, heat of adsorption, adsorption isotherm, and 13C NMR measurements are used to study the sorption properties of linear alkanes in ferrierite. Some remarkable chain length effects are found in these properties. While propane, n-butane, and n-pentane fill the

  1. Communication: Proton NMR dipolar-correlation effect as a method for investigating segmental diffusion in polymer melts

    Science.gov (United States)

    Lozovoi, A.; Mattea, C.; Herrmann, A.; Rössler, E. A.; Stapf, S.; Fatkullin, N.

    2016-06-01

    A simple and fast method for the investigation of segmental diffusion in high molar mass polymer melts is presented. The method is based on a special function, called proton dipolar-correlation build-up function, which is constructed from Hahn Echo signals measured at times t and t/2. The initial rise of this function contains additive contributions from both inter- and intramolecular magnetic dipole-dipole interactions. The intermolecular contribution depends on the relative mean squared displacements (MSDs) of polymer segments from different macromolecules, while the intramolecular part reflects segmental reorientations. Separation of both contributions via isotope dilution provides access to segmental displacements in polymer melts at millisecond range, which is hardly accessible by other methods. The feasibility of the method is illustrated by investigating protonated and deuterated polybutadiene melts with molecular mass 196 000 g/mol at different temperatures. The observed exponent of the power law of the segmental MSD is close to 0.32 ± 0.03 at times when the root MSD is in between 45 Å and 75 Å, and the intermolecular proton dipole-dipole contribution to the total proton Hahn Echo NMR signal is larger than 50% and increases with time.

  2. 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.

  3. NMR and EPR Studies of Free-Radical Intermediates from Experiments Mimicking the Winds on Mars

    DEFF Research Database (Denmark)

    Jakobsen, Hans J.; Song, Likai; Gan, Zhehong

    2016-01-01

    A new kind of solid gas chemical reactions has been investigated using solid-state powder H-2, C-13, and Si-29 NMR and EPR spectroscopies. These studies involve reactions between a silicate-created Si free-radical intermediate and a few ordinary gases such as isotopically H-2-, C-13-, and O-17......)-C-13, (encapsulation of the gas) and the indication of a congested methyl group in the product from reaction with methane....

  4. Determination of structural topology of a membrane protein in lipid bilayers using polarization optimized experiments (POE) for static and MAS solid state NMR spectroscopy.

    Science.gov (United States)

    Mote, Kaustubh R; Gopinath, T; Veglia, Gianluigi

    2013-10-01

    The low sensitivity inherent to both the static and magic angle spinning techniques of solid-state NMR (ssNMR) spectroscopy has thus far limited the routine application of multidimensional experiments to determine the structure of membrane proteins in lipid bilayers. Here, we demonstrate the advantage of using a recently developed class of experiments, polarization optimized experiments, for both static and MAS spectroscopy to achieve higher sensitivity and substantial time-savings for 2D and 3D experiments. We used sarcolipin, a single pass membrane protein, reconstituted in oriented bicelles (for oriented ssNMR) and multilamellar vesicles (for MAS ssNMR) as a benchmark. The restraints derived by these experiments are then combined into a hybrid energy function to allow simultaneous determination of structure and topology. The resulting structural ensemble converged to a helical conformation with a backbone RMSD ~0.44 Å, a tilt angle of 24° ± 1°, and an azimuthal angle of 55° ± 6°. This work represents a crucial first step toward obtaining high-resolution structures of large membrane proteins using combined multidimensional oriented solid-state NMR and magic angle spinning solid-state NMR.

  5. Determination of structural topology of a membrane protein in lipid bilayers using polarization optimized experiments (POE) for static and MAS solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Mote, Kaustubh R. [University of Minnesota, Department of Chemistry (United States); Gopinath, T. [University of Minnesota, Department of Biochemistry, Molecular Biology and Biophysics (United States); Veglia, Gianluigi, E-mail: vegli001@umn.edu [University of Minnesota, Department of Chemistry (United States)

    2013-10-15

    The low sensitivity inherent to both the static and magic angle spinning techniques of solid-state NMR (ssNMR) spectroscopy has thus far limited the routine application of multidimensional experiments to determine the structure of membrane proteins in lipid bilayers. Here, we demonstrate the advantage of using a recently developed class of experiments, polarization optimized experiments, for both static and MAS spectroscopy to achieve higher sensitivity and substantial time-savings for 2D and 3D experiments. We used sarcolipin, a single pass membrane protein, reconstituted in oriented bicelles (for oriented ssNMR) and multilamellar vesicles (for MAS ssNMR) as a benchmark. The restraints derived by these experiments are then combined into a hybrid energy function to allow simultaneous determination of structure and topology. The resulting structural ensemble converged to a helical conformation with a backbone RMSD {approx}0.44 A, a tilt angle of 24 Degree-Sign {+-} 1 Degree-Sign , and an azimuthal angle of 55 Degree-Sign {+-} 6 Degree-Sign . This work represents a crucial first step toward obtaining high-resolution structures of large membrane proteins using combined multidimensional oriented solid-state NMR and magic angle spinning solid-state NMR.

  6. The “long tail” of the protein tumbling correlation function: observation by {sup 1}H NMR relaxometry in a wide frequency and concentration range

    Energy Technology Data Exchange (ETDEWEB)

    Roos, Matthias [Martin-Luther-Universität Halle-Wittenberg, Institut für Physik (Germany); Hofmann, Marius [Universität Bayreuth, Lehrstuhl Experimentalphysik II, Universitätsstr. 30 (Germany); Link, Susanne; Ott, Maria; Balbach, Jochen [Martin-Luther-Universität Halle-Wittenberg, Institut für Physik (Germany); Rössler, Ernst [Universität Bayreuth, Lehrstuhl Experimentalphysik II, Universitätsstr. 30 (Germany); Saalwächter, Kay, E-mail: kay.saalwaechter@physik.uni-halle.de; Krushelnitsky, Alexey, E-mail: krushelnitsky@physik.uni-halle.de [Martin-Luther-Universität Halle-Wittenberg, Institut für Physik (Germany)

    2015-12-15

    Inter-protein interactions in solution affect the auto-correlation function of Brownian tumbling not only in terms of a simple increase of the correlation time, they also lead to the appearance of a weak slow component (“long tail”) of the correlation function due to a slowly changing local anisotropy of the microenvironment. The conventional protocol of correlation time estimation from the relaxation rate ratio R{sub 1}/R{sub 2} assumes a single-component tumbling correlation function, and thus can provide incorrect results as soon as the “long tail” is of relevance. This effect, however, has been underestimated in many instances. In this work we present a detailed systematic study of the tumbling correlation function of two proteins, lysozyme and bovine serum albumin, at different concentrations and temperatures using proton field-cycling relaxometry combined with R{sub 1ρ} and R{sub 2} measurements. Unlike high-field NMR relaxation methods, these techniques enable a detailed study of dynamics on a time scale longer than the normal protein tumbling correlation time and, thus, a reliable estimate of the parameters of the “long tail”. In this work we analyze the concentration dependence of the intensity and correlation time of the slow component and perform simulations of high-field {sup 15}N NMR relaxation data demonstrating the importance of taking the “long tail” in the analysis into account.

  7. Improving the accuracy of pulsed field gradient NMR diffusion experiments: Correction for gradient non-uniformity

    Science.gov (United States)

    Connell, Mark A.; Bowyer, Paul J.; Adam Bone, P.; Davis, Adrian L.; Swanson, Alistair G.; Nilsson, Mathias; Morris, Gareth A.

    2009-05-01

    Pulsed field gradient NMR is a well-established technique for the determination of self-diffusion coefficients. However, a significant source of systematic error exists in the spatial variation of the applied pulsed field gradient. Non-uniform pulsed field gradients cause the decay of peak amplitudes to deviate from the expected exponential dependence on gradient squared. This has two undesirable effects: the apparent diffusion coefficient will deviate from the true value to an extent determined by the choice of experimental parameters, and the error estimated by the nonlinear least squares fitting will contain a significant systematic contribution. In particular, the apparent diffusion coefficient determined by exponential fitting of the diffusional attenuation of NMR signals will depend both on the exact pulse widths used and on the range of gradient amplitudes chosen. These problems can be partially compensated for if experimental attenuation data are fitted to a function corrected for the measured spatial dependence of the gradient and signal strength. This study describes a general alternative to existing methods for the calibration of NMR diffusion measurements. The dominant longitudinal variation of the pulsed field gradient amplitude and the signal strength are mapped by measuring pulsed field gradient echoes in the presence of a weak read gradient. These data are then used to construct a predicted signal decay function for the whole sample, which is parameterised as the exponential of a power series. Results are presented which compare diffusion coefficients obtained using the new calibration method with previous literature values.

  8. Using 31P-NMR to investigate dynamics of soil phosphorus compounds in the Rothamsted Long Term Experiments

    Science.gov (United States)

    Blackwell, Martin; Turner, Ben; Granger, Steve; Hooper, Tony; Darch, Tegan; Hawkins, Jane; Yuan, Huimin; McGrath, Steve

    2015-04-01

    The technique of 31P-NMR spectroscopy has done more to advance the knowledge of phosphorus forms (especially organic phosphorus) in environmental samples than any other method. The technique has advanced such that specific compounds can be identified where previously only broad categories such as orthophosphate monoesters and diesters were distinguishable. The Soil Archive and Long Term Experiments at Rothamsted Research, UK, potentially provides an unequalled opportunity to use this technique to observe changes in soil phosphorus compounds with time and under different treatments, thereby enhancing our understanding of phosphorus cycling and use by plants. Some of the earliest work using this technique on soils was carried out by Hawkes et al. in 1984 and this used soils from two of the oldest Rothamsted Long Term Experiments, namely Highfield and Park Grass. Here we revisit the samples studied in this early work and reanalyse them using current methodology to demonstrate how the 31P-NMR technique has advanced. We also present results from a study on the phosphorus chemistry in soils along the Hoosfield acid strip (Rothamsted, UK), where a pH gradient from 3.7 to 7.8 occurs in a single soil with little variation in total phosphorus (mean ± standard deviation 399 ± 27 mg P kg-1). Soil pH was found to be an important factor in determining the proportion of phosphomonoesters and phosphodiesters in the soil organic phosphorus, although total organic phosphorus concentrations were a relatively consistent proportion of the total soil phosphorus (36 ± 2%) irrespective of soil pH. Key words. 31P-NMR, soil organic phosphorus, long term experiments, Hoosfield acid strip

  9. 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.

  10. The experience of mathematical beauty and its neural correlates.

    Science.gov (United States)

    Zeki, Semir; Romaya, John Paul; Benincasa, Dionigi M T; Atiyah, Michael F

    2014-01-01

    Many have written of the experience of mathematical beauty as being comparable to that derived from the greatest art. This makes it interesting to learn whether the experience of beauty derived from such a highly intellectual and abstract source as mathematics correlates with activity in the same part of the emotional brain as that derived from more sensory, perceptually based, sources. To determine this, we used functional magnetic resonance imaging (fMRI) to image the activity in the brains of 15 mathematicians when they viewed mathematical formulae which they had individually rated as beautiful, indifferent or ugly. Results showed that the experience of mathematical beauty correlates parametrically with activity in the same part of the emotional brain, namely field A1 of the medial orbito-frontal cortex (mOFC), as the experience of beauty derived from other sources.

  11. The experience of mathematical beauty and its neural correlates

    Directory of Open Access Journals (Sweden)

    Semir eZeki

    2014-02-01

    Full Text Available Many have written of the experience of mathematical beauty as being comparable to that derived from the greatest art. This makes it interesting to learn whether the experience of beauty derived from such a highly intellectual and abstract source such as mathematics correlates with activity in the same part of the emotional brain as that derived from more sensory, perceptually based, sources. To determine this, we used functional magnetic resonance imaging (fMRI to image the activity in the brains of 15 mathematicians when they viewed mathematical formulae which they had individually rated as beautiful, indifferent or ugly. Results showed that the experience of mathematical beauty correlates parametrically with activity in the same part of the emotional brain, namely field A1 of the medial orbito-frontal cortex (mOFC, as the experience of beauty derived from other sources.

  12. Correlations between (51)V solid-state NMR parameters and chemical structure of vanadium (V) complexes as models for related metalloproteins and catalysts.

    Science.gov (United States)

    Fenn, Annika; Wächtler, Maria; Gutmann, Torsten; Breitzke, Hergen; Buchholz, Axel; Lippold, Ines; Plass, Winfried; Buntkowsky, Gerd

    2009-12-01

    The parameters describing the quadrupolar and CSA interactions of 51V solid-state MAS NMR investigations of model complexes mimicking vanadoenzymes as well as vanadium containing catalysts and enzyme complexes are interpreted with respect to the chemical structure. The interpretation is based on the data of 15 vanadium complexes including two new complexes with previously unpublished data and 13 complexes with data previously published by us. Correlations between the chemical structure and the 51V solid-state NMR data of this class of compounds have been established. Especially for the isotropic chemical shift delta(iso) and the chemical shift anisotropy delta(sigma), correlations with specific structural features like the coordination number of the vanadium atom, the number of coordinating nitrogens, the number of oxygen atoms and the chemical surrounding of the complex could be established for these compounds. Moreover, quantitative correlations between the solid-state NMR parameters and specific bond angles and bond lengths have been obtained. Our results can be of particular interest for future investigations concerning the structure and the mode of action of related vanadoenzymes and vanadate protein assemblies, including the use of vanadate adducts as transition state analogs for phosphate metabolizing systems.

  13. The experience of mathematical beauty and its neural correlates.

    OpenAIRE

    Semir eZeki; John Paul Romaya; Benincasa, Dionigi M. T.; Atiyah, Michael F.

    2014-01-01

    Many have written of the experience of mathematical beauty as being comparable to that derived from the greatest art. This makes it interesting to learn whether the experience of beauty derived from such a highly intellectual and abstract source such as mathematics correlates with activity in the same part of the emotional brain as that derived from more sensory, perceptually based, sources. To determine this, we used functional magnetic resonance imaging (fMRI) to image the activity in the b...

  14. Diffusion coefficient distribution from NMR-DOSY experiments using Hopfield neural network

    Science.gov (United States)

    Sebastião, Rita C. O.; Pacheco, Carlos N.; Braga, J. P.; Piló-Veloso, Dorila

    2006-09-01

    Diffusion ordered spectroscopy (DOSY) is a powerful two-dimensional NMR method to study molecular translation in various systems. The diffusion coefficients are usually retrieved, at each frequency, from a fit procedure on the experimental data, considering a unique coefficient for each molecule or mixture. However, the fit can be improved if one regards the decaying curve as a multiexponential function and the diffusion coefficient as a distribution. This work presents a computer code based on the Hopfield neural network to invert the data. One small-molecule binary mixture with close diffusion coefficients is treated with this approach, demonstrating the effectiveness of the method.

  15. Phase cycling schemes for finite-pulse-RFDR MAS solid state NMR experiments.

    Science.gov (United States)

    Zhang, Rongchun; Nishiyama, Yusuke; Sun, Pingchuan; Ramamoorthy, Ayyalusamy

    2015-03-01

    The finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used in 2D homonuclear chemical shift correlation experiments under magic angle spinning (MAS). A recent study demonstrated the advantages of using a short phase cycle, XY4, and its super-cycle, XY4(1)4, for the fp-RFDR pulse sequence employed in 2D (1)H/(1)H single-quantum/single-quantum correlation experiments under ultrafast MAS conditions. In this study, we report a comprehensive analysis on the dipolar recoupling efficiencies of XY4, XY4(1)2, XY4(1)3, XY4(1)4, and XY8(1)4 phase cycles under different spinning speeds ranging from 10 to 100 kHz. The theoretical calculations reveal the presence of second-order terms (T(10)T(2,±2), T(1,±1)T(2,±1), etc.) in the recoupled homonuclear dipolar coupling Hamiltonian only when the basic XY4 phase cycle is utilized, making it advantageous for proton-proton magnetization transfer under ultrafast MAS conditions. It is also found that the recoupling efficiency of fp-RFDR is quite dependent on the duty factor (τ180/τR) as well as on the strength of homonuclear dipolar couplings. The rate of longitudinal magnetization transfer increases linearly with the duty factor of fp-RFDR for all the XY-based phase cycles investigated in this study. Examination of the performances of different phase cycles against chemical shift offset and RF field inhomogeneity effects revealed that XY4(1)4 is the most tolerant phase cycle, while the shortest phase cycle XY4 suppressed the RF field inhomogeneity effects most efficiently under slow spinning speeds. Our results suggest that the difference in the fp-RFDR recoupling efficiencies decreases with the increasing MAS speed, while ultrafast (>60 kHz) spinning speed is advantageous as it recouples a large amount of homonuclear dipolar couplings and therefore enable fast magnetization exchange. The effects of higher-order terms and cross terms between various interactions in the effective Hamiltonian of fp

  16. Relaxation-compensated difference spin diffusion NMR for detecting {sup 13}C–{sup 13}C long-range correlations in proteins and polysaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Tuo; Williams, Jonathan K. [Massachusetts Institute of Technology, Department of Chemistry (United States); Schmidt-Rohr, Klaus [Brandeis University, Department of Chemistry (United States); Hong, Mei, E-mail: meihong@mit.edu [Massachusetts Institute of Technology, Department of Chemistry (United States)

    2015-02-15

    The measurement of long-range distances remains a challenge in solid-state NMR structure determination of biological macromolecules. In 2D and 3D correlation spectra of uniformly {sup 13}C-labeled biomolecules, inter-residue, inter-segmental, and intermolecular {sup 13}C–{sup 13}C cross peaks that provide important long-range distance constraints for three-dimensional structures often overlap with short-range cross peaks that only reflect the covalent structure of the molecule. It is therefore desirable to develop new approaches to obtain spectra containing only long-range cross peaks. Here we show that a relaxation-compensated modification of the commonly used 2D {sup 1}H-driven spin diffusion (PDSD) experiment allows the clean detection of such long-range cross peaks. By adding a z-filter to keep the total z-period of the experiment constant, we compensate for {sup 13}C T{sub 1} relaxation. As a result, the difference spectrum between a long- and a scaled short-mixing time spectrum show only long-range correlation signals. We show that one- and two-bond cross peaks equalize within a few tens of milliseconds. Within ∼200 ms, the intensity equilibrates within an amino acid residue and a monosaccharide to a value that reflects the number of spins in the local network. With T{sub 1} relaxation compensation, at longer mixing times, inter-residue and inter-segmental cross peaks increase in intensity whereas intra-segmental cross-peak intensities remain unchanged relative to each other and can all be subtracted out. Without relaxation compensation, the difference 2D spectra exhibit both negative and positive intensities due to heterogeneous T{sub 1} relaxation in most biomolecules, which can cause peak cancellation. We demonstrate this relaxation-compensated difference PDSD approach on amino acids, monosaccharides, a crystalline model peptide, a membrane-bound peptide and a plant cell wall sample. The resulting difference spectra yield clean multi-bond, inter

  17. 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.

  18. Optimal Design of Experiments Subject to Correlated Errors

    OpenAIRE

    Pazman, Andrej; Müller, Werner

    2000-01-01

    In this paper we consider optimal design of experiments in the case of correlated observations, when no replications are possible. This situation is typical when observing a random process or random field with known covariance structure. We present a theorem which demonstrates that the computation of optimum exact designs corresponds to solving minimization problems in terms of design measures. (author's abstract)

  19. Correlations and fluctuations in high energy heavy ion collision experiments

    Institute of Scientific and Technical Information of China (English)

    ZHOU Dai-Mei; WANG Ya-Ping; WEI Li-Hua; CAI Xu

    2008-01-01

    An overview of research status of soft physics in high energy heavy-ion collision experiments and recent experimental results are presented.The experimental status on fluctuations and correlations has been reviewed and the outlook for research status of soft physics in LHC/ALICE has been introduced in this paper.

  20. Assignment of methyl NMR resonances of a 52 kDa protein with residue-specific 4D correlation maps

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Subrata H.; Frueh, Dominique P., E-mail: dfrueh@jhmi.edu [Johns Hopkins University School of Medicine, Department of Biophysics and Biophysical Chemistry (United States)

    2015-07-15

    Methyl groups have become key probes for structural and functional studies by nuclear magnetic resonance. However, their NMR signals cluster in a small spectral region and assigning their resonances can be a tedious process. Here, we present a method that facilitates assignment of methyl resonances from assigned amide groups. Calculating the covariance between sensitive methyl and amide 3D spectra, each providing correlations to C{sup α} and C{sup β} separately, produces 4D correlation maps directly correlating methyl groups to amide groups. Optimal correlation maps are obtained by extracting residue-specific regions, applying derivative to the dimensions subject to covariance, and multiplying 4D maps stemming from different 3D spectra. The latter procedure rescues weak signals that may be missed in traditional assignment procedures. Using these covariance correlation maps, nearly all assigned isoleucine, leucine, and valine amide resonances of a 52 kDa nonribosomal peptide synthetase cyclization domain were paired with their corresponding methyl groups.

  1. Correlates of New Graduate Nurses' Experiences of Workplace Mistreatment.

    Science.gov (United States)

    Read, Emily; Laschinger, Heather K

    2015-10-01

    This study explores correlates of new graduate nurses’ experiences of workplace mistreatment. New graduate nurses’ experiences of workplace mistreatment, such as bullying, coworker incivility, and supervisor incivility, negatively influence nurses’ work and health. It is unclear whether these forms of workplace mistreatment have similar precipitating factors and outcomes. We surveyed 342 new graduate nurses in Ontario to explore correlates of 3 forms of workplace mistreatment. Workplace incivility and bullying were significantly related to authentic leadership, structural empowerment, worklife fit, and psychological capital. Bullying was more strongly related to job satisfaction, emotional exhaustion, and mental and physical health outcomes than supervisor and coworker incivility. New graduate nurses’ experiences of 3 types of workplace mistreatment are related to organizational and health factors, although bullying appears to have stronger negative effects.

  2. 13C-detected NMR experiments for measuring chemical shifts and coupling constants in nucleic acid bases.

    Science.gov (United States)

    Fiala, Radovan; Sklenár, Vladimír

    2007-10-01

    The paper presents a set of two-dimensional experiments that utilize direct (13)C detection to provide proton-carbon, carbon-carbon and carbon-nitrogen correlations in the bases of nucleic acids. The set includes a (13)C-detected proton-carbon correlation experiment for the measurement of (13)C-(13)C couplings, the CaCb experiment for correlating two quaternary carbons, the HCaCb experiment for the (13)C-(13)C correlations in cases where one of the carbons has a proton attached, the HCC-TOCSY experiment for correlating a proton with a network of coupled carbons, and a (13)C-detected (13)C-(15)N correlation experiment for detecting the nitrogen nuclei that cannot be detected via protons. The IPAP procedure is used for extracting the carbon-carbon couplings and/or carbon decoupling in the direct dimension, while the S(3)E procedure is preferred in the indirect dimension of the carbon-nitrogen experiment to obtain the value of the coupling constant. The experiments supply accurate values of (13)C and (15)N chemical shifts and carbon-carbon and carbon-nitrogen coupling constants. These values can help to reveal structural features of nucleic acids either directly or via induced changes when the sample is dissolved in oriented media.

  3. Analysis of electron correlation effects and contributions of NMR J-couplings from occupied localized molecular orbitals.

    Science.gov (United States)

    Zarycz, Natalia; Aucar, Gustavo A

    2012-02-02

    NMR J-coupling calculations at the second-order of polarization propagator approach, SOPPA, are among the most reliable. They include a high percentage of the total electron correlation effects in saturated and unsaturated molecular systems. Furthermore, J-couplings are quite sensitive to the whole electronic molecular framework. We present in this article the first study of all three response mechanisms, Fermi contact, FC, spin-dipolar, SD and paramagnetic spin-orbital, PSO, for J-couplings with occupied localized molecular orbitals at the SOPPA level of approach. Even though SOPPA results are not invariant under unitary transformations, the difference between results obtained with canonical and localized molecular orbitals, LMOs, are small enough to permit its application with confidence. The following small-size saturated and unsaturated compounds were analyzed: CH(4), CH(3)F, C(2)H(6), NH(3), C(2)H(4), CH(2)NH, H(2)C═CHF, and FHC═CHF. The local character of the FC mechanism that appears in J-couplings of these molecular models is shown through the analysis of contributions from LMOs. The importance of including the electron correlation on the engaged bonding orbitals for one-bond couplings is emphasized. Almost all electron correlation effects are included in such orbitals. Interesting findings were the large contributions by s-type LMOs to the C-H and C-C J-couplings; they are responsible for the variation of (1)J(C-C) when going from ethane to ethene and to 1,2-difluoroethene. The previously proposed hyperconjugative transfer mechanism has been tested. Among other tests we found the difference anti-syn of one-bond (1)J(C-H) in imine as due to both the corresponding σ(C-H) and the lone-pair, LP, contribution. Geminal and vicinal J-couplings were also analyzed. Our findings are in accord with a previous work by Pople and Bothner-by, who considered results taken from calculations or empirical data. For all geminal couplings the pattern of J-couplings, like

  4. Solvent dynamical behavior in an organogel phase as studied by NMR relaxation and diffusion experiments.

    Science.gov (United States)

    Yemloul, Mehdi; Steiner, Emilie; Robert, Anthony; Bouguet-Bonnet, Sabine; Allix, Florent; Jamart-Grégoire, Brigitte; Canet, Daniel

    2011-03-24

    An organogelation process depends on the gelator-solvent pair. This study deals with the solvent dynamics once the gelation process is completed. The first approach used is relaxometry, i.e., the measurement of toluene proton longitudinal relaxation time T(1) as a function of the proton NMR resonance frequency (here in the 5 kHz to 400 MHz range). Pure toluene exhibits an unexpected T(1) variation, which has been identified as paramagnetic relaxation resulting from an interaction of toluene with dissolved oxygen. In the gel phase, this contribution is retrieved with, in addition, a strong decay at low frequencies assigned to toluene molecules within the gel fibers. Comparison of dispersion curves of pure toluene and toluene in the gel phase leads to an estimate of the proportion of toluene embedded within the organogel (found around 40%). The second approach is based on carbon-13 T(1) and nuclear Overhauser effect measurements, the combination of these two parameters providing direct information about the reorientation of C-H bonds. It appears clearly that reorientation of toluene is the same in pure liquid and in the gel phase. The only noticeable changes in carbon-13 longitudinal relaxation times are due to the so-called chemical shift anisotropy (csa) mechanism and reflect slight modifications of the toluene electronic distribution in the gel phase. NMR diffusion measurements by the pulse gradient spin-echo (PGSE) method allow us to determine the diffusion coefficient of toluene inside the organogel. It is roughly two-thirds of the one in pure toluene, thus indicating that self-diffusion is the only dynamical parameter to be slightly affected when the solvent is inside the gel structure. The whole set of experimental observations leads to the conclusion that, once the gel is formed, the solvent becomes essentially passive, although an important fraction is located within the gel structure.

  5. Diels-Alder Cycloadditions: A MORE Experiment in the Organic Laboratory Including a Diene Identification Exercise Involving NMR Spectroscopy and Molecular Modeling

    Science.gov (United States)

    Shaw, Roosevelt; Severin, Ashika; Balfour, Miguel; Nettles, Columbus

    2005-01-01

    Two Diels-Alder reactions are described that are suitable for a MORE (microwave-induced organic reaction enhanced) experiment in the organic chemistry laboratory course. A second experiment in which the splitting patterns of the vinyl protons in the nuclear magnetic resonance (NMR) spectra of two MORE adducts are used in conjunction with molecular…

  6. Determination of Solvent Effects on Keto-Enol Equilibria of 1,3-Dicarbonyl Compounds Using NMR: Revisiting a Classic Physical Chemistry Experiment

    Science.gov (United States)

    Cook, A. Gilbert; Feltman, Paul M.

    2007-01-01

    The use of proton NMR to determine the equilibrium position of tautomeric 1,3-dicarbonyl compounds in various solvents has been a classic physical chemistry experiment. We are presenting an expansion of the excellent description of this experiment by Garland, Shoemaker, and Nibler. Often the assumption is made that the keto tautomer is always the…

  7. Automobile ride quality experiments correlated to iso-weighted criteria

    Science.gov (United States)

    Healey, A. J.; Young, R. K.; Smith, C. C.

    1975-01-01

    As part of an overall study to evaluate the usefulness of ride quality criteria for the design of improved ground transportation systems an experiment was conducted involving subjective and objective measurement of ride vibrations found in an automobile riding over roadways of various roughness. Correlation of the results led to some very significant relationships between passenger rating and ride accelerations. The latter were collapsed using a frequency-weighted root mean square measure of the random vibration. The results suggest the form of a design criterion giving the relationship between ride vibration and acceptable automobile ride quality. Further the ride criterion is expressed in terms that relate to rides with which most people are familiar. The design of the experiment, the ride vibration data acquisition, the concept of frequency weighting and the correlations found between subjective and objective measurements are presented.

  8. Correlations among experimental and theoretical NMR data to determine the absolute stereochemistry of darcyribeirine, a pentacyclic indole alkaloid isolated from Rauvolfia grandiflora

    Science.gov (United States)

    Cancelieri, Náuvia Maria; Ferreira, Thiago Resende; Vieira, Ivo José Curcino; Braz-Filho, Raimundo; Piló-Veloso, Dorila; Alcântara, Antônio Flávio de Carvalho

    2015-10-01

    Darcyribeirine (1) is a pentacyclic indole alkaloid isolated from Rauvolfia grandiflora. Stereochemistry of 1 was previously proposed based on 1D (coupling constant data) and 2D (NOESY correlations) NMR techniques, having been established a configuration 3R, 15S, and 20R (isomer 1a). Stereoisomers of 1 (i.e., 1a-1h) can be grouped into four sets of enantiomers. Carbon chemical shifts and hydrogen coupling constants were calculated using BLYP/6-31G* theory level for the eight isomers of 1. Calculated NMR data of 1a-1h were correlated with the corresponding experimental data of 1. The best correlations between theoretical and experimental carbon chemical shift data were obtained for the set of enantiomers 1e/1f to structures in the gaseous phase and considering solvent effects (using PCM and explicit models). Similar results were obtained when the same procedure was performed to correlations between theoretical and experimental coupling constant data. Finally, optical rotation calculations indicate 1e as its absolute stereochemistry. Orbital population analysis indicates that the hydrogen bonding between N-H of 1e and DMSO is due to contributions of its frontier unoccupied molecular orbitals, mainly LUMO+1, LUMO+2, and LUMO+3.

  9. Subjective experiences in psychotic disorders: diagnostic value and clinical correlates.

    Science.gov (United States)

    Peralta, V; Cuesta, M J

    1998-01-01

    This study evaluated the prevalence and clinical correlates of abnormal subjective experiences across functional psychotic disorders. Patients were recruited from consecutive admissions with the following diagnoses; schizophrenia (n = 40), schizophreniform disorder (n = 40), schizoaffective disorder (n = 21), mood disorder (n = 18), brief reactive psychosis (n = 15), and atypical psychosis (n = 16). Subjective experiences were assessed using the Frankfurt Complaint Questionnaire (FCQ), and the clinical status was assessed with the Scales for the Assessment of Positive and Negative Symptoms (SAPS and SANS) and the Manual for the Assessment and Documentation of Psychopathology (AMDP). Neither the FCQ total score nor individual subjective experiences displayed significant differences across diagnoses. When the clinical predictors of subjective experiences were studied by multiple regression analyses, a different pattern resulted for individual psychotic disorders. In schizophrenic patients, subjective experiences were predicted by female gender, euphoria, lack of insight, greater illness severity, and more positive symptoms. The only predictors of subjective experiences in the schizophreniform disorder group were the negative symptoms. Within the affective disorders group, subjective experiences had no clinical predictors.

  10. Vacuolar glyphosate-sequestration correlates with glyphosate resistance in ryegrass (Lolium spp.) from Australia, South America, and Europe: a 31P NMR investigation.

    Science.gov (United States)

    Ge, Xia; d'Avignon, D André; Ackerman, Joseph J H; Collavo, Alberto; Sattin, Maurizio; Ostrander, Elizabeth L; Hall, Erin L; Sammons, R Douglas; Preston, Christopher

    2012-02-01

    Lolium spp., ryegrass, variants from Australia, Brazil, Chile, and Italy showing differing levels of glyphosate resistance were examined by (31)P NMR. Extents of glyphosate (i) resistance (LD(50)), (ii) inhibition of 5-enopyruvyl-shikimate-3-phosphate synthase (EPSPS) activity (IC(50)), and (iii) translocation were quantified for glyphosate-resistant (GR) and glyphosate-sensitive (GS) Lolium multiflorum Lam. variants from Chile and Brazil. For comparison, LD(50) and IC(50) data for Lolium rigidum Gaudin variants from Italy were also analyzed. All variants showed similar cellular uptake of glyphosate by (31)P NMR. All GR variants showed glyphosate sequestration within the cell vacuole, whereas there was minimal or no vacuole sequestration in the GS variants. The extent of vacuole sequestration correlated qualitatively with the level of resistance. Previous (31)P NMR studies of horseweed ( Conyza canadensis (L.) Cronquist) revealed that glyphosate sequestration imparted glyphosate resistance. Data presented herein suggest that glyphosate vacuolar sequestration is strongly contributing, if not the major contributing, resistance mechanism in ryegrass as well.

  11. 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.

  12. Transport Experiments on 2D Correlated Electron Physics in Semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Tsui, Daniel

    2014-03-24

    This research project was designed to investigate experimentally the transport properties of the 2D electrons in Si and GaAs, two prototype semiconductors, in several new physical regimes that were previously inaccessible to experiments. The research focused on the strongly correlated electron physics in the dilute density limit, where the electron potential energy to kinetic energy ratio rs>>1, and on the fractional quantum Hall effect related physics in nuclear demagnetization refrigerator temperature range on samples with new levels of purity and controlled random disorder.

  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. Enzymatic Resolution of 1-Phenylethanol and Formation of a Diastereomer: An Undergraduate [superscript 1]H NMR Experiment to Introduce Chiral Chemistry

    Science.gov (United States)

    Faraldos, Juan A.; Giner, Jos-Luis; Smith, David H.; Wilson, Mark; Ronhovde, Kyla; Wilson, Erin; Clevette, David; Holmes, Andrea E.; Rouhier, Kerry

    2011-01-01

    This organic laboratory experiment introduces students to stereoselective enzyme reactions, resolution of enantiomers, and NMR analysis of diastereomers. The reaction between racemic 1-phenylethanol and vinyl acetate in hexane to form an ester is catalyzed by acylase I. The unreacted alcohol is then treated with a chiral acid and the resulting…

  15. What Is the True Color of Fresh Meat? A Biophysical Undergraduate Laboratory Experiment Investigating the Effects of Ligand Binding on Myoglobin Using Optical, EPR, and NMR Spectroscopy

    Science.gov (United States)

    Linenberger, Kimberly; Bretz, Stacey Lowery; Crowder, Michael W.; McCarrick, Robert; Lorigan, Gary A.; Tierney, David L.

    2011-01-01

    With an increased focus on integrated upper-level laboratories, we present an experiment integrating concepts from inorganic, biological, and physical chemistry content areas. Students investigate the effects of ligand strength on the spectroscopic properties of the heme center in myoglobin using UV-vis, [superscript 1]H NMR, and EPR…

  16. What Is the True Color of Fresh Meat? A Biophysical Undergraduate Laboratory Experiment Investigating the Effects of Ligand Binding on Myoglobin Using Optical, EPR, and NMR Spectroscopy

    Science.gov (United States)

    Linenberger, Kimberly; Bretz, Stacey Lowery; Crowder, Michael W.; McCarrick, Robert; Lorigan, Gary A.; Tierney, David L.

    2011-01-01

    With an increased focus on integrated upper-level laboratories, we present an experiment integrating concepts from inorganic, biological, and physical chemistry content areas. Students investigate the effects of ligand strength on the spectroscopic properties of the heme center in myoglobin using UV-vis, [superscript 1]H NMR, and EPR…

  17. A J-modulated protonless NMR experiment characterizes the conformational ensemble of the intrinsically disordered protein WIP.

    Science.gov (United States)

    Rozentur-Shkop, Eva; Goobes, Gil; Chill, Jordan H

    2016-12-01

    Intrinsically disordered proteins (IDPs) are multi-conformational polypeptides that lack a single stable three-dimensional structure. It has become increasingly clear that the versatile IDPs play key roles in a multitude of biological processes, and, given their flexible nature, NMR is a leading method to investigate IDP behavior on the molecular level. Here we present an IDP-tailored J-modulated experiment designed to monitor changes in the conformational ensemble characteristic of IDPs by accurately measuring backbone one- and two-bond J((15)N,(13)Cα) couplings. This concept was realized using a unidirectional (H)NCO (13)C-detected experiment suitable for poor spectral dispersion and optimized for maximum coverage of amino acid types. To demonstrate the utility of this approach we applied it to the disordered actin-binding N-terminal domain of WASp interacting protein (WIP), a ubiquitous key modulator of cytoskeletal changes in a range of biological systems. One- and two-bond J((15)N,(13)Cα) couplings were acquired for WIP residues 2-65 at various temperatures, and in denaturing and crowding environments. Under native conditions fitted J-couplings identified in the WIP conformational ensemble a propensity for extended conformation at residues 16-23 and 45-60, and a helical tendency at residues 28-42. These findings are consistent with a previous study of the based upon chemical shift and RDC data and confirm that the WIP(2-65) conformational ensemble is biased towards the structure assumed by this fragment in its actin-bound form. The effects of environmental changes upon this ensemble were readily apparent in the J-coupling data, which reflected a significant decrease in structural propensity at higher temperatures, in the presence of 8 M urea, and under the influence of a bacterial cell lysate. The latter suggests that crowding can cause protein unfolding through protein-protein interactions that stabilize the unfolded state. We conclude that J-couplings are

  18. Computational Chemistry Meets Experiments for Explaining the Behavior of Bibenzyl: A Thermochemical and Spectroscopic (Infrared, Raman, and NMR) Investigation.

    Science.gov (United States)

    Latouche, Camille; Barone, Vincenzo

    2014-12-09

    The structure, conformational behavior, and spectroscopic parameters of bibenzyl have been investigated by a computational protocol including proper treatment of anharmonic and hindered rotor contributions. Conventional hybrid functionals overstabilize the anti conformer while low-order post-Hartree-Fock (MP2) approaches strongly favor the gauche conformer. However, inclusion of semiempirical dispersion effects in density functionals or coupled cluster post-Hartree-Fock models agree in forecasting the simultaneous presence of both conformers in the gas phase with a slightly larger stability (0.7 kcal·mol(-1)) of the gauche conformer. Addition of thermal and entropic effects finally leads to very close Gibbs free energies for both conformers and, thus, to a slight preference for the gauche form due to statistical factors (2 vs 1). The situation remains essentially the same in solution. On these grounds, perturbative vibrational computations including both electrical and mechanical anharmonicities lead to IR and Raman spectra in remarkable agreement with experiment. Full assignment of the IR spectra explains the presence of peaks from gauche or anti conformers. Comparison between computed and experimental Raman spectra confirms that both conformers are present in liquid phase, whereas the anti conformer seems to be preponderant in the solid state. Also computed NMR parameters are in good agreement with experiment.

  19. Determination of Molecular Self-Diffusion Coefficients Using Pulsed-Field-Gradient NMR: An Experiment for Undergraduate Physical Chemistry Laboratory

    Science.gov (United States)

    Harmon, Jennifer; Coffman, Cierra; Villarrial, Spring; Chabolla, Steven; Heisel, Kurt A.; Krishnan, Viswanathan V.

    2012-01-01

    NMR spectroscopy has become one of the primary tools that chemists utilize to characterize a range of chemical species in the solution phase, from small organic molecules to medium-sized proteins. A discussion of NMR spectroscopy is an essential component of physical and biophysical chemistry lecture courses, and a number of instructional…

  20. Determination of Molecular Self-Diffusion Coefficients Using Pulsed-Field-Gradient NMR: An Experiment for Undergraduate Physical Chemistry Laboratory

    Science.gov (United States)

    Harmon, Jennifer; Coffman, Cierra; Villarrial, Spring; Chabolla, Steven; Heisel, Kurt A.; Krishnan, Viswanathan V.

    2012-01-01

    NMR spectroscopy has become one of the primary tools that chemists utilize to characterize a range of chemical species in the solution phase, from small organic molecules to medium-sized proteins. A discussion of NMR spectroscopy is an essential component of physical and biophysical chemistry lecture courses, and a number of instructional…

  1. Solution NMR analysis of the interaction between the actinoporin sticholysin I and DHPC micelles--correlation with backbone dynamics.

    Science.gov (United States)

    López-Castilla, Aracelys; Pazos, Fabiola; Schreier, Shirley; Pires, José Ricardo

    2014-06-01

    Sticholysin I (StI), an actinoporin expressed as a water-soluble protein by the sea anemone Stichodactyla helianthus, binds to natural and model membranes, forming oligomeric pores. It is proposed that the first event of a multistep pore formation mechanism consists of the monomeric protein attachment to the lipid bilayer. To date there is no high-resolution structure of the actinoporin pore or other membrane-bound form available. Here we evaluated StI:micelle complexes of variable lipid composition to look for a suitable model for NMR studies. Micelles of pure or mixed lysophospholipids and of dihexanoyl phosphatidylcholine (DHPC) were examined. The StI:DHPC micelle was found to be the best system, yielding a stable sample and good quality spectra. A comprehensive chemical shift perturbation analysis was performed to map the StI membrane recognition site in the presence of DHPC micelles. The region mapped (residues F(51), R(52), S(53) in loop 3; F(107), D(108), Y(109), W(111), Y(112), W(115) in loop 7; Q(129), Y(132), D(134), M(135), Y(136), Y(137), G(138) in helix-α2) is in agreement with previously reported data, but additional residues were found to interact, especially residues V(81), A(82), T(83), G(84) in loop 5, and A(85), A(87) in strand-β5. Backbone dynamics measurements of StI free in solution and bound to micelles highlighted the relevance of protein flexibility for membrane binding and suggested that a conformer selection process may take place during protein-membrane interaction. We conclude that the StI:DHPC micelles system is a suitable model for further characterization of an actinoporin membrane-bound form by solution NMR.

  2. Nuclear Spins as Quantum Testbeds: Singlet States, Quantum Correlations, and Delayed-choice Experiments

    CERN Document Server

    Roy, Soumya Singha

    2012-01-01

    Nuclear Magnetic Resonance (NMR) forms a natural test-bed to perform quantum information processing (QIP) and has so far proven to be one of the most successful quantum information processors. The nuclear spins in a molecule treated as quantum bits or qubits which are the basic building blocks of a quantum computer. The development of NMR over half a century puts it in a platform where we can utilize its excellent control techniques over an ensemble of spin systems and perform quantum computation in a highly controlled way. Apart from a successful quantum information processor, NMR is also a highly powerful quantum platform where many of the potentially challenging quantum mechanical experiments can be performed.

  3. 最高量子相关谱技术在同核偶合常数测定中的应用%MEASUREMENT OF HOMONUCLEAR COUPLING CONSTANTS USING TWO-DIMENSIONAL MAXIMUM-QUANTUM CORRELATION NMR SPECTROSCOPY (MAXY-NMR)

    Institute of Scientific and Technical Information of China (English)

    张许; 刘买利

    1999-01-01

    It has been a continuous interest in measurement of homonuclear scalar coupling constants using two-dimensional NMR spectroscopy because large chemical shift dispersions can efficiently increase spectral resolution. Numerous methods have been developed using homo- and hetero-nuclear correlation and successfully used for a variety of samples. Here we demonstrate an alternative approach based on maximum-quantum correlation NMR spectroscopy (MAXY NMR). The new method combines the advantages of two-dimensional chemical shift dispersion and the spectral editing feature of the MAXY approach and results in separated correlations of CH, CH2, and CH3 groups in a single experiment with enhanced chemical shift resolution. The method had been tested on a middle-sized molecule, dexamethasone, and a tridecapeptide, neurotensin.%偶合常数是一个重要的NMR参数,其数值与分子中化学键的二面角有关,可以为分子结构研究提供很重要的信息.多维NMR谱由于具有较大的化学位移分辨率,因此常常被用来测定同核或异核自旋-自旋偶合常数.本文介绍了利用最高量子相关技术(MAXY)测定同核偶合常数的方法.MAXY是最近发展的一种多维NMR谱编辑技术,可以使不同官能团(CH, CH2, CH3)的相关峰分布于不同的图谱区域,因此比常规的二维谱具有更高的化学位移分辨率.而且被分离开来的NMR相关峰呈吸收性线型,能清楚地展示各自的偶合分裂特征,可以直接用于测定偶合常数.

  4. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoaceticum metabolic profiles

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Junfeng; Isern, Nancy G.; Ewing, R James; Liyu, Andrey V.; Sears, Jesse A.; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R.; Ahring, Birgitte K.; Majors, Paul D.

    2014-06-20

    An in-situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch-growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution, high sensitivity NMR (HR-NMR) spectroscopy. In-situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at an NMR frequency of 500 MHz, and aliquots of the bioreactor contents were taken for 600 MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in-situ NMR bioreactor facilitated monitoring of the fermentation process in real time, enabling identification of intermediate and end-point metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with the HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts.

  5. Discovery of New E-Selectin Inhibitors by Virtual Screening, Fluorescence Binding Assays, and STD NMR Experiments.

    Science.gov (United States)

    Barra, Pabla A; Jiménez, Verónica A; Gavin, José A; Daranas, Antonio H; Alderete, Joel B

    2016-05-06

    E-selectin is an endothelial protein that participates in the adhesion of metastatic cancer cells, and is therefore a relevant target for antitumor therapeutic intervention. In this work, virtual screening was used to identify new E-selectin inhibitors from a subset of drug-like molecules retrieved from the ZINC database, including the physiological ligand sLe(x) as reference structure (PDB ID: 1G1T). Four hits were chosen and subjected to molecular dynamics simulations and fluorescence binding assays, which led to the determination of experimental dissociation constants between 333 and 1012 μm. The candidate with the highest affinity was studied by saturation transfer difference (STD) NMR experiments and complete relaxation and conformational exchange matrix analysis of saturation transfer (CORCEMA-ST), aimed at identifying the preferable binding mode with E-selectin. Our results revealed that this new inhibitor binds more strongly than sLe(x) in the E-selectin binding site, in good agreement with simulation predictions. These properties will prove valuable for the future design of drugs that target E-selectin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The application of 199Hg NMR and 199mHg perturbed angular correlation (PAC) spectroscopy to define the biological chemistry of HgII

    DEFF Research Database (Denmark)

    Iranzo, Olga; Thulstrup, Peter Waaben; Ryu, Seung-baek;

    2007-01-01

    H values and at peptide/HgII ratios of 3:1 with an unusual trigonal thiolate coordination mode. The resulting HgII complexes are good water-soluble models for HgII binding to the protein MerR. We have carried out a parallel study using 199Hg NMR and 199mHg perturbed angular correlation (PAC) spectroscopy...... to characterize the distinct species that are generated under different pH conditions and peptide TRI L9C/HgII ratios. These studies prove for the first time the formation of [Hg{(TRI L9C)2-(TRI L9C H)}], a dithiolate-HgII complex in the hydrophobic interior of the three-stranded coiled coil (TRI L9C)3. 199Hg NMR...... and 199mHg PAC data demonstrate that this dithiolate-HgII complex is different from the dithiolate [Hg(TRI L9C)2], and that the presence of third -helix, containing a protonated cysteine, breaks the symmetry of the coordination environment present in the complex [Hg(TRI L9C)2]. As the pH is raised...

  7. Knowing about tools: neural correlates of tool familiarity and experience.

    Science.gov (United States)

    Vingerhoets, Guy

    2008-04-15

    The observation of tools is known to elicit a distributed cortical network that reflects close-knit relations of semantic, action-related, and perceptual knowledge. The neural correlates underlying the critical knowledge of skilled tool use, however, remain to be elucidated. In this study, functional magnetic resonance imaging in 14 volunteers compares neural activation during the observation of familiar tools versus equally graspable unfamiliar tools of which the observers have little, if any, functional knowledge. In a second paradigm, the level of tool-experience is investigated by comparing the neural effects of observing frequently versus infrequently used familiar tools. Both familiar and unfamiliar tools activate the classic neural network associated with tool representations. Direct comparison of the activation patterns during the observation of familiar and unfamiliar tools in a priori determined regions of interest (ptool-use knowledge, with supramarginal gyrus storing information about limb and hand positions, and precuneus storing visuospatial information about hand-tool interactions. As no frontal activation survived this contrast, it appears that premotor activity is unrelated to experience based motor knowledge of tool use/function, but rather, is elicited by any graspable tool. Confrontation with unfamiliar or infrequently used tools reveals an increase in inferior temporal and medial and lateral occipital activation, predominantly in the left hemisphere, suggesting that these regions reflect visual feature processing for tool identification.

  8. Analysis and optimization of saturation transfer difference NMR experiments designed to map early self-association events in amyloidogenic peptides.

    Science.gov (United States)

    Huang, Hao; Milojevic, Julijana; Melacini, Giuseppe

    2008-05-08

    Saturation transfer difference (STD) methods recently have been proposed to be a promising tool for self-recognition mapping at residue and atomic resolution in amyloidogenic peptides. Despite the significant potential of the STD approach for systems undergoing oligomer/monomer (O/M) equilibria, a systematic analysis of the possible artifacts arising in this novel application of STD experiments is still lacking. Here, we have analyzed the STD method as applied to O/M peptides, and we have identified three major sources of possible biases: offset effects, intramonomer cross-relaxation, and partial spin-diffusion within the oligomers. For the purpose of quantitatively assessing these artifacts, we employed a comparative approach that relies on 1-D and 2-D STD data acquired at different saturation frequencies on samples with different peptide concentrations and filtration states. This artifact evaluation protocol was applied to the Abeta(12-28) model system, and all three types of artifacts appear to affect the measured STD spectra. In addition, we propose a method to minimize the biases introduced by these artifacts in the Halpha STD distributions used to obtain peptide self-recognition maps at residue resolution. This method relies on the averaging of STD data sets acquired at different saturation frequencies and provides results comparable to those independently obtained through other NMR pulse sequences that probe oligomerization, such as nonselective off-resonance relaxation experiments. The artifact evaluation protocol and the multiple frequencies averaging strategy proposed here are of general utility for the growing family of amyloidogenic peptides, as they provide a reliable analysis of STD spectra in terms of polypeptide self-recognition epitopes.

  9. Low-power broadband homonuclear dipolar recoupling without decoupling: Double-quantum 13C NMR correlations at very fast magic-angle spinning

    Science.gov (United States)

    Teymoori, Gholamhasan; Pahari, Bholanath; Stevensson, Baltzar; Edén, Mattias

    2012-09-01

    We report novel symmetry-based radio-frequency (rf) pulse sequences for efficient excitation of double-quantum (2Q) coherences under very fast (>60 kHz) magic-angle spinning (MAS) conditions. The recursively generated pulse-scheme series, R22p1R22p-1(p=1,2,3,…), offers broadband 13C-13C recoupling in organic solids at a very low rf power. No proton decoupling is required. A high-order average Hamiltonian theory analysis reveals a progressively enhanced resonance-offset compensation for increasing p, as verified both by numerical simulations and 2Q filtration NMR experiments on 13C2-glycine, [2,3-13C2]alanine, and [U-13C]tyrosine at 14.1 T and 66 kHz MAS, where the pulse schemes with p⩾3 compare favorably to current state-of-the-art recoupling options.

  10. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoacetica metabolic profiles.

    Science.gov (United States)

    Xue, Junfeng; Isern, Nancy G; Ewing, R James; Liyu, Andrei V; Sears, Jesse A; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R; Ahring, Birgitte K; Majors, Paul D

    2014-10-01

    An in situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution NMR (HR-NMR) spectroscopy. In situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at 500 MHz, and aliquots of the bioreactor contents were taken for 600-MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol, and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in situ NMR bioreactor facilitated monitoring of the fermentation process, enabling identification of intermediate and endpoint metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts.

  11. A refined model of the chlorosomal antennae of the green bacterium chlorobium tepidum from proton chemical shift constraints obtained with high-field 2-D and 3-D MAS NMR dipolar correlation spectroscopy

    NARCIS (Netherlands)

    Rossum, van B.E.J.; Steengaard, D.B.; Boender, G.J.; Schaffner, K.; Holzwarth, A.R.; Groot, de H.J.M.

    2001-01-01

    Heteronuclear 2-D and 3-D magic-angle spinning NMR dipolar correlation spectroscopy was applied to determine solid-state 1H shifts for aggregated bacteriochlorophyll c (BChl c) in uniformly 13C-enriched light harvesting chlorosomes of the green photosynthetic bacterium Chlorobium tepidum. A complete

  12. A refined model of the chlorosomal antennae of the green bacterium chlorobium tepidum from proton chemical shift constraints obtained with high-field 2-D and 3-D MAS NMR dipolar correlation spectroscopy

    NARCIS (Netherlands)

    Rossum, van B.E.J.; Steengaard, D.B.; Boender, G.J.; Schaffner, K.; Holzwarth, A.R.; Groot, de H.J.M.

    2001-01-01

    Heteronuclear 2-D and 3-D magic-angle spinning NMR dipolar correlation spectroscopy was applied to determine solid-state 1H shifts for aggregated bacteriochlorophyll c (BChl c) in uniformly 13C-enriched light harvesting chlorosomes of the green photosynthetic bacterium Chlorobium tepidum. A complete

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

    Science.gov (United States)

    Chesick, John P.

    1989-01-01

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

  14. Direct study of minor extra-virgin olive oil components without any sample modification. (1)H NMR multisupression experiment: A powerful tool.

    Science.gov (United States)

    Ruiz-Aracama, Ainhoa; Goicoechea, Encarnación; Guillén, María D

    2017-08-01

    Proton Nuclear Magnetic Resonance ((1)H NMR) was employed to study monovarietal commercial Spanish extra-virgin olive oils (EVOO) (Arbequina, Arroniz, Cornicabra, Hojiblanca and Picual). Each sample was analyzed by a standard pulse and by an experiment suppressing the main lipid signals, enabling the detection of signals of minor components. The aim was to determine the possibilities of both (1)H NMR approaches to characterize EVOO composition, focusing on acyl groups, squalene, sterols, triterpene acids/esters, fatty alcohols, wax esters and phenols (lignans, tyrosol, hydroxytyrosol, oleocanthal, oleacein, oleokoronal, oleomissional, ligstrodials and oleuropeindials), and to determine hydrolysis and oxidation levels. The signal assignments (in deuterated chloroform) are thoroughly described, identifying for the first time those of the protons of esters of phytol and of geranylgeraniol. Correct signal assignment is fundamental for obtaining sound results when interpreting statistical data from metabolomic studies of EVOO composition and adulteration, making it possible to differentiate and classify oils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. NMR CHARACTERIZATIONS OF PROPERTIES OF HETEROGENEOUS MEDIA

    Energy Technology Data Exchange (ETDEWEB)

    C.T. Philip Chang; Changho Choi; Jeromy T. Hollenshead; Rudi Michalak; Jack Phan; Ramon Saavedra; John C. Slattery; Jinsoo Uh; Randi Valestrand; A. Ted Watson; Song Xue

    2005-01-01

    developed methodology using that data to determine spatially resolved permeability distributions. We investigate the use of intrinsic properties for developing improved correlations for predicting permeability from NMR well-logging data and for obtaining more accurate estimates of multiphase flow properties--the relative permeability and capillary pressure--from displacement experiments. We demonstrate the use of MRI measurements of saturation and relaxation for prediction wetting-phase relative permeability for unstable experiments. Finally, we developed an improved method for determining surface relaxivity with NMR experiments, which can provide better descriptions of permeable media microstructures and improved correlations for permeability predictions.

  16. Correlates of Bulimia Nervosa: Early Family Mealtime Experiences.

    Science.gov (United States)

    Miller, Debra A. F.; And Others

    1993-01-01

    Examined relationship of early mealtime experiences to later bulimia in 128 female college students. Found significant group differences among bulimics, nonbulimics, and repeat dieters on early meal experience questionnaire, with bulimic group reporting most negative and unusual experiences. Found significant differences among groups on depression…

  17. NMR Study of Water Distribution inside Tomato Cells: Effects of Water Stress

    OpenAIRE

    Musse, M.; Cambert, M.; Mariette, F.

    2010-01-01

    Tomato pericarp tissue was studied by low-field nuclear magnetic res-onance (NMR) relaxometry. Two kinds of experiments were performed to inves-tigate the correlation between multi-exponential NMR relaxation and the subcellular compartments. The longitudinal (T 1 ) versus transverse (T 2 ) relaxation times were first measured on fresh samples and then the transverse relaxation time was measured on samples exposed to water stress. Four signal components were found in all experiments. The resul...

  18. Correlation between electronic parameters and corrosion inhibition of benzothiazole derivatives- NMR parameters as important and neglected descriptors

    Science.gov (United States)

    Behzadi, Hadi; Forghani, Ali

    2017-03-01

    The relation between electronic properties and corrosion inhibitive performance of three benzothiazole derivatives 1,3-benzothiazol-2-amine (BTA), 6-methyl-1,3-benzothiazol-2-amine (MBTA) and 2-amino-1,3-benzthiazole-6-thiol (TBTA) has been investigated by density functional theory. The electronic properties including EHOMO, ELUMO and related parameters were calculated at the B3LYP/6-311++G(d,p) level. The chemical shielding CS tensors were introduced as important and neglected descriptors to evaluate inhibitive efficiency of corrosion inhibitors. Nuclear independent chemical shift (NICS) components, as an aromaticity criterion, were also investigated as local descriptor. Polarizability and CS descriptors, as second rank tensors, show the best correlations with inhibition efficiencies of studied inhibitors.

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

    Science.gov (United States)

    Cavaleiro, Jose A. S.

    1987-01-01

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

  20. Revised NMR data for incartine: an alkaloid from Galanthus elwesii.

    Science.gov (United States)

    Berkov, Strahil; Reyes-Chilpa, Ricardo; Codina, Carles; Viladomat, Francesc; Bastida, Jaume

    2007-07-12

    Phytochemical studies on Galanthus elwesii resulted in the isolation of five alkaloids: incartine, hordenine, hippeastrine, 8-O-demethylhomolycorine and lycorine. The NMR data given previously for incartine were revised and completed by two-dimensional 1H-1H and 1H-13C chemical shift correlation experiments. In vitro studies on the bioactivity of incartine were carried out.

  1. Revised NMR data for Incartine: an Alkaloid from Galanthus elwesii

    Directory of Open Access Journals (Sweden)

    Jaume Bastida

    2007-07-01

    Full Text Available Phytochemical studies on Galanthus elwesii resulted in the isolation of five alkaloids: incartine, hordenine, hippeastrine, 8-O-demethylhomolycorine and lycorine. The NMR data given previously for incartine were revised and completed by two-dimensional 1H-1H and 1H-13C chemical shift correlation experiments. In vitro studies on the bioactivity of incartine were carried out.

  2. Interfaces in polymer nanocomposites – An NMR study

    Energy Technology Data Exchange (ETDEWEB)

    Böhme, Ute; Scheler, Ulrich, E-mail: scheler@ipfdd.de [Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, 01069 Dresden (Germany)

    2016-03-09

    Nuclear Magnetic Resonance (NMR) is applied for the investigation of polymer nanocomposites. Solid-state NMR is applied to study the modification steps to compatibilize layered double hydroxides with non-polar polymers. {sup 1}H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T{sub 2} is most suited. In this presentation we report on two applications of T{sub 2} measurements under external mechanical stress. In a low-field system relaxation NMR studies are performed in-situ under uniaxial stress. High-temperature experiments in a Couette cell permit the investigation of the polymer dynamics in the melt under shear flow.

  3. Proposed experiment to test the bounds of quantum correlations

    CERN Document Server

    Cabello, A

    2004-01-01

    The combination of quantum correlations appearing in the Clauser-Horne-Shimony-Holt inequality can give values between the classical bound, 2, and Cirel'son's bound, 2\\sqrt 2. However, for a given set of local observables, there are values in this range which no quantum state can attained. For a given parametrization of the local observables, we provide the analytical expression for the bounds of quantum correlations and describe how to experimentally trace it using a source of singlet states.

  4. Proton detection for signal enhancement in solid-state NMR experiments on mobile species in membrane proteins

    Energy Technology Data Exchange (ETDEWEB)

    Ward, Meaghan E.; Ritz, Emily [University of Guelph, Department of Physics (Canada); Ahmed, Mumdooh A. M. [Suez University, The Department of Physics, Faculty of Science (Egypt); Bamm, Vladimir V.; Harauz, George [University of Guelph, Biophysics Interdepartmental Group (Canada); Brown, Leonid S.; Ladizhansky, Vladimir, E-mail: vladizha@uoguelph.ca [University of Guelph, Department of Physics (Canada)

    2015-12-15

    Direct proton detection is becoming an increasingly popular method for enhancing sensitivity in solid-state nuclear magnetic resonance spectroscopy. Generally, these experiments require extensive deuteration of the protein, fast magic angle spinning (MAS), or a combination of both. Here, we implement direct proton detection to selectively observe the mobile entities in fully-protonated membrane proteins at moderate MAS frequencies. We demonstrate this method on two proteins that exhibit different motional regimes. Myelin basic protein is an intrinsically-disordered, peripherally membrane-associated protein that is highly flexible, whereas Anabaena sensory rhodopsin is composed of seven rigid transmembrane α-helices connected by mobile loop regions. In both cases, we observe narrow proton linewidths and, on average, a 10× increase in sensitivity in 2D insensitive nuclear enhancement of polarization transfer-based HSQC experiments when proton detection is compared to carbon detection. We further show that our proton-detected experiments can be easily extended to three dimensions and used to build complete amino acid systems, including sidechain protons, and obtain inter-residue correlations. Additionally, we detect signals which do not correspond to amino acids, but rather to lipids and/or carbohydrates which interact strongly with membrane proteins.

  5. Avoiding bias effects in NMR experiments for heteronuclear dipole-dipole coupling determinations: principles and application to organic semiconductor materials.

    Science.gov (United States)

    Kurz, Ricardo; Cobo, Marcio Fernando; de Azevedo, Eduardo Ribeiro; Sommer, Michael; Wicklein, André; Thelakkat, Mukundan; Hempel, Günter; Saalwächter, Kay

    2013-09-16

    Carbon-proton dipole-dipole couplings between bonded atoms represent a popular probe of molecular dynamics in soft materials or biomolecules. Their site-resolved determination, for example, by using the popular DIPSHIFT experiment, can be challenged by spectral overlap with nonbonded carbon atoms. The problem can be solved by using very short cross-polarization (CP) contact times, however, the measured modulation curves then deviate strongly from the theoretically predicted shape, which is caused by the dependence of the CP efficiency on the orientation of the CH vector, leading to an anisotropic magnetization distribution even for isotropic samples. Herein, we present a detailed demonstration and explanation of this problem, as well as providing a solution. We combine DIPSHIFT experiments with the rotor-directed exchange of orientations (RODEO) method, and modifications of it, to redistribute the magnetization and obtain undistorted modulation curves. Our strategy is general in that it can also be applied to other types of experiments for heteronuclear dipole-dipole coupling determinations that rely on dipolar polarization transfer. It is demonstrated with perylene-bisimide-based organic semiconductor materials, as an example, in which measurements of dynamic order parameters reveal correlations of the molecular dynamics with the phase structure and functional properties.

  6. Correlation between Facial Expressions and the Game Experience Questionnaire

    NARCIS (Netherlands)

    Tan, C.T.; Bakkes, S.; Pisan, Y.

    2014-01-01

    Quantitative methods in the domain of player experience evaluation provide continuous and real-time analyses of player experiences. However, current quantitative methods are mostly either too confined within in-game statistics, or require non-typical laboratory play setups to monitor real-life behav

  7. Classic Hallucinogens and Mystical Experiences: Phenomenology and Neural Correlates.

    Science.gov (United States)

    Barrett, Frederick S; Griffiths, Roland R

    2017-03-26

    This chapter begins with a brief review of descriptions and definitions of mystical-type experiences and the historical connection between classic hallucinogens and mystical experiences. The chapter then explores the empirical literature on experiences with classic hallucinogens in which claims about mystical or religious experiences have been made. A psychometrically validated questionnaire is described for the reliable measurement of mystical-type experiences occasioned by classic hallucinogens. Controlled laboratory studies show that under double-blind conditions that provide significant controls for expectancy bias, psilocybin can occasion complete mystical experiences in the majority of people studied. These effects are dose-dependent, specific to psilocybin compared to placebo or a psychoactive control substance, and have enduring impact on the moods, attitudes, and behaviors of participants as assessed by self-report of participants and ratings by community observers. Other studies suggest that enduring personal meaning in healthy volunteers and therapeutic outcomes in patients, including reduction and cessation of substance abuse behaviors and reduction of anxiety and depression in patients with a life-threatening cancer diagnosis, are related to the occurrence of mystical experiences during drug sessions. The final sections of the chapter draw parallels in human neuroscience research between the neural bases of experiences with classic hallucinogens and the neural bases of meditative practices for which claims of mystical-type experience are sometimes made. From these parallels, a functional neural model of mystical experience is proposed, based on changes in the default mode network of the brain that have been observed after the administration of classic hallucinogens and during meditation practices for which mystical-type claims have been made.

  8. Functional Groups Determine Biochar Properties (pH and EC) as Studied by Two-Dimensional (13)C NMR Correlation Spectroscopy.

    Science.gov (United States)

    Li, Xiaoming; Shen, Qirong; Zhang, Dongqing; Mei, Xinlan; Ran, Wei; Xu, Yangchun; Yu, Guanghui

    2013-01-01

    While the properties of biochar are closely related to its functional groups, it is unclear under what conditions biochar develops its properties. In this study, two-dimensional (2D) (13)C nuclear magnetic resonance (NMR) correlation spectroscopy was for the first time applied to investigate the development of functional groups and establish their relationship with biochar properties. The results showed that the agricultural biomass carbonized to biochars was a dehydroxylation/dehydrogenation and aromatization process, mainly involving the cleavage of O-alkylated carbons and anomeric O-C-O carbons in addition to the production of fused-ring aromatic structures and aromatic C-O groups. With increasing charring temperature, the mass cleavage of O-alkylated groups and anomeric O-C-O carbons occurred prior to the production of fused-ring aromatic structures. The regression analysis between functional groups and biochar properties (pH and electrical conductivity) further demonstrated that the pH and electrical conductivity of rice straw derived biochars were mainly determined by fused-ring aromatic structures and anomeric O-C-O carbons, but the pH of rice bran derived biochars was determined by both fused-ring aromatic structures and aliphatic O-alkylated (HCOH) carbons. In summary, this work suggests a novel tool for characterising the development of functional groups in biochars.

  9. Functional Groups Determine Biochar Properties (pH and EC as Studied by Two-Dimensional (13C NMR Correlation Spectroscopy.

    Directory of Open Access Journals (Sweden)

    Xiaoming Li

    Full Text Available While the properties of biochar are closely related to its functional groups, it is unclear under what conditions biochar develops its properties. In this study, two-dimensional (2D (13C nuclear magnetic resonance (NMR correlation spectroscopy was for the first time applied to investigate the development of functional groups and establish their relationship with biochar properties. The results showed that the agricultural biomass carbonized to biochars was a dehydroxylation/dehydrogenation and aromatization process, mainly involving the cleavage of O-alkylated carbons and anomeric O-C-O carbons in addition to the production of fused-ring aromatic structures and aromatic C-O groups. With increasing charring temperature, the mass cleavage of O-alkylated groups and anomeric O-C-O carbons occurred prior to the production of fused-ring aromatic structures. The regression analysis between functional groups and biochar properties (pH and electrical conductivity further demonstrated that the pH and electrical conductivity of rice straw derived biochars were mainly determined by fused-ring aromatic structures and anomeric O-C-O carbons, but the pH of rice bran derived biochars was determined by both fused-ring aromatic structures and aliphatic O-alkylated (HCOH carbons. In summary, this work suggests a novel tool for characterising the development of functional groups in biochars.

  10. NMR in pulsed magnetic field

    KAUST Repository

    Abou-Hamad, Edy

    2011-09-01

    Nuclear magnetic resonance (NMR) experiments in pulsed magnetic fields up to 30.4 T focused on 1H and 93Nb nuclei are reported. Here we discuss the advantage and limitation of pulsed field NMR and why this technique is able to become a promising research tool. © 2011 Elsevier Inc. All Rights Reserved.

  11. T2-Filtered T2 - T2 Exchange NMR

    Science.gov (United States)

    d'Eurydice, Marcel Nogueira; Montrazi, Elton Tadeu; Fortulan, Carlos Alberto; Bonagamba, Tito José

    2016-05-01

    This work introduces an alternative way to perform the T2 - T2 Exchange NMR experiment. Rather than varying the number of π pulses in the first CPMG cycle of the T2 - T2 Exchange NMR pulse sequence, as used to obtain the 2D correlation maps, it is fixed and small enough to act as a short T2-filter. By varying the storage time, a set of 1D measurements of T2 distributions can be obtained to reveal the effects of the migration dynamics combined with relaxation effects. This significantly reduces the required time to perform the experiment, allowing a more in-depth study of exchange dynamics and relaxation processes with improved signal-to-noise ratio. These aspects stand as basis of this novel experiment, T2-Filtered T2 - T2 Exchange NMR or simply T2 F-TREx.

  12. Two-meson Correlation Femtoscopy in the SELEX Experiment

    Science.gov (United States)

    Nigmatkulov, Grigory

    The two-particle correlations at low relative momenta provide spatio-temporal information about the evolution of the system created in particle and heavy ion collisions. In this paper we discuss the basic concepts of the method and give a short review of recent experimental results obtained at Tevatron and LHC.

  13. High resolution NMR theory and chemical applications

    CERN Document Server

    Becker, Edwin D

    1969-01-01

    High Resolution NMR: Theory and Chemical Applications focuses on the applications of nuclear magnetic resonance (NMR), as well as chemical shifts, lattices, and couplings. The book first offers information on the theory of NMR, including nuclear spin and magnetic moment, spin lattice relaxation, line widths, saturation, quantum mechanical description of NMR, and ringing. The text then ponders on instrumentation and techniques and chemical shifts. Discussions focus on the origin of chemical shifts, reference compounds, empirical correlations of chemical shifts, modulation and phase detection,

  14. 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.

  15. First Measurements of Pion Correlations by the PHENIX Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, S C

    2001-04-11

    First identical-pion correlations measured at RHIC energies by PHENIX are presented. Two analyses with separate detectors, systematics, and statistics provide consistent results. The resulting HBT radii are moderately larger than those measured at lower energies. The k{sub t} dependence of the Bertsch-Pratt HBT radii is also similar to previous measures and is consistent with the conjecture of an expanding source.

  16. Neural correlates of the LSD experience revealed by multimodal neuroimaging

    Science.gov (United States)

    Carhart-Harris, Robin L.; Muthukumaraswamy, Suresh; Roseman, Leor; Kaelen, Mendel; Droog, Wouter; Murphy, Kevin; Tagliazucchi, Enzo; Schenberg, Eduardo E.; Nest, Timothy; Orban, Csaba; Leech, Robert; Williams, Luke T.; Williams, Tim M.; Bolstridge, Mark; Sessa, Ben; McGonigle, John; Sereno, Martin I.; Nichols, David; Hobden, Peter; Evans, John; Singh, Krish D.; Wise, Richard G.; Curran, H. Valerie; Feilding, Amanda; Nutt, David J.

    2016-01-01

    Lysergic acid diethylamide (LSD) is the prototypical psychedelic drug, but its effects on the human brain have never been studied before with modern neuroimaging. Here, three complementary neuroimaging techniques: arterial spin labeling (ASL), blood oxygen level-dependent (BOLD) measures, and magnetoencephalography (MEG), implemented during resting state conditions, revealed marked changes in brain activity after LSD that correlated strongly with its characteristic psychological effects. Increased visual cortex cerebral blood flow (CBF), decreased visual cortex alpha power, and a greatly expanded primary visual cortex (V1) functional connectivity profile correlated strongly with ratings of visual hallucinations, implying that intrinsic brain activity exerts greater influence on visual processing in the psychedelic state, thereby defining its hallucinatory quality. LSD’s marked effects on the visual cortex did not significantly correlate with the drug’s other characteristic effects on consciousness, however. Rather, decreased connectivity between the parahippocampus and retrosplenial cortex (RSC) correlated strongly with ratings of “ego-dissolution” and “altered meaning,” implying the importance of this particular circuit for the maintenance of “self” or “ego” and its processing of “meaning.” Strong relationships were also found between the different imaging metrics, enabling firmer inferences to be made about their functional significance. This uniquely comprehensive examination of the LSD state represents an important advance in scientific research with psychedelic drugs at a time of growing interest in their scientific and therapeutic value. The present results contribute important new insights into the characteristic hallucinatory and consciousness-altering properties of psychedelics that inform on how they can model certain pathological states and potentially treat others. PMID:27071089

  17. Neural correlates of the LSD experience revealed by multimodal neuroimaging.

    Science.gov (United States)

    Carhart-Harris, Robin L; Muthukumaraswamy, Suresh; Roseman, Leor; Kaelen, Mendel; Droog, Wouter; Murphy, Kevin; Tagliazucchi, Enzo; Schenberg, Eduardo E; Nest, Timothy; Orban, Csaba; Leech, Robert; Williams, Luke T; Williams, Tim M; Bolstridge, Mark; Sessa, Ben; McGonigle, John; Sereno, Martin I; Nichols, David; Hellyer, Peter J; Hobden, Peter; Evans, John; Singh, Krish D; Wise, Richard G; Curran, H Valerie; Feilding, Amanda; Nutt, David J

    2016-04-26

    Lysergic acid diethylamide (LSD) is the prototypical psychedelic drug, but its effects on the human brain have never been studied before with modern neuroimaging. Here, three complementary neuroimaging techniques: arterial spin labeling (ASL), blood oxygen level-dependent (BOLD) measures, and magnetoencephalography (MEG), implemented during resting state conditions, revealed marked changes in brain activity after LSD that correlated strongly with its characteristic psychological effects. Increased visual cortex cerebral blood flow (CBF), decreased visual cortex alpha power, and a greatly expanded primary visual cortex (V1) functional connectivity profile correlated strongly with ratings of visual hallucinations, implying that intrinsic brain activity exerts greater influence on visual processing in the psychedelic state, thereby defining its hallucinatory quality. LSD's marked effects on the visual cortex did not significantly correlate with the drug's other characteristic effects on consciousness, however. Rather, decreased connectivity between the parahippocampus and retrosplenial cortex (RSC) correlated strongly with ratings of "ego-dissolution" and "altered meaning," implying the importance of this particular circuit for the maintenance of "self" or "ego" and its processing of "meaning." Strong relationships were also found between the different imaging metrics, enabling firmer inferences to be made about their functional significance. This uniquely comprehensive examination of the LSD state represents an important advance in scientific research with psychedelic drugs at a time of growing interest in their scientific and therapeutic value. The present results contribute important new insights into the characteristic hallucinatory and consciousness-altering properties of psychedelics that inform on how they can model certain pathological states and potentially treat others.

  18. On Storks and Babies: Correlation, Causality and Field Experiments

    Directory of Open Access Journals (Sweden)

    Lambrecht Anja

    2016-11-01

    Full Text Available The explosion of available data has created much excitement among marketing practitioners about their ability to better understand the impact of marketing investments. Big data allows for detecting patterns and often it seems plausible to interpret them as causal. While it is quite obvious that storks do not bring babies, marketing relationships are usually less clear. Apparent “causalities” often fail to hold up under examination. If marketers want to be sure not to walk into a causality trap, they need to conduct field experiments to detect true causal relationships. In the present digital environment, experiments are easier than ever to execute. However, they need to be prepared and interpreted with great care in order to deliver meaningful and genuinely causal results that help improve marketing decisions.

  19. A metabolic network analysis & NMR experiment design tool with user interface-driven model construction for depth-first search analysis.

    Science.gov (United States)

    Zhu, T; Phalakornkule, C; Ghosh, S; Grossmann, I E; Koepsel, R R; Ataai, M M; Domach, M M

    2003-04-01

    A Windows program for metabolic engineering analysis and experimental design has been developed. A graphical user interface enables the pictorial, "on-screen" construction of a metabolic network. Once a model is composed, balance equations are automatically generated. Model construction, modification and information exchange between different users is thus considerably simplified. For a given model, the program can then be used to predict all the extreme point flux distributions that optimize an objective function while satisfying balances and constraints by using a depth-first search strategy. One can also find the minimum reaction set that satisfies different conditions. Based on the identified flux distributions or linear combinations, the user can simulate the NMR and GC/MS spectra of selected signal molecules. Alternately, spectra vectorization allows for the automated optimization of labeling experiments that are intended to distinguish between different, yet plausible flux extreme point distributions. The example provided entails predicting the flux distributions associated with deleting pyruvate kinase and designing 13C NMR experiments that can maximally discriminate between the flux distributions.

  20. Correlation between experience targets and competence for general surgery certification.

    Science.gov (United States)

    De Siqueira, J R; Gough, M J

    2016-06-01

    Working time restrictions and public expectation have stimulated competence-based assessment in surgery. Nevertheless, certification of completion of training, and board accreditation across the developed world, still rely on experiential models based on indicative numbers as markers of operative competence. This study assessed the correlation between trainer assessment of competence and completion of indicative numbers. Analysis of UK Intercollegiate Surgical Curriculum Programme portfolios of general surgical trainees in a single Local Education and Training Board allowed comparison of Procedure Based Assessment (PBA) scores (level of competence) for cholecystectomy, segmental colectomy and Hartmann's procedure with operative numbers. Among 121 trainees, there was a positive correlation between operative numbers and 1058 PBA scores for cholecystectomy (rs  = 0·532, P < 0·001), segmental colectomy (rs  = 0·552, P < 0·001) and Hartmann's procedure (rs  = 0·663, P < 0·001). Of those who completed the indicative numbers defined for each procedure to achieve certification of completion of training, only eight of 30 performing cholecystectomy, eight of 52 undertaking segmental colectomy and seven of 36 performing Hartmann's procedure had achieved three PBAs at the level considered to represent independent operating (level 4). More than half of all assessments (259 of 428, 60·5 per cent; 85 of 132 cholecystectomy, 140 of 217 colectomy and 34 of 79 Hartmann's) performed after trainees had completed their indicative numbers were scored below level 4. A minimum number of index procedures did not reflect competence in a significant proportion of trainees. A more reliable tool is required for certification. © 2016 BJS Society Ltd Published by John Wiley & Sons Ltd.

  1. 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.

  2. Causality, relativity and quantum correlation experiments with moving reference frames

    Indian Academy of Sciences (India)

    H Zbinden; J Brendel; W Tittel; N Gisin

    2001-02-01

    Entanglement, one of the most important features of quantum mechanics, is at the core of the famous Einstein–Bohr philosophical debate [1] and is the principal resource for quantum information processing [2]. We report on new experimental investigations of the properties of entangled photon pairs with emphasis on the tension between quantum mechanics and relativity [3,4]. Entangled photons are sent via an optical fiber network to two villages near Geneva, separated by more than 10 km where they are analyzed by interferometers [5]. The photon pair source is set as precisely as possible in the center so that the two photons arrive at the detectors within a time interval of less than 5 ps (corresponding to a path length difference of less than 1 mm). This sets a lower bound on the ‘speed of quantum information’ to 107 times the speed of light. Next, one detector is set in motion [6] so that both detectors, each in its own inertial reference frame, are first to do the measurement! The data always reproduces the quantum correlations.

  3. 1H-NMR assignments of GM1-oligosaccharide in deuterated water at 500 MHz by two-dimensional spin-echo J-correlated spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ong, R.L.; Yu, R.K.

    1986-02-15

    The 1H-NMR spectra of the oligosaccharide derived from monosialoganglioside GM1 (GM1 = beta-D-galactosyl-(1-3)-beta-D-N-acetylgalactosaminyl-(1-4)- (alpha-N-acetylneuraminyl-(2-3)-)-beta-D-galactosyl-(1-4)-b eta-D-glucosylceramide) (GM1OS) and its reduced form (GM1OS-R) have been obtained at 500 MHz in D2O. Through the combined use of one-dimensional and homonuclear two-dimensional spin-echo J-correlated (2D SECSY) spectra of GM1OS-R, the assignments for the ring protons of GM1OS are made. Data on chemical shifts and coupling constants of GM1OS including the alpha-linked neuraminic acid protons, in aqueous solution, are tabulated. Due to the very small coupling constants (less than 2 Hz) and the closeness in chemical shifts (less than 0.04 ppm) for the pair of correlated peaks in the two-dimensional spectrum, the information on the connectivities of the H5 ring protons of the neutral sugar residues is missing. Second-order coupling also blurs this information. Data are compared with those obtained for ganglioside GM1 in dimethyl sulfoxide (DMSO; the actual composition therein was 97% DMSO-d6 and 3% D2O) by T. A. W. Koerner, J. H. Prestegard, P. C. Demou, and R. K. Yu. While the heterogeneity of chemical shifts for the H5, H6a, and H6b protons diminishes in D2O, that for A-9a and A-9b remains. The latter suggests an intraneuraminic acid conformation involving the glycerol side chain unaffected by the solvent. Moreover, the chemical shifts of the III-1, III-2, and A-4 protons (and perhaps the II-4, IV-2, and A-8 protons) in D2O exhibit unusual upfield shifts compared with those in DMSO. This indicates that the intramolecular interactions between GalNAc residue III and neuraminic acid present in DMSO are weakened in D2O. The effect of temperature on the conformation is also examined and appears to be minimal (less than 0.02 ppm) in the range 22-50 degrees C.

  4. Quantum irreversible decoherence behaviour in open quantum systems with few degrees of freedom. Application to 1H NMR reversion experiments in nematic liquid crystals

    CERN Document Server

    Segnorile, H H

    2013-01-01

    An experimental study of NMR spin decoherence in nematic liquid crystals is presented. The outcome of the experiments are analyzed in the framework of a theory that considers the spins as an open quantum system coupled to a quantum molecular environment, presented by the authors recently. Decoherence dynamics can be put in evidence by means of refocusing experiments of the dipolar interactions. The experimental technique used in this work is based on the MREV8 pulse sequence. Non-idealities of the experimental setting, like external field inhomogeneity, pulse misadjustments and the presence of non-reverted spin interaction terms are analysed in detail and their effects on the observed signal decay are estimated. It is found that, though all these non-idealities could in principle affect the evolution of the spin dynamics, their influence can be mitigated and they do not present the characteristic behaviour of the irreversible spin decoherence. As unique characteristic of decoherence, the experimental results ...

  5. Slow or swift, your patients' experience won't drift: absence of correlation between physician productivity and the patient experience.

    Science.gov (United States)

    Lenz, Kasia; McRae, Andrew; Wang, Dongmei; Higgins, Benjamin; Innes, Grant; Cook, Timothy; Lang, Eddy

    2017-09-01

    Absract OBJECTIVES: To evaluate the relationship between Emergency Physician (EP) productivity and patient satisfaction with Emergency Department (ED) care. This retrospective observational study linked administrative and patient experience databases to measure correlations between the patient experience and EP productivity. The study was performed across three Calgary EDs (from June 2010 to July 2013). Patients>16 years old with completed Health Quality Council of Alberta (HQCA) ED Patient Experience Surveys were included. EP productivity was measured at the individual physician level and defined as the average number of patients seen per hour. The association between physician productivity and patient experience scores from six composite domains of the HQCA ED Patient Experience Survey were examined using Pearson correlation coefficients, linear regression modelling, and a path analysis. We correlated 3,794 patient experience surveys with productivity data for 130 EPs. Very weak non-significant negative correlations existed between productivity and survey composites: "Staff Care and Communication" (r=-0.057, p=0.521), "Discharge Communication" (r=-0.144, p=0.102), and "Respect" (r=-0.027, p=0.760). Very weak, non-significant positive correlations existed between productivity and the composite domains: "Medication Communication" (r=0.003, p=0.974) and "Pain management" (r=0.020, p=0.824). A univariate general linear model yielded no statistically significant correlations between EP productivity and patient experience, and the path analysis failed to show a relationship between the variables. We found no correlation between EP productivity and the patient experience.

  6. NMR of geophysical drill cores with a mobile Halbach scanner

    Energy Technology Data Exchange (ETDEWEB)

    Talnishnikh, E.

    2007-08-21

    This thesis is devoted to a mobile NMR with an improved Halbach scanner. This is a lightweight tube-shaped magnet with sensitive volume larger and a homogeneity of the magnetic field higher than the previous prototype version. The improved Halbach scanner is used for analysis of water-saturated drill cores and plugs with diameters up to 60 mm. To provide the analysis, the standard 1D technique with the CPMG sequence as well as 2D correlation experiments were successfully applied and adapted to study properties of fluid-saturated sediments. Afterwards the Halbach scanner was calibrated to fast non-destructive measurements of porosity, relaxation time distributions, and estimation of permeability. These properties can be calculated directly from the NMR data using the developed methodology. Any independent measurements of these properties with other methods are not needed. One of the main results of this work is the development of a new NMR on-line core scanner for measurements of porosity in long cylindrical and semi cylindrical drill cores. Also dedicated software was written to operate the NMR on-line core scanner. The physical background of this work is the study of the diffusion influence on transverse relaxation. The diffusion effect in the presence of internal gradients in porous media was probed by 1D and 2D experiments. The transverse relaxation time distributions obtained from 1D and from 2D experiments are comparable but different in fine details. Two new methodologies were developed based on the results of this study. First is the methodology quantifying the influence of diffusion in the internal gradients of water-saturated sediments on transverse relaxation from 2D correlation experiments. The second one is the correction of the permeability estimation from the NMR data taking in account the influence of the diffusion. Furthermore, PFG NMR technique was used to study restricted diffusion in the same kind of samples. Preliminary results are reported

  7. Proton-detected MAS NMR experiments based on dipolar transfers for backbone assignment of highly deuterated proteins

    Science.gov (United States)

    Chevelkov, Veniamin; Habenstein, Birgit; Loquet, Antoine; Giller, Karin; Becker, Stefan; Lange, Adam

    2014-05-01

    Proton-detected solid-state NMR was applied to a highly deuterated insoluble, non-crystalline biological assembly, the Salmonella typhimurium type iii secretion system (T3SS) needle. Spectra of very high resolution and sensitivity were obtained at a low protonation level of 10-20% at exchangeable amide positions. We developed efficient experimental protocols for resonance assignment tailored for this system and the employed experimental conditions. Using exclusively dipolar-based interspin magnetization transfers, we recorded two sets of 3D spectra allowing for an almost complete backbone resonance assignment of the needle subunit PrgI. The additional information provided by the well-resolved proton dimension revealed the presence of two sets of resonances in the N-terminal helix of PrgI, while in previous studies employing 13C detection only a single set of resonances was observed.

  8. Fundamentals of Protein NMR Spectroscopy

    CERN Document Server

    Rule, Gordon S

    2006-01-01

    NMR spectroscopy has proven to be a powerful technique to study the structure and dynamics of biological macromolecules. Fundamentals of Protein NMR Spectroscopy is a comprehensive textbook that guides the reader from a basic understanding of the phenomenological properties of magnetic resonance to the application and interpretation of modern multi-dimensional NMR experiments on 15N/13C-labeled proteins. Beginning with elementary quantum mechanics, a set of practical rules is presented and used to describe many commonly employed multi-dimensional, multi-nuclear NMR pulse sequences. A modular analysis of NMR pulse sequence building blocks also provides a basis for understanding and developing novel pulse programs. This text not only covers topics from chemical shift assignment to protein structure refinement, as well as the analysis of protein dynamics and chemical kinetics, but also provides a practical guide to many aspects of modern spectrometer hardware, sample preparation, experimental set-up, and data pr...

  9. NMR spectrometers as "magnetic tongues"

    DEFF Research Database (Denmark)

    Malmendal, Anders; Amoresano, Claudia; Trotta, Roberta

    2011-01-01

    opened up the possibility to calibrate the sensory perception. In this frame, we have tested the potentiality of nuclear magnetic resonance spectroscopy as a predictive tool to measure sensory descriptors. In particular, we have used an NMR metabolomic approach that allowed us to differentiate...... the analyzed samples based on their chemical composition. We were able to correlate the NMR metabolomic fingerprints recorded for canned tomato samples to the sensory descriptors bitterness, sweetness, sourness, saltiness, tomato and metal taste, redness, and density, suggesting that NMR might be a very useful...

  10. A triple resonance hyperfine sublevel correlation experiment for assignment of electron-nuclear double resonance lines

    Science.gov (United States)

    Potapov, Alexey; Epel, Boris; Goldfarb, Daniella

    2008-02-01

    A new, triple resonance, pulse electron paramagnetic resonance (EPR) sequence is described. It provides spin links between forbidden electron spin transitions (ΔMS=±1, ΔMI≠0) and allowed nuclear spin transitions (ΔMI=±1), thus, facilitating the assignment of nuclear frequencies to their respective electron spin manifolds and paramagnetic centers. It also yields the relative signs of the hyperfine couplings of the different nuclei. The technique is based on the combination of electron-nuclear double resonance (ENDOR) and electron-electron double resonance (ELDOR)-detected NMR experiments in a way similar to the TRIPLE experiment. The feasibility and the information content of the method are demonstrated first on a single crystal of Cu-doped L-histidine and then on a frozen solution of a Cu-histidine complex.

  11. Determination of Critical Experiment Correlations Using the Sampler Sequence Within SCALE 6.2

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, William BJ J [ORNL; Rearden, Bradley T [ORNL

    2015-01-01

    The validation of neutron transport methods used in nuclear criticality safety analyses is required by consensus American National Standards Institute/American Nuclear Society (ANSI/ANS) standards. In the last decade, there has been an increased interest in correlations among critical experiments used in validation that have shared physical attributes and which impact the independence of each measurement. The statistical methods included in many of the frequently cited guidance documents on performing validation calculations incorporate the assumption that all individual measurements are independent, so little guidance is available to practitioners on the topic. Typical guidance includes recommendations to select experiments from multiple facilities and experiment series in an attempt to minimize the impact of correlations or common-cause errors in experiments. Recent efforts have been made both to determine the magnitude of such correlations between experiments and to develop and apply methods for adjusting the bias and bias uncertainty to account for the correlations. This paper describes recent work performed at Oak Ridge National Laboratory using the Sampler sequence from the SCALE code system to develop experimental correlations using a Monte Carlo sampling technique. Sampler will be available for the first time with the release of SCALE 6.2, and a brief introduction to the methods used to calculate experiment correlations within this new sequence is presented in this paper. Techniques to utilize these correlations in the establishment of upper subcritical limits are the subject of a companion paper and will not be discussed here. Example experimental uncertainties and correlation coefficients are presented for a variety of low-enriched uranium water-moderated lattice experiments selected for use in a benchmark exercise by the Working Party on Nuclear Criticality Safety Subgroup on Uncertainty Analysis in Criticality Safety Analyses. The results include

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

    Science.gov (United States)

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

    2016-08-10

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

  13. Differential susceptibility experiments: going beyond correlational evidence: comment on beyond mental health, differential susceptibility articles.

    Science.gov (United States)

    van IJzendoorn, Marinus H; Bakermans-Kranenburg, Marian J

    2012-05-01

    Reviewing the studies on differential susceptibility presented in this section, we argue that the time is ripe to go beyond correlational designs to differential susceptibility experiments. In such experiments, randomization prevents hidden moderator effects on the environment and guarantees the independence of moderator and outcome, while the environment is manipulated and assessed in standard ways. Correlational studies generate a priori expectations about crucial moderators (e.g., temperament, biological sensitivity, and genetics). We discuss the differential susceptibility experiments available up until now and conclude that these experiments are feasible and contribute in unique ways to our conceptions of differential susceptibility.

  14. Review and proposal for heat transfer predictions at supercritical water conditions using existing correlations and experiments

    Energy Technology Data Exchange (ETDEWEB)

    Jaeger, Wadim, E-mail: wadim.jaeger@kit.edu [Karlsruhe Institute of Technology, Institute for Neutron Physics and Reactor Technology, DE-76344 Eggenstein-Leopoldshafen (Germany); Sanchez Espinoza, Victor Hugo [Karlsruhe Institute of Technology, Institute for Neutron Physics and Reactor Technology, DE-76344 Eggenstein-Leopoldshafen (Germany); Hurtado, Antonio [Technical University of Dresden, Institute of Power Engineering, DE-01062 Dresden (Germany)

    2011-06-15

    Highlights: > Implementation of heat transfer correlations for supercritical water into TRACE. > Simulation of several heat transfer experiments with modified TRACE version. > Most correlations are not able to reproduce the experimental results. > Bishop, Sandberg and Tong correlation is most suitable for TRACE applications. - Abstract: This paper summarizes the activities of the TRACE code validation at the Institute for Neutron Physics and Reactor Technology related to supercritical water conditions. In particular, the providing of the thermo physical properties and its appropriate use in the wall-to-fluid heat transfer models in the frame of the TRACE code is the object of this investigation. In a first step, the thermo physical properties of the original TRACE code were modified in order to account for supercritical conditions. In a second step, existing Nusselt correlations were reviewed and implemented into TRACE and available experiments were simulated to identify the most suitable Nusselt correlation(s).

  15. On the correlation of nonlinear variables containing secular trend variations: numerical experiments

    Institute of Scientific and Technical Information of China (English)

    Shi Neng; Yi Yan-Ming; Gu Jun-Qiang; Xia Dong-Dong

    2006-01-01

    Due to global warming, the general circulation, underlying surfaces characteristics, and geophysical and meteorological elements all show evident secular trends. This paper points out that when calculating the correlation of two variables containing their own obvious secular trends, the interannual correlation characteristics between the two variables may be distorted (overestimated or underestimated). Numerical experiments in this paper show that if two variables have opposite secular trends, the correlation coefficient between the two variables is reduced (the positive correlation is underestimated, or the negative correlation is overestimated); and if the two variables have the same sign of secular trends, the correlation coefficient between the two variables is increased (the positive correlation is overestimated,or the negative correlation is underestimated). Numerical experiments also suggest that the effect of secular trends on the interannual correlation of the two variables is interchangeable, that is to say, as long as the values of the two trends are not changed, the two variables interchange their positions, and the effect of the secular trends on the interannual correlation coefficient of the two variables remains the same. If the two variables have the same-(opposite-) sign trends,the effect of secular trends on the interannual correlation coefficient is more (less) distinctive. A meteorological example is given.

  16. Variable angle correlation spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y K [Univ. of California, Berkeley, CA (United States)

    1994-05-01

    In this dissertation, a novel nuclear magnetic resonance (NMR) technique, variable angle correlation spectroscopy (VACSY) is described and demonstrated with {sup 13}C nuclei in rapidly rotating samples. These experiments focus on one of the basic problems in solid state NMR: how to extract the wealth of information contained in the anisotropic component of the NMR signal while still maintaining spectral resolution. Analysis of the anisotropic spectral patterns from poly-crystalline systems reveal information concerning molecular structure and dynamics, yet in all but the simplest of systems, the overlap of spectral patterns from chemically distinct sites renders the spectral analysis difficult if not impossible. One solution to this problem is to perform multi-dimensional experiments where the high-resolution, isotropic spectrum in one dimension is correlated with the anisotropic spectral patterns in the other dimensions. The VACSY technique incorporates the angle between the spinner axis and the static magnetic field as an experimental parameter that may be incremented during the course of the experiment to help correlate the isotropic and anisotropic components of the spectrum. The two-dimensional version of the VACSY experiments is used to extract the chemical shift anisotropy tensor values from multi-site organic molecules, study molecular dynamics in the intermediate time regime, and to examine the ordering properties of partially oriented samples. The VACSY technique is then extended to three-dimensional experiments to study slow molecular reorientations in a multi-site polymer system.

  17. 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

    Natural soil: Comparison of Relaxometric Imaging, T1 - T2 Correlation and Fast-Field Cycling NMR." The Open Magnetic Resonance Journal: in print. Pohlmeier, A., S. Haber-Pohlmeier, et al. (2009). "A Fast Field Cycling NMR Relaxometry Study of Natural Soils." Vadose Zone J. 8: 735-742. Stingaciu, L. R., A. Pohlmeier, et al. (2009). "Characterization of unsaturated porous media by high-field and low-field NMR relaxometry." Water Resources Research 45: W08412

  18. Differential Susceptibility Experiments: Going beyond Correlational Evidence--Comment on beyond Mental Health, Differential Susceptibility Articles

    Science.gov (United States)

    van IJzendoorn, Marinus H.; Bakermans-Kranenburg, Marian J.

    2012-01-01

    Reviewing the studies on differential susceptibility presented in this section, we argue that the time is ripe to go beyond correlational designs to differential susceptibility experiments. In such experiments, randomization prevents hidden moderator effects on the environment and guarantees the independence of moderator and outcome, while the…

  19. Experiments with Tris(ethylenediamine)cobalt(III) Compounds: 59Co NMR and the Resolution of Enantiomeric [Co(en)3] 3+ Ion and Analysis by Formation of Diastereomeric Ion Pairs

    Science.gov (United States)

    Borer, L. L.; Russell, J. G.; Settlage, R. E.; Bryant, R. G.

    2002-04-01

    Cobalt(III) complexes have been used in the undergraduate inorganic laboratory to demonstrate various techniques in coordination chemistry. This report describes an experiment involving the synthesis and resolution of enantiomeric tris(ethylenediamine)cobalt(III) compounds followed by the analysis of enantiomeric purity by optical rotation and 59Co NMR spectroscopy through the formation of diastereomeric ion pairs.

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

    Science.gov (United States)

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

    2016-01-01

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

  1. NMR experiments for the measurement of proton-proton and carbon-carbon residual dipolar couplings in uniformly labelled oligosaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Pastor, Manuel [Universidad de Santiago de Compostela, Laboratorio Integral de Estructura de Biomoleculas Jose. R. Carracido, Unidade de Resonancia Magnetica, RIAIDT (Spain)], E-mail: mmartin@usc.es; Canales-Mayordomo, Angeles; Jimenez-Barbero, Jesus [Departamento de Estructura y funcion de proteinas, Centro de Investigaciones Biologicas, CSIC (Spain)], E-mail: jjbarbero@cib.csic.es

    2003-08-15

    A 2D-HSQC-carbon selective/proton selective-constant time COSY, 2D-HSQC-(sel C, sel H)-CT COSY experiment, which is applicable to uniformly {sup 13}C isotopically enriched samples (U-{sup 13}C) of oligosaccharides or oligonucleotides is proposed for the measurement of proton-proton RDC in crowded regions of 2D-spectra. In addition, a heteronuclear constant time-COSY experiment, {sup 13}C-{sup 13}C CT-COSY, is proposed for the measurement of one bond carbon-carbon RDC in these molecules. These two methods provide an extension, to U-{sup 13}C molecules, of the original homonuclear constant time-COSY experiment proposed by Tian et al. (1999) for saccharides. The combination of a number of these RDC with NOE data may provide the method of choice to study oligosaccharide conformation in the free and receptor-bound state.

  2. 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.

  3. 3D H2BC: A novel experiment for small-molecule and biomolecular NMR at natural isotopic abundance

    DEFF Research Database (Denmark)

    Meier, Sebastian; Benie, Andrew J; Duus, Jens Øllgaard

    2009-01-01

    3D H2BC is introduced for heteronuclear assignment on natural abundance samples even for biomolecules up to at least 10 kDa in low millimolar concentrations as an overnight experiment using the latest generation of cryogenically cooled probes. The short pulse sequence duration of H2BC is maintained...

  4. Local environments and lithium adsorption on the iron oxyhydroxides lepidocrocite (gamma-FeOOH) and goethite (alpha-FeOOH): A 2H-2 and 7Li solid-state MAS NMR study

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Grey, Clare P.; Paik, Jonkim

    2008-01-01

    2H and 7LiMAS NMR spectroscopy techniques were applied to study the local surface and bulk environments of iron oxyhydroxide lepiclocrocite (gamma-FeOOH). 2H variable-temperature (VT) MAS NMR experiments were performed, showing the presence of short-range, strong antiferromagnetic correlations, e...

  5. Theoretical Modeling of 99 Tc NMR Chemical Shifts

    Energy Technology Data Exchange (ETDEWEB)

    Hall, Gabriel B.; Andersen, Amity; Washton, Nancy M.; Chatterjee, Sayandev; Levitskaia, Tatiana G.

    2016-09-06

    Technetium (Tc) displays a rich chemistry due to the wide range of oxidation states (from -I to +VII) and ability to form coordination compounds. Determination of Tc speciation in complex mixtures is a major challenge, and 99Tc NMR spec-troscopy is widely used to probe chemical environments of Tc in odd oxidation states. However interpretation of the 99Tc NMR data is hindered by the lack of reference compounds. DFT computations can help fill this gap, but to date few com-putational studies have focused on 99Tc NMR of compounds and complexes. This work systematically evaluates the inclu-sion small percentages of Hartree-Fock exchange correlation and relativistic effects in DFT computations to support in-terpretation of the 99Tc NMR spectra. Hybrid functionals are found to perform better than their pure GGA counterparts, and non-relativistic calculations have been found to generally show a lower mean absolute deviation from experiment. Overall non-relativistic PBE0 and B3PW91 calculations are found to most accurately predict 99Tc NMR chemical shifts.

  6. Optical pumping and xenon NMR

    Energy Technology Data Exchange (ETDEWEB)

    Raftery, M. Daniel [Univ. of California, Berkeley, CA (United States)

    1991-11-01

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

  7. Optical pumping and xenon NMR

    Energy Technology Data Exchange (ETDEWEB)

    Raftery, M.D.

    1991-11-01

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

  8. Correlation of adverse childhood experiences with psychiatric disorders and aggressiveness in adulthood

    Directory of Open Access Journals (Sweden)

    Samardžić Ljiljana

    2010-01-01

    Full Text Available Background/Aim. Consequences of individual adverse childhood experiences for adult mental health have been precisely studied during past decades. The focus of past research was mainly on childhood maltreatment and neglect. The aim of this paper was to determine association between multiple adverse childhood experiences and psychiatric disorders, as well as their correlation to the degree and type of aggressiveness in adult psychiatric patients. Methods. One hundred and thirteen psychiatric outpatients were divided into three diagnostic groups: psychotics, non-psychotics and alcoholics and compared with fourty healthy individuals. Adverse childhood experiences data were gathered retrospectively, using the Adverse childhood experiences questionnaire and explanatory interview. Aggressiveness was assessed using Buss-Perry Aggression Questionnaire. The Student's t test, ANOVA and correlational analysis were used for evaluation of statistical significance of differences among the groups. A value p < 0.05 was considered statistically significant. Results. Our results showed that the mean number of adverse childhood experiences in each group of psychiatric patients, as well as in the whole group of patients, was statistically significantly higher than in the group of healthy individuals (p < 0.001; there was a statistically significant difference in score of physical aggressiveness between the patients exposed to adverse childhood experiences and those who were not exposed to them (p < 0.05; scores of physical aggressiveness were in positive correlation with the number of adverse childhood experiences (p < 0.05. The highest mean score of adverse childhood experiences was evidenced in the group of patients with psychotic disorders. Conclusion. Multiple adverse childhood experiences are significantly associated with psychotic disorders, nonpsychotic disorders and alcohol dependence in adulthood and their presence is important morbidity risk factor for

  9. Solid-state NMR of the Yersinia pestis outer membrane protein Ail in lipid bilayer nanodiscs sedimented by ultracentrifugation

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Yi; Fujimoto, L. Miya; Yao, Yong; Marassi, Francesca M., E-mail: fmarassi@sbmri.org [Sanford-Burnham Medical Research Institute (United States)

    2015-04-15

    Solid-state NMR studies of sedimented soluble proteins has been developed recently as an attractive approach for overcoming the size limitations of solution NMR spectroscopy while bypassing the need for sample crystallization or precipitation (Bertini et al. Proc Natl Acad Sci USA 108(26):10396–10399, 2011). Inspired by the potential benefits of this method, we have investigated the ability to sediment lipid bilayer nanodiscs reconstituted with a membrane protein. In this study, we show that nanodiscs containing the outer membrane protein Ail from Yersinia pestis can be sedimented for solid-state NMR structural studies, without the need for precipitation or lyophilization. Optimized preparations of Ail in phospholipid nanodiscs support both the structure and the fibronectin binding activity of the protein. The same sample can be used for solution NMR, solid-state NMR and activity assays, facilitating structure–activity correlation experiments across a wide range of timescales.

  10. The transverse momentum dependence of charged kaon Bose–Einstein correlations in the SELEX experiment

    Directory of Open Access Journals (Sweden)

    G.A. Nigmatkulov

    2016-02-01

    Full Text Available We report the measurement of the one-dimensional charged kaon correlation functions using 600GeV/c Σ−, π− and 540GeV/c p beams from the SELEX (E781 experiment at the Fermilab Tevatron. K±K± correlation functions are studied for three transverse pair momentum, kT, ranges and parameterized by a Gaussian form. The emission source radii, R, and the correlation strength, λ, are extracted. The analysis shows a decrease of the source radii with increasing kaon transverse pair momentum for all beam types.

  11. The transverse momentum dependence of charged kaon Bose-Einstein correlations in the SELEX experiment

    Science.gov (United States)

    Nigmatkulov, G. A.; Ponosov, A. K.; Akgun, U.; Alkhazov, G.; Amaro-Reyes, J.; Asratyan, A.; Atamantchouk, A. G.; Ayan, A. S.; Balatz, M. Y.; Blanco-Covarrubias, A.; Bondar, N. F.; Cooper, P. S.; Dauwe, L. J.; Davidenko, G. V.; Dersch, U.; Dolgolenko, A. G.; Dzyubenko, G. B.; Edelstein, R.; Emediato, L.; Endler, A. M. F.; Engelfried, J.; Eschrich, I.; Escobar, C. O.; Estrada, N.; Evdokimov, A. V.; Filimonov, I. S.; Flores-Castillo, A.; Garcia, F. G.; Giller, I.; Golovtsov, V. L.; Gouffon, P.; Gülmez, E.; Iori, M.; Jun, S. Y.; Kaya, M.; Kilmer, J.; Kim, V. T.; Kochenda, L. M.; Konorov, I.; Kozhevnikov, A. P.; Krivshich, A. G.; Krüger, H.; Kubantsev, M. A.; Kubarovsky, V. P.; Kulyavtsev, A. I.; Kuropatkin, N. P.; Kurshetsov, V. F.; Kushnirenko, A.; Lach, J.; Landsberg, L. G.; Larin, I.; Leikin, E. M.; López-Hinojosa, G.; Lungov, T.; Maleev, V. P.; Mao, D.; Mathew, P.; Mattson, M.; Matveev, V.; McCliment, E.; Moinester, M. A.; Molchanov, V. V.; Morelos, A.; Nemitkin, A. V.; Neoustroev, P. V.; Newsom, C.; Nilov, A. P.; Nurushev, S. B.; Ocherashvili, A.; Onel, Y.; Ozkorucuklu, S.; Penzo, A.; Petrenko, S. V.; Procario, M.; Prutskoi, V. A.; Razmyslovich, B. V.; Romanov, D. A.; Rud, V. I.; Russ, J.; Sánchez-López, J. L.; Savchenko, A. A.; Simon, J.; Sinev, G. V.; Sitnikov, A. I.; Smith, V. J.; Srivastava, M.; Steiner, V.; Stepanov, V.; Stutte, L.; Svoiski, M.; Tarasov, V. V.; Terentyev, N. K.; Torres, I.; Uvarov, L. N.; Vasiliev, A. N.; Vavilov, D. V.; Vázquez-Jáuregui, E.; Verebryusov, V. S.; Victorov, V. A.; Vishnyakov, V. E.; Vorobyov, A. A.; Vorwalter, K.; You, J.; Zukanovich-Funchal, R.

    2016-02-01

    We report the measurement of the one-dimensional charged kaon correlation functions using 600GeV / cΣ-, π- and 540GeV / cp beams from the SELEX (E781) experiment at the Fermilab Tevatron. K±K± correlation functions are studied for three transverse pair momentum, kT, ranges and parameterized by a Gaussian form. The emission source radii, R, and the correlation strength, λ, are extracted. The analysis shows a decrease of the source radii with increasing kaon transverse pair momentum for all beam types.

  12. A Discovery-Based Experiment Involving Rearrangement in the Conversion of Alcohols to Alkyl Halides: Permanent Magnet [to the thirteenth power]C NMR in the First-Semester Organic Chemistry Lab

    Science.gov (United States)

    Kjonaas, Richard A.; Tucker, Ryand J. F.

    2008-01-01

    The use of permanent magnet [to the thirteenth power]C NMR in large-section first-semester organic chemistry lab courses is limited by the availability of experiments that not only hinge on first-semester lecture topics, but which also produce at least 0.5 mL of neat liquid sample. This article reports a discovery-based experiment that meets both…

  13. 3D H2BC: a novel experiment for small-molecule and biomolecular NMR at natural isotopic abundance.

    Science.gov (United States)

    Meier, Sebastian; Benie, Andrew J; Duus, Jens Ø; Sørensen, Ole W

    2009-10-01

    3D H2BC is introduced for heteronuclear assignment on natural abundance samples even for biomolecules up to at least 10 kDa in low millimolar concentrations as an overnight experiment using the latest generation of cryogenically cooled probes. The short pulse sequence duration of H2BC is maintained in the 3D version due to multiple use of the constant-time delay. Applications ranging from a small lipid to a non-recombinant protein demonstrate the merits of 3D H2BC and the ease of obtaining assignments in chains of protonated carbons.

  14. Recent results on correlations and particle spectra from experiment NA44

    CERN Document Server

    Humanic, T J; Bøggild, H; Boissevain, J G; Dodd, J; Erazmus, B; Esumi, S C; Fabjan, Christian Wolfgang; Ferenc, D; Fields, D E; Franz, A; Gaardhøje, J J; Hamelin, M; Hansen, A G; Hansen, O; Hardtke, D; van Hecke, H; Holzer, E B; Humanic, T J; Hummel, P; Jacak, B V; Jayanti, R; Kaimi, K; Kaneta, M; Kohama, T; Kopytine, M L; Leltchouk, M; Ljubicic, A; Lörstad, B; Maeda, N; Malina, R; Medvedev, A; Murray, M; Ohnishi, H; Paic, G; Pandey, S U; Piuz, François; Pluta, J; Polychronakos, V; Potekhin, M V; Poulard, G; Reichhold, D M; Sakaguchi, A; Simon-Gillo, J; Schmidt-Sørensen, J; Sondheim, W E; Spegel, M; Sugitate, T; Sullivan, J P; Sumi, Y; Willis, W J; Wolf, K L; Xu, N; Zachary, D S

    2000-01-01

    Recent results for both single particle spectra and two particle interferometry from CERN experiment NA44 are presented. Experiment NA44 is a focussing spectrometer with both excellent momentum resolution and particle identification. The results shown are mainly from 158 GeV/nucleon Pb+Pb running. These include single pion, kaon, proton, antiproton, deuteron, and triton spectra and two pion, two kaon and two proton correlation functions. (15 refs).

  15. {sup 13}C NMR hyperfine couplings, {ital T}{sub 1} anisotropy, and Korringa relations in Rb{sub 2}CsC{sub 60}: Search for effects of strong correlation

    Energy Technology Data Exchange (ETDEWEB)

    Pennington, C.H.; Stenger, V.A.; Recchia, C.H.; Hahm, C.; Gorny, K.; Nandor, V. [Department of Physics, The Ohio State University, 174 West 18th Avenue, Columbus, Ohio 43210 (United States); Buffinger, D.R.; Lee, S.M.; Ziebarth, R.P. [Department of Chemistry, The Ohio State University, 120 West 18th Avenue, Columbus, Ohio 43210 (United States)

    1996-02-01

    Initial considerations lead one to suspect that effects of strong correlation might be present in the alkali fulleride superconductors. We report {ital direct} measurements of {sup 13}C {ital T}{sub 1} anisotropy at 80 K in Rb{sub 2}CsC{sub 60} and compare, in the context of the Korringa relation, the inferred spin-dipolar contribution to 1/{ital T}{sub 1} with the widths of the measured powder pattern line shape. The results demonstrate that the Korringa relation, valid in the limit of noninteracting electrons, holds in this case. Taken together with other normal-state NMR behavior this result makes important effects of strong correlation appear unlikely. {copyright} {ital 1996 The American Physical Society.}

  16. A novel low-E field coil to minimize heating of biological samples in solid-state multinuclear NMR experiments

    Science.gov (United States)

    Dillmann, Baudouin; Elbayed, Karim; Zeiger, Heinz; Weingertner, Marie-Catherine; Piotto, Martial; Engelke, Frank

    2007-07-01

    A novel coil, called Z coil, is presented. Its function is to reduce the strong thermal effects produced by rf heating at high frequencies. The results obtained at 500 MHz in a 50 μl sample prove that the Z coil can cope with salt concentrations that are one order of magnitude higher than in traditional solenoidal coils. The evaluation of the rf field is performed by numerical analysis based on first principles and by carrying out rf field measurements. Reduction of rf heating is probed with a DMPC/DHPC membrane prepared in buffers of increasing salt concentrations. The intricate correlation that exists between the magnetic and electric field is presented. It is demonstrated that, in a multiply tuned traditional MAS coil, the rf electric field E1 cannot be reduced without altering the rf magnetic field. Since the detailed distribution differs when changing the coil geometry, a comparison involving the following three distinct designs is discussed: (1) a regular coil of 5.5 turns, (2) a variable pitch coil with the same number of turns, (3) the new Z coil structure. For each of these coils loaded with samples of different salt concentrations, the nutation fields obtained at a certain power level provide a basis to discuss the impact of the dielectric and conductive losses on the rf efficiency.

  17. A novel low-E field coil to minimize heating of biological samples in solid-state multinuclear NMR experiments.

    Science.gov (United States)

    Dillmann, Baudouin; Elbayed, Karim; Zeiger, Heinz; Weingertner, Marie-Catherine; Piotto, Martial; Engelke, Frank

    2007-07-01

    A novel coil, called Z coil, is presented. Its function is to reduce the strong thermal effects produced by rf heating at high frequencies. The results obtained at 500MHz in a 50 microl sample prove that the Z coil can cope with salt concentrations that are one order of magnitude higher than in traditional solenoidal coils. The evaluation of the rf field is performed by numerical analysis based on first principles and by carrying out rf field measurements. Reduction of rf heating is probed with a DMPC/DHPC membrane prepared in buffers of increasing salt concentrations. The intricate correlation that exists between the magnetic and electric field is presented. It is demonstrated that, in a multiply tuned traditional MAS coil, the rf electric field E(1) cannot be reduced without altering the rf magnetic field. Since the detailed distribution differs when changing the coil geometry, a comparison involving the following three distinct designs is discussed: (1) a regular coil of 5.5 turns, (2) a variable pitch coil with the same number of turns, (3) the new Z coil structure. For each of these coils loaded with samples of different salt concentrations, the nutation fields obtained at a certain power level provide a basis to discuss the impact of the dielectric and conductive losses on the rf efficiency.

  18. Cross-Correlated Relaxation of Dipolar Coupling and Chemical-Shift Anisotropy in Magic-Angle Spinning R1ρ NMR Measurements: Application to Protein Backbone Dynamics Measurements.

    Science.gov (United States)

    Kurauskas, Vilius; Weber, Emmanuelle; Hessel, Audrey; Ayala, Isabel; Marion, Dominique; Schanda, Paul

    2016-09-01

    Transverse relaxation rate measurements in magic-angle spinning solid-state nuclear magnetic resonance provide information about molecular motions occurring on nanosecond-to-millisecond (ns-ms) time scales. The measurement of heteronuclear ((13)C, (15)N) relaxation rate constants in the presence of a spin-lock radiofrequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins have been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely, (1) the role of CSA/dipolar cross-correlated relaxation (CCR) and (2) the impact of fast proton spin flips (i.e., proton spin diffusion and relaxation). We show that CSA/D CCR in R1ρ experiments is measurable and that the CCR rate constant depends on ns-ms motions; it can thus provide insight into dynamics. We find that proton spin diffusion attenuates this CCR due to its decoupling effect on the doublet components. For measurements of dynamics, the use of R1ρ rate constants has practical advantages over the use of CCR rates, and this article reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation.

  19. Effects of a type I antifreeze protein (AFP) on the melting of frozen AFP and AFP+solute aqueous solutions studied by NMR microimaging experiment.

    Science.gov (United States)

    Ba, Yong; Mao, Yougang; Galdino, Luiz; Günsen, Zorigoo

    2013-01-01

    The effects of a type I AFP on the bulk melting of frozen AFP solutions and frozen AFP+solute solutions were studied through an NMR microimaging experiment. The solutes studied include sodium chloride and glucose and the amino acids alanine, threonine, arginine, and aspartic acid. We found that the AFP is able to induce the bulk melting of the frozen AFP solutions at temperatures lower than 0 °C and can also keep the ice melted at higher temperatures in the AFP+solute solutions than those in the corresponding solute solutions. The latter shows that the ice phases were in super-heated states in the frozen AFP+solute solutions. We have tried to understand the first experimental phenomenon via the recent theoretical prediction that type I AFP can induce the local melting of ice upon adsorption to ice surfaces. The latter experimental phenomenon was explained with the hypothesis that the adsorption of AFP to ice surfaces introduces a less hydrophilic water-AFP-ice interfacial region, which repels the ionic/hydrophilic solutes. Thus, this interfacial region formed an intermediate chemical potential layer between the water phase and the ice phase, which prevented the transfer of water from the ice phase to the water phase. We have also attempted to understand the significance of the observed melting phenomena to the survival of organisms that express AFPs over cold winters.

  20. Teachers' Experiences with Multiple Victimization: Identifying Demographic, Cognitive, and Contextual Correlates

    Science.gov (United States)

    Martinez, Andrew; McMahon, Susan D.; Espelage, Dorothy; Anderman, Eric M.; Reddy, Linda A.; Sanchez, Bernadette

    2016-01-01

    Extant scholarship has primarily examined demographic predictors of teacher victimization. Teacher multiple victimization, or the extent to which teachers experience multiple types of violence, has not been examined. Using social-ecological theory, we examine correlates of violence among 2,324 teachers who reported having been victimized at least…

  1. Estimating adhesive seed-dispersal distances : field experiments and correlated random walks

    NARCIS (Netherlands)

    Mouissie, AM; Lengkeek, W; van Diggelen, R

    1. In this study we aimed to estimate distance distributions of adhesively dispersed seeds and the factors that determine them. 2. Seed attachment and detachment were studied using field experiments with a real sheep, a sheep dummy and a cattle dummy. Seed-retention data were used in correlated

  2. Results of the Baikal experiment on observations of macroscopic nonlocal correlations in reverse time

    CERN Document Server

    Korotaev, S M; Kiktenko, E O; Budnev, N M; Gorohov, J V

    2015-01-01

    Although the general theory macroscopic quantum entanglement of is still in its infancy, consideration of the matter in the framework of action-at-a distance electrodynamics predicts for the random dissipative processes observability of the advanced nonlocal correlations. These correlations were really revealed in our previous experiments with some large-scale heliogeophysical processes as the source ones and the lab detectors as the probe ones. Recently a new experiment has been performing on the base of Baikal Deep Water Neutrino Observatory. The thick water layer is an excellent shield against any local impacts on the detectors. The first annual series 2012/2013 has demonstrated that detector signals respond to the heliogeophysical processes and causal connection of the signals directed downwards: from the Earth surface to the Baikal floor. But this nonlocal connection proved to be in reverse time. In addition advanced nonlocal correlation of the detector signal with the regional source-process: the random...

  3. 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.

  4. The transverse momentum dependencies of charged kaon Bose-Einstein correlations in the SELEX experiment

    CERN Document Server

    Nigmatkulov, G A; Akgun, U; Alkhazov, G; Amaro-Reyes, J; Asratyan, A; Atamantchouk, A G; Ayan, A S; Balatz, M Y; Blanco-Covarrubias, A; Bondar, N F; Cooper, P S; Dauwe, L J; Davidenko, G V; Dersch, U; Dolgolenko, A G; Dzyubenko, G B; Edelstein, R; Emediato, L; Endler, A M F; Engelfried, J; Eschrich, I; Escobar, C O; Estrada, N; Evdokimov, A V; Filimonov, I S; Flores-Castillo, A; Garcia, F G; Golovtsov, V L; Gouffon, P; Gülmez, E; Iori, M; Jun, S Y; Kaya, M; Kilmer, J; Kim, V T; Kochenda, L M; Konorov, I; Kozhevnikov, A P; Krivshich, A G; Krüger, H; Kubantsev, M A; Kubarovsky, V P; Kulyavtsev, A I; Kuropatrkin, N P; Kurshetsov, V F; Kushnirenko, A; Lach, J; Landsberg, L G; Larin, I; Leikin, E M; López-Hinojosa, G; Lungov, T; Maleev, V P; Mao, D; Mathew, P; Mattson, M; Matveev, V; McCliment, E; Moinester, M A; Molchanov, V V; Morelos, A; Nemitkin, A V; Neoustroev, P V; Newsom, C; Nilov, A P; Nurushev, S B; Ocherashvili, A; Onel, Y; Ozkorucuklu, S; Penzo, A; Petrenko, S V; Procario, M; Prutskoi, V A; Razmyslovich, B V; Romanov, D A; Rud, V I; Russ, J; Sánchez-López, J L; Savchenko, A A; Simon, J; Sinev, G V; Sitnikov, A I; Smith, V J; Srivastava, M; Steiner, V; Stepanov, V; Stutte, L; Svoiski, M; Tarasov, V V; Terentyev, N K; Torres, I; Uvarov, L N; Vasiliev, A N; Vavilov, D V; Vázquez-Jáuregui, E; Verebryusov, V S; Victorov, V A; Vishnyakov, V E; Vorobyov, A A; Vorwalter, K; You, J; Zukanovich-Funchal, R

    2015-01-01

    We report on the measurement of the charged kaon correlation functions $k_T$ dependencies using 600 GeV/$c$ $\\Sigma^-$, $\\pi^-$ and 540 GeV/$c$ $p$ beams from the SELEX (E781) experiment at Tevatron. One-dimentional $K^{ch}K^{ch}$ correlation functions are constructed in three transverse momentum ranges. The emission source parameters $\\lambda$ and $R$ are extracted. The analysis shows a decrease of the source radii with the kaon pair transverse momentum for all beam types

  5. Hexameric Capsules Studied by Magic Angle Spinning Solid-State NMR Spectroscopy: Identifying Solvent Molecules in Pyrogallol[4]arene Capsules.

    Science.gov (United States)

    Avram, Liat; Goldbourt, Amir; Cohen, Yoram

    2016-01-18

    Powders of pyrogallol[4]arene hexamers were produced by evaporation from organic solvents and were studied, for the first time, by magic angle spinning solid-state NMR (MAS ssNMR). Evaporation selectively removed non-encapsulated solvent molecules leaving stable hexameric capsules encapsulating solvent molecules. After exposure of the powder to solvent vapors, (1)H/(13)C heteronuclear correlation MAS ssNMR experiments were used to assign the signals of the external and encapsulated solvent molecules. The formed capsules were stable for months and the process of solvent encapsulation was reversible. According to the ssNMR experiments, the encapsulated solvent molecules occupy different sites and those sites differ in their mobility. The presented approach paves the way for studying guest exchange, guest affinity, and gas storage in hexamers of this type in the solid state.

  6. Effect of solvent on proton location and dynamic behavior in short intramolecular hydrogen bonds studied by molecular dynamics simulations and NMR experiments

    Science.gov (United States)

    Mori, Yukie; Masuda, Yuichi

    2015-09-01

    Hydrogen phthalate anion has a short strong O-H-O hydrogen bond (H-bond). According to previous experimental studies, the H-bond is asymmetric and two tautomers are interconverted in aqueous solutions. In the present study, the effects of polar solvents on the H-bond in a zwitterionic hydrogen phthalate derivative 1 were investigated by quantum mechanics/molecular mechanics molecular dynamics (MD) simulations. The analyses of the trajectories for the methanol solution showed that the H-bonding proton tends to be located closer to the carboxylate group that forms fewer intermolecular H-bonds, than to the other carboxylate group and that the intramolecular proton transfer in 1 is triggered by the breakage and/or formation of an intermolecular H-bond. The enol form of dibenzoylmethane (2) also has a short H-bond, and the OH bond is reported to be rather long (>1.1 Å) in the crystal. In the present study, the effects of the solvent on the H-bond in 2 were investigated by molecular orbital (MO) calculations, MD simulations and nuclear magnetic resonance (NMR) spectroscopy. Density functional theory (DFT) calculations for 2 in vacuum indicated that the barrier height for the intramolecular proton transfer is almost the same as the zero-point energy of the vibrational ground state, resulting in broad distribution of the proton density along the H-bond, owing to the nuclear quantum effect. The OH distances were determined in CCl4, acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the 17O and 1H nuclei monitoring the nuclear magnetic relaxation times of 1H. The experimental results indicated that the H-bond geometry of 2 is influenced by the interactions with dimethylsulfoxide, suggesting the formation of a bifurcated H-bond, which was supported by the DFT calculations. The MD simulations for the methanol solution of 2 showed that the asymmetry of the OH distance is correlated with the asymmetry in the electrostatic field of the

  7. Correlating steric hydration forces with water dynamics through surface force and diffusion NMR measurements in a lipid–DMSO–H2O system

    Science.gov (United States)

    Schrader, Alex M.; Donaldson, Stephen H.; Song, Jinsuk; Cheng, Chi-Yuan; Lee, Dong Woog; Han, Songi; Israelachvili, Jacob N.

    2015-01-01

    Dimethyl sulfoxide (DMSO) is a common solvent and biological additive possessing well-known utility in cellular cryoprotection and lipid membrane permeabilization, but the governing mechanisms at membrane interfaces remain poorly understood. Many studies have focused on DMSO–lipid interactions and the subsequent effects on membrane-phase behavior, but explanations often rely on qualitative notions of DMSO-induced dehydration of lipid head groups. In this work, surface forces measurements between gel-phase dipalmitoylphosphatidylcholine membranes in DMSO–water mixtures quantify the hydration- and solvation-length scales with angstrom resolution as a function of DMSO concentration from 0 mol% to 20 mol%. DMSO causes a drastic decrease in the range of the steric hydration repulsion, leading to an increase in adhesion at a much-reduced intermembrane distance. Pulsed field gradient NMR of the phosphatidylcholine (PC) head group analogs, dimethyl phosphate and tetramethylammonium ions, shows that the ion hydrodynamic radius decreases with increasing DMSO concentration up to 10 mol% DMSO. The complementary measurements indicate that, at concentrations below 10 mol%, the primary effect of DMSO is to decrease the solvated volume of the PC head group and that, from 10 mol% to 20 mol%, DMSO acts to gradually collapse head groups down onto the surface and suppress their thermal motion. This work shows a connection between surface forces, head group conformation and dynamics, and surface water diffusion, with important implications for soft matter and colloidal systems. PMID:26261313

  8. 基于NMR指纹谱相关分析的生物类似药高级结构评价%Higher Order Structure Assessment of Biosimilars Based on the Correlation of NMR Spectral Fingerprints

    Institute of Scientific and Technical Information of China (English)

    许美凤; 方均建; 董芳霆; 颜贤忠

    2015-01-01

    A procedure based on the1H NMR fingerprints of biologics was established for the assessment of higher order structure of biosimilar samples. The global correlation coefficientsr andR2 of binned NMR spectra were used to quantify structural similarity between biosimilars and originators, and a local correlation analysis method was used to find out the specific regions that contribute to the structure differences. This method was applied to the quantitative assessment of daptomycin, a lipopeptide antibiotic with a molecular weight of 1 620, by comparing the higher order structure of the biosimilar active pharmaceutical ingredient (API), its injection and originator injection Cubicin. The results showed that there were significant spectral differences among daptomycin samples, indicating structural differences between daptomycin originator and its biosimilars. Local correlation analysis further revealed the specific spectral regions that contributed to these differences. The method was also applied to a monoclonal antibody drug Trastuzumab, which is a large protein with a molecular weight of 145 423.1H NMR spectra of the originator drug Herceptin and four lots of its biosimilar were recorded and binned for statistical analysis. The correlation coefficientsr andR2 showed that Trastuzumab biosimilars seem to be highly similar to Herceptin. These results demonstrated that the combination of NMR fingerprints and statistical analysis is a powerful and robust technique in biosimilar quality control.%建立了基于1H NMR指纹技术的生物类似药高级结构相似性分析方法,利用相关系数r和决定系数R2定量评估生物类似药与其原研药的结构相似度。将该方法应用在一种分子量为1620的抗菌性脂肽达托霉素上,比较了其类似药的活性原料成分(API)、类似药制剂与原研药克必信的高级结构相似性。实验结果显示,3个达托霉素样品的谱图存在显著差异,表明达托霉素类似药与

  9. Further Evidence That Cannabis Moderates Familial Correlation of Psychosis-Related Experiences.

    Directory of Open Access Journals (Sweden)

    Ruud van Winkel

    Full Text Available Familial correlations underlie heritability estimates of psychosis. If gene-environment interactions are important, familial correlation will vary as a function of environmental exposure.Associations between sibling and parental schizotypy (n = 669 pairs, n = 1222 observations, and between sibling schizotypy and patient CAPE psychosis (n = 978 pairs, n = 1723 observations were examined as a function of sibling cannabis use. This design is based on the prediction that in unaffected siblings who are not exposed, vulnerability for psychosis will remain latent, whereas in case of exposure, latent psychosis vulnerability may become expressed, at the level of schizotypal symptoms, causing the phenotypic correlation between relatives to become "visible" under the influence of cannabis.Siblings exposed to recent cannabis use resembled their patient-relative more closely in terms of positive schizotypy (urinalysis(+:B = 0.30, P<.001; urinalysis(-:B = 0.10, p<0.001; p-interaction = 0.0135. Similarly, the familial correlation in positive schizotypy between parent and sibling was significantly greater in siblings recently exposed to cannabis (urinalysis(+:B = 0.78, P<.001; urinalysis(-:B = 0.43, p<0.001; p interaction = 0.0017. Results were comparable when using lifetime cannabis frequency of use as exposure instead of recent use. Parental schizotypy did not predict cannabis use in the healthy sibling, nor in the patient. Similarly, parental cannabis use was not associated with level of schizotypy in the sibling, nor with psychotic symptoms in the patient, making gene-environment correlation unlikely.Familial correlation of psychosis-related experiences varies considerably as a function of exposure to cannabis, confirming the importance of gene-cannabis interaction in shifts of expression of psychosis-related experiences.

  10. Does operative experience during residency correlate with reported competency of recent general surgery graduates?

    Science.gov (United States)

    Safavi, Arash; Lai, Sarah; Butterworth, Sonia; Hameed, Morad; Schiller, Dan; Skarsgard, Erik

    2012-01-01

    Background Identification of attributes of residency training that predict competency would improve surgical education. We hypothesized that case experience during residency would correlate with self-reported competency of recent graduates. Methods Aggregate case log data of residents enrolled in 2 general surgery programs were collected over a 12-month period and stratified into Surgical Council on Resident Education (SCORE) categories. We surveyed recent (surgery (4, 0.04%), and the least common EU procedure was abdomen–spleen (1, 0.1%). The questionnaire response rate was 45%. For EC procedures, self-reported competency was highest in skin and soft tissue, thoracic and head and neck (each 100%) and lowest in vascular–venous (54%), whereas for EU procedures it was highest in abdomen–general (100%) and lowest in vascular–arterial (62%). The correlation between case volume and self-reported competency was poor (R = 0.2 for EC procedures). Conclusion Self-reported competency correlates poorly with operative case experience during residency. Other curriculum factors, including specific rotations and timing, balance between inpatient and outpatient surgical experience and competition for cases, may contribute to procedural competency acquisition during residency. PMID:22854144

  11. An Ultra-Wideband Cross-Correlation Radiometer for Mesoscopic Experiments

    Science.gov (United States)

    Toonen, Ryan; Haselby, Cyrus; Qin, Hua; Eriksson, Mark; Blick, Robert

    2007-03-01

    We have designed, built and tested a cross-correlation radiometer for detecting statistical order in the quantum fluctuations of mesoscopic experiments at sub-Kelvin temperatures. Our system utilizes a fully analog front-end--operating over the X- and Ku-bands (8 to 18 GHz)--for computing the cross-correlation function. Digital signal processing techniques are used to provide robustness against instrumentation drifts and offsets. The economized version of our instrument can measure, with sufficient correlation efficiency, noise signals having power levels as low as 10 fW. We show that, if desired, we can improve this performance by including cryogenic preamplifiers which boost the signal-to-noise ratio near the signal source. By adding a few extra components, we can measure both the real and imaginary parts of the cross-correlation function--improving the overall signal-to-noise ratio by a factor of sqrt[2]. We demonstrate the utility of our cross-correlator with noise power measurements from a quantum point contact.

  12. Assignment of the absolute configuration of hepatoprotective highly oxygenated triterpenoids using X-ray, ECD, NMR J-based configurational analysis and HSQC overlay experiments.

    Science.gov (United States)

    Wang, Xiaojuan; Liu, Jiabao; Pandey, Pankaj; Chen, Jiabao; Fronczek, Frank R; Parnham, Stuart; Qi, Xinzhu; Doerksen, Robert J; Ferreira, Daneel; Sun, Hua; Li, Shuai; Hamann, Mark T

    2017-09-14

    The plants of the genus Kadsura are widely distributed in China, South Korea, and Japan. Their roots and stems are traditionally used to treat blood diseases and pain. The main bioactive constituents of Kadsura longipedunculata comprise highly oxygenated triterpenoids. Schiartane-type nortriterpenoids showed anti-HIV, anti-HBV, and cytotoxic bioactivities. For such compounds, the absolute configuration influences the bioactivities, and hence its unambiguous determination is essential. In this work, the absolute configurations of three highly oxygenated schiartane-type nortriterpenoids were unequivocally assigned using X-ray, ECD, and J-based configuration analysis and HSQC overlay data. The ethanol extract of Kadsura longipedunculata Finet et Gagnep was purified by column chromatography using silica, Sephadex LH-20, and ODS as substrates. To help assign the absolute configuration of schiartane-type nortriterpenoids, X-ray diffraction analysis, ECD experiment compared to ab initio computed data, DP4+ analysis, HSQC overlay, NOESY, and J-based configuration analysis were carried out. Hetero- and homo-nuclear coupling constants were extracted from HETLOC experiments. Three new highly oxygenated triterpenoids, micrandilactone I (1), micrandilactone J (2), and 22, 23-di-epi-micrandilactone J (3) were isolated. Their 2D structures were solved using NMR and HRESIMS data and their absolute configurations were elucidated using X-ray diffraction analysis, ECD experimental results compared to ab initio computed spectra, HSQC overlay, DP4 plus, NOESY, and J-based configuration analysis. Micrandilactone I (1) and 22, 23-di-epi-micrandilactone J (3) showed moderate hepatoprotective activity against APAP-induced toxicity in HepG2 cells with cell survival rates of 53.0 and 50.2%, respectively, at 10μM (bicyclol, 49.0%), while micrandilactone J (2) was inactive. This is the first comprehensive stereochemical assignment of a non-crystalline schiartane-type nortriterpenoid like 3

  13. 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...

  14. Constant time tensor correlation experiments by non-gamma-encoded recoupling pulse sequences.

    Science.gov (United States)

    Mou, Yun; Tsai, Tim W T; Chan, Jerry C C

    2012-10-28

    Constant-time tensor correlation under magic-angle spinning conditions is an important technique in solid-state nuclear magnetic resonance spectroscopy for the measurements of backbone or side-chain torsion angles of polypeptides and proteins. We introduce a general method for the design of constant-time tensor correlation experiments under magic-angle spinning. Our method requires that the amplitude of the average Hamiltonian must depend on all the three Euler angles bringing the principal axis system to the rotor-fixed frame, which is commonly referred to as non-gamma encoding. We abbreviate this novel approach as COrrelation of Non-Gamma-Encoded Experiment (CONGEE), which exploits the orientation-dependence of non-gamma-encoded sequences with respect to the magic-angle rotation axis. By manipulating the relative orientation of the average Hamiltonians created by two non-gamma-encoded sequences, one can obtain a modulation of the detected signal, from which the structural information can be extracted when the tensor orientations relative to the molecular frame are known. CONGEE has a prominent feature that the number of rf pulses and the total pulse sequence duration can be maintained to be constant so that for torsion angle determination the effects of systematic errors owing to the experimental imperfections and/or T(2) effects could be minimized. As a proof of concept, we illustrate the utility of CONGEE in the correlation between the C' chemical shift tensor and the C(α)-H(α) dipolar tensor for the backbone psi angle determination. In addition to a detailed theoretical analysis, numerical simulations and experiments measured for [U-(13)C, (15)N]-L-alanine and N-acetyl-[U-(13)C, (15)N]-D,L-valine are used to validate our approach at a spinning frequency of 20 kHz.

  15. MUSIC in triple-resonance experiments: amino acid type-selective (1)H-(15)N correlations

    Science.gov (United States)

    Schubert; Smalla; Schmieder; Oschkinat

    1999-11-01

    Amino acid type-selective triple-resonance experiments can be of great help for the assignment of protein spectra, since they help to remove ambiguities in either manual or automated assignment procedures. Here, modified triple-resonance experiments that yield amino acid type-selective (1)H-(15)N correlations are presented. They are based on novel coherence transfer schemes, the MUSIC pulse sequence elements, that replace the initial INEPT transfer and are selective for XH(2) or XH(3) (X can be (15)N or (13)C). The desired amino acid type is thereby selected based on the topology of the side chain. Experiments for Gly (G-HSQC); Ala (A-HSQC); Thr, Val, Ile, and Ala (TAVI-HSQC); Thr and Ala (TA-HSQC), as well as Asn and Gln (N-HSQC and QN-HSQC), are described. The new experiments are recorded as two-dimensional experiments and therefore need only small amounts of spectrometer time. The performance of the experiments is demonstrated with the application to two protein domains. Copyright 1999 Academic Press.

  16. 'Unconventional' experiments in biology and medicine with optimized design based on quantum-like correlations.

    Science.gov (United States)

    Beauvais, Francis

    2017-02-01

    In previous articles, a description of 'unconventional' experiments (e.g. in vitro or clinical studies based on high dilutions, 'memory of water' or homeopathy) using quantum-like probability was proposed. Because the mathematical formulations of quantum logic are frequently an obstacle for physicians and biologists, a modified modeling that rests on classical probability is described in the present article. This modeling is inspired from a relational interpretation of quantum physics that applies not only to microscopic objects, but also to macroscopic structures, including experimental devices and observers. In this framework, any outcome of an experiment is not an absolute property of the observed system as usually considered but is expressed relatively to an observer. A team of interacting observers is thus described from an external view point based on two principles: the outcomes of experiments are expressed relatively to each observer and the observers agree on outcomes when they interact with each other. If probability fluctuations are also taken into account, correlations between 'expected' and observed outcomes emerge. Moreover, quantum-like correlations are predicted in experiments with local blind design but not with centralized blind design. No assumption on 'memory' or other physical modification of water is necessary in the present description although such hypotheses cannot be formally discarded. In conclusion, a simple modeling of 'unconventional' experiments based on classical probability is now available and its predictions can be tested. The underlying concepts are sufficiently intuitive to be spread into the homeopathy community and beyond. It is hoped that this modeling will encourage new studies with optimized designs for in vitro experiments and clinical trials. Copyright © 2017 The Faculty of Homeopathy. Published by Elsevier Ltd. All rights reserved.

  17. Selective One-Dimensional Total Correlation Spectroscopy Nuclear Magnetic Resonance Experiments for a Rapid Identification of Minor Components in the Lipid Fraction of Milk and Dairy Products: Toward Spin Chromatography?

    Science.gov (United States)

    Papaemmanouil, Christina; Tsiafoulis, Constantinos G; Alivertis, Dimitrios; Tzamaloukas, Ouranios; Miltiadou, Despoina; Tzakos, Andreas G; Gerothanassis, Ioannis P

    2015-06-10

    We report a rapid, direct, and unequivocal spin-chromatographic separation and identification of minor components in the lipid fraction of milk and common dairy products with the use of selective one-dimensional (1D) total correlation spectroscopy (TOCSY) nuclear magnetic resonance (NMR) experiments. The method allows for the complete backbone spin-coupling network to be elucidated even in strongly overlapped regions and in the presence of major components from 4 × 10(2) to 3 × 10(3) stronger NMR signal intensities. The proposed spin-chromatography method does not require any derivatization steps for the lipid fraction, is selective with excellent resolution, is sensitive with quantitation capability, and compares favorably to two-dimensional (2D) TOCSY and gas chromatography-mass spectrometry (GC-MS) methods of analysis. The results of the present study demonstrated that the 1D TOCSY NMR spin-chromatography method can become a procedure of primary interest in food analysis and generally in complex mixture analysis.

  18. 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...

  19. Correlation between Knowledge, Experience and Common Sense, with Critical Thinking Capability of Medical Faculty's Students at Indonesia Christian University

    Science.gov (United States)

    Nadeak, Bernadetha

    2015-01-01

    This research discusses correlation between knowledge, experience and common sense with critical thinking of Medical Faculty's Student. As to the objective of this research is to find the correlation between knowledge, experience and common sense with critical thinking of Medical Faculty's Students at Christian University of Indonesia. It is…

  20. Characterization of mantle convection experiments using two-point correlation functions

    Science.gov (United States)

    Puster, Peter; Jordan, Thomas H.; Hager, Bradford H.

    1995-04-01

    Snapshots of the temperature T(r, phi, t), horizontal flow velocity u(r, phi, t), and radial flow velocity w(r, phi, t) obtained from numerical convection experiments of time-dependent flows in annular cylindrical geometry are taken to be samples of stationary, rotationally invariant random fields. For such a field f(r, phi, t), the spatio-temporal two-point correlation function, C(sub ff)(r, r-prime, delta, t(sub *)), is constructed by averaging over rotational transformations of this ensemble. To assess the structural differences among mantle convection experiments we construct three spartial subfunctions of C(sub ff)(r, r-prime, delta, t(sub *)): the rms variation, sigma(sub f)(r), the radial correlation function, R(sub f)(r, r-prime), and the angular correlation function, A(sub f)(r, delta). R(sub f)(r, r-prime) and A(sub f)(r, r-prime) are symmetric about the loci r = r-prime and delta = 0, respectively, where they achieve their maximum value of unity. The falloff of R(sub f) and A(sub f) away from their symmetry can be quantified by a correlation length rho(sub f)(r) and a correlation angle alpha(sub f)(r), which we define to be the half widths of the central peaks at the correlation level 0.75. The behavior of rho(sub f) is a diagnostic of radial structure, while alpha(sub f) measures average plume width. We have used two-point correlation functions of the temperature field (T-diagnostics) and flow velocity fields (V-diagnostics) to quantify some important aspects of mantle convection experiments. We explore the dependence of different correlation diagnostics on Rayleigh number, internal heating rate, and depth- and temperature-dependent viscosity. For isoviscous flows in an annulus, we show how radial averages of sigma(sub T), rho(sub T), and alpha(sub T) scale with Rayleigh number for various internal heating rates. A break in the power-law relationship at the transition from steady to time-dependent regimes is evident for rho(sub T) and alpha(sub T) but

  1. Correlations between nuclear data and results of integral slab experiments. Case of hafnium; Correlations entre donnees nucleaires et experiences integrales a plaques: le cas du hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Palau, J.M

    1997-10-22

    The aim of this thesis was to evaluate how much integral slab experiments can both reduce discrepancies between experimental results and calculations, and improve the knowledge of hafnium isotopes neutronic parameters by an adapted sensitivity and uncertainty method. A statistical approach, based on the generalized least squares method and perturbation theory, has been incorporated into our calculation system in order to deduce microscopic cross-section adjustments from observed integral measurements on this particular `mock-up` reactor. In this study it has been established that the correlations between integral parameters and hafnium capture cross-sections enable specific variations in the region of resolved resonances at the level of multigroup and punctual cross-sections recommended data (JEF-2.2 evaluation) to be highlighted. The use of determinist methods (APOLLO2 code) together with Monte Carlo- type simulations (TRIPOLI4 code) enabled a depth analysis of the modelling approximations to be carried out. Furthermore, the sensitivity coefficient validation technique employed leads to a reliable assessment of the quality of the new basic nuclear data. In this instance, the adjustments proposed for certain isotope {sup 177}Hf resonance parameters reduce, after error propagation, by 3 to 5 per cent the difference between experimental results and calculations related to this absorbent`s efficiency. Beyond this particular application, the qualification methodology integrated in our calculation system should enable other basic sizing parameters to be treated (chemical / geometric data or other unexplored nuclear data) to make technological requirements less stringent. (author) 128 refs.

  2. Correlations between nuclear data and integral slab experiments: the case of hafnium; Correlations entre donnees nucleaires et experiences integrales a plaques: le cas du hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Palau, J.M

    1999-07-01

    The aim of this work was to evaluate how much integral slab experiments can both reduce discrepancies between experimental results and calculations, and improve the knowledge of hafnium isotopes neutronic parameters by an adapted sensitivity and uncertainty method. A statistical approach, based on the generalized least squares method and perturbation theory, has been incorporated into our calculation system in order to deduce microscopic cross-section adjustments from observed integral measurements on this particular 'mock-up' reactor.In this study it has been established that the correlations between integral parameters and hafnium capture cross-sections enable specific variations in the region of resolved resonances at the level of multigroup and punctual cross-sections recommended data (JEF-2.2 evaluation) to be highlighted. The use of determinist methods together with Monte Carlo- type simulations enabled a depth analysis of the modelling approximations to be carried out. Furthermore, the sensitivity coefficient validation technique employed leads to a reliable assessment of the quality of the new basic nuclear data. In this instance, the adjustments proposed for certain isotope {sup 177}Hf resonance parameters reduce, after error propagation, by 3 to 5 per cent the difference between experimental results and calculations related to this absorbent's efficiency. Beyond this particular application, the qualification methodology integrated in our calculation system should enable other basic sizing parameters to be treated (chemical / geometric data or other unexplored nuclear data) to make technological requirements less stringent. (author)

  3. Correlations between nuclear data and results of integral slab experiments. Case of hafnium; Correlations entre donnees nucleaires et experiences integrales a plaques: le cas du hafnium

    Energy Technology Data Exchange (ETDEWEB)

    Palau, J.M

    1997-10-22

    The aim of this thesis was to evaluate how much integral slab experiments can both reduce discrepancies between experimental results and calculations, and improve the knowledge of hafnium isotopes neutronic parameters by an adapted sensitivity and uncertainty method. A statistical approach, based on the generalized least squares method and perturbation theory, has been incorporated into our calculation system in order to deduce microscopic cross-section adjustments from observed integral measurements on this particular `mock-up` reactor. In this study it has been established that the correlations between integral parameters and hafnium capture cross-sections enable specific variations in the region of resolved resonances at the level of multigroup and punctual cross-sections recommended data (JEF-2.2 evaluation) to be highlighted. The use of determinist methods (APOLLO2 code) together with Monte Carlo- type simulations (TRIPOLI4 code) enabled a depth analysis of the modelling approximations to be carried out. Furthermore, the sensitivity coefficient validation technique employed leads to a reliable assessment of the quality of the new basic nuclear data. In this instance, the adjustments proposed for certain isotope {sup 177}Hf resonance parameters reduce, after error propagation, by 3 to 5 per cent the difference between experimental results and calculations related to this absorbent`s efficiency. Beyond this particular application, the qualification methodology integrated in our calculation system should enable other basic sizing parameters to be treated (chemical / geometric data or other unexplored nuclear data) to make technological requirements less stringent. (author) 128 refs.

  4. Fractioning of sodium polyphosphate and characterization by {sup 31}P NMR: a experience to physical-chemistry lessons; Fracionamento de polifosfato de sodio e caracterizacao por RMN de 31P: um experimento para aulas de Fisico-Quimica

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Emilia Celma de Oliveira; Alcantara, Glaucia Braz Alcantara; Damasceno, Fernando Cruvinel, E-mail: elima@quimica.ufg.b [Universidade Federal de Goias (UFG), Goiania, GO (Brazil). Inst. de Quimica; Moita Neto, Jose Machado [Universidade Federal do Piaui (UFPI), Teresina, PI (Brazil). Dept. de Quimica; Galembeck, Fernando [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

    2010-07-01

    This text describes an experiment on fractional precipitation of a polymer together with determination of average degree of polymerization by NMR. Commercial sodium polyphosphate was fractionated by precipitation from aqueous solution by adding increasing amounts of acetone. The polydisperse salt and nine fractions obtained from it were analyzed by {sup 31}P nuclear magnetic resonance and the degree of polymerization of the salts and of the fractions were calculated. Long-chain sodium polyphosphate was also synthesized and analyzed. This experiment was tested in a PChem lab course but it can be used also to illustrate topics of inorganic polymers and analytical chemistry. (author)

  5. Retrospective North American CFL Experience Curve Analysis and Correlation to Deployment Programs

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Sarah J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Wei, Max [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Sohn, Michael D. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-07-01

    Retrospective experience curves are a useful tool for understanding historic technology development, and can contribute to investment program analysis and future cost estimation efforts. This work documents our development of an analysis approach for deriving retrospective experience curves with a variable learning rate, and its application to develop an experience curve for compact fluorescent lamps for the global and North American markets over the years 1990-2007. Uncertainties and assumptions involved in interpreting data for our experience curve development are discussed, including the processing and transformation of empirical data, the selection of system boundaries, and the identification of historical changes in the learning rate over the course of 15 years. In the results that follow, we find that that the learning rate has changed at least once from 1990-2007. We also explore if, and to what degree, public deployment programs may have contributed to an increased technology learning rate in North America. We observe correlations between the changes in the learning rate and the initiation of new policies, abrupt technological advances, including improvements to ballast technology, and economic and political events such as trade tariffs and electricity prices. Finally, we discuss how the findings of this work (1) support the use of segmented experience curves for retrospective and prospective analysis and (2) may imply that investments in technological research and development have contributed to a change in market adoption and penetration.

  6. Reducing acquisition times in multidimensional NMR with a time-optimized Fourier encoding algorithm

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhiyong [Department of Chemical Physics, Weizmann Institute of Science, Rehovot 76100 (Israel); Department of Electronic Science, Fujian Provincial Key Laboratory of Plasma and Magnetic Resonance, Xiamen University, Xiamen, Fujian 361005 (China); Smith, Pieter E. S.; Frydman, Lucio, E-mail: lucio.frydman@weizmann.ac.il [Department of Chemical Physics, Weizmann Institute of Science, Rehovot 76100 (Israel)

    2014-11-21

    Speeding up the acquisition of multidimensional nuclear magnetic resonance (NMR) spectra is an important topic in contemporary NMR, with central roles in high-throughput investigations and analyses of marginally stable samples. A variety of fast NMR techniques have been developed, including methods based on non-uniform sampling and Hadamard encoding, that overcome the long sampling times inherent to schemes based on fast-Fourier-transform (FFT) methods. Here, we explore the potential of an alternative fast acquisition method that leverages a priori knowledge, to tailor polychromatic pulses and customized time delays for an efficient Fourier encoding of the indirect domain of an NMR experiment. By porting the encoding of the indirect-domain to the excitation process, this strategy avoids potential artifacts associated with non-uniform sampling schemes and uses a minimum number of scans equal to the number of resonances present in the indirect dimension. An added convenience is afforded by the fact that a usual 2D FFT can be used to process the generated data. Acquisitions of 2D heteronuclear correlation NMR spectra on quinine and on the anti-inflammatory drug isobutyl propionic phenolic acid illustrate the new method's performance. This method can be readily automated to deal with complex samples such as those occurring in metabolomics, in in-cell as well as in in vivo NMR applications, where speed and temporal stability are often primary concerns.

  7. An experiment-based comparative investigation of correlations for microtube gas flow

    Indian Academy of Sciences (India)

    K Tang; J L Huang; T Jin; M X Wu

    2015-04-01

    An experimental system was built to measure the gas (nitrogen and helium) flow characteristics in circular microchannels with diameters of 50, 20 and 5 m. The Reynolds number of the flow was controlled in the large range of 15 to 2550. The highest Mach number could reach a magnitude of 0.625 and the highest Knudsen number was over 0.021. Four available empirical correlations were comparatively studied, in terms of the influence from compressibility and rarefaction. The accuracy of each correlation was investigated, and qualitative explanations were given according to the essence of fluid dynamics. The compressibility is found to be the dominant parameter in the experiments carried out. The results obtained by gas flow in holey optical fibres are helpful for the design of micro-scale pulse tube cryocoolers.

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

    Science.gov (United States)

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

    2009-01-01

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

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

    Science.gov (United States)

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

    2009-01-01

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

  10. Gradient-Diffusion Methods for Simulating Decoherence by NMR Spectroscopy

    CERN Document Server

    Havel, T F; Viola, L; Cory, D G; Havel, Timothy F.; Sharf, Yehuda; Viola, Lorenza; Cory, David G.

    2001-01-01

    Theoretical techniques are developed for designing nuclear magnetic resonance (NMR) experiments to simulate a variety of adiabatic decoherence (aka T_2 relaxation) processes, using sequences of pulsed field gradients and diffusion periods. To this end an efficient Hadamard product formalism is introduced and used to derive Lindblad master equations from NMR pulse sequences for both collective and independent phase damping on any number of spins. The Kraus operator sum form is shown to be related to the Hadamard form by diagonalization, and explicit Lindblad and Kraus operators given for arbitrary correlations between two spins. Finally, gradient-diffusion methods are outlined for more complex forms of decoherence, including the three-axis collective model.

  11. Heterogeneities in gelatin film formation using single-sided NMR.

    Science.gov (United States)

    Ghoshal, Sushanta; Mattea, Carlos; Denner, Paul; Stapf, Siegfried

    2010-12-16

    Gelatin solutions were prepared in D(2)O. The drying process of cast solutions was followed with a single-sided nuclear magnetic resonance (NMR) scanner until complete solidification occurred. Spin-spin relaxation times (T(2)) were measured at different layers with microscopic resolution and were correlated with the drying process during film formation. Additionally, the evaporation of the gelatin solution was observed optically from the reduction of the sample thickness, revealing that at the macroscopic level, the rate of evaporation is not uniform throughout the experiment. A crossover in the spatial evolution of the drying process is observed from the NMR results. At the early stages, the gel appears to be drier in the upper layers near the evaporation front, while this tendency is inverted at the later stages, when drying is faster from the bottom. XRD (X-ray diffraction) data showed that a structural heterogeneity persists in the final film.

  12. TDPAC and β-NMR applications in chemistry and biochemistry

    Science.gov (United States)

    Jancso, Attila; Correia, Joao G.; Gottberg, Alexander; Schell, Juliana; Stachura, Monika; Szunyogh, Dániel; Pallada, Stavroula; Lupascu, Doru C.; Kowalska, Magdalena; Hemmingsen, Lars

    2017-06-01

    Time differential perturbed angular correlation (TDPAC) of γ-rays spectroscopy has been applied in chemistry and biochemistry for decades. Herein we aim to present a comprehensive review of chemical and biochemical applications of TDPAC spectroscopy conducted at ISOLDE over the past 15 years, including elucidation of metal site structure and dynamics in proteins and model systems. β-NMR spectroscopy is well established in nuclear physics, solid state physics, and materials science, but only a limited number of applications in chemistry have appeared. Current endeavors at ISOLDE advancing applications of β-NMR towards chemistry and biochemistry are presented, including the first experiment on 31Mg2+ in an ionic liquid solution. Both techniques require the production of radioisotopes combined with advanced spectroscopic instrumentation present at ISOLDE.

  13. Localized molecular orbital analysis of the effect of electron correlation on the anomalous isotope effect in the NMR spin-spin coupling constant in methane

    DEFF Research Database (Denmark)

    Zarycz, M. Natalia C.; Sauer, Stephan P. A.; Provasi, Patricio F.

    2014-01-01

    We discuss the effect of electron correlation on the unexpected differential sensitivity (UDS) in the 1J(C-H) coupling constant of CH4 using a decomposition into contributions from localized molecular orbitals and compare with the 1J(N-H) coupling constant in NH3. In particular we discuss the well...... known fact that uncorrelated coupled Hartree-Fock (CHF) calculations are not able to reproduce the UDS in methane. For this purpose we have implemented for the first time a localized molecular orbital analysis for the second order polarization propagator approximation with coupled cluster singles...... and doubles amplitudes - SOPPA(CCSD) in the DALTON program. Comparing the changes in the localized orbital contributions at the correlated SOPPA and SOPPA(CCSD) levels and at the uncorrelated CHF level, we find that the latter overestimates the effect of stretching the bond between the coupled atoms...

  14. Maternal anxiety and its correlation with pain experience during chorion villus sampling and amniocentesis

    Science.gov (United States)

    Klages, Katharina; Kundu, Sudip; Erlenwein, Joachim; Elsaesser, Michael; Hillemanns, Peter; Scharf, Alexander; Staboulidou, Ismini

    2017-01-01

    Purpose Invasive prenatal diagnostic procedures, such as chorion villus sampling (CVS) and amniocentesis (AC), are routinely performed to exclude or diagnose fetal chromosomal abnormalities. The aim of this study was to investigate anxiety-dependent pain experience during CVS and AC and the potential factors that increase anxiety and pain levels. Patients and methods During a 2-year period, women undergoing invasive procedures in three specialist centers were asked to participate in the study. Anxiety was evaluated before the procedure using the Spielberger State-Trait-Anxiety-Inventory, and pain was evaluated directly after the procedure using a verbal rating scale. Results Among the women, 348/480 (73%) underwent AC, while 131/480 (27%) underwent CVS. There was a significant correlation between state and trait anxiety (p<0.0001). A positive correlation existed between the degree of anxiety and the level of pain experienced (p=0.01). There was a positive correlation for trait anxiety (p=0.0283) as well as for state anxiety (p=0.0001) and pain perception (p=0.0061) when invasive procedure was performed owing to abnormal ultrasound finding or to a history of fetal aneuploidy. Maternal age was found to be another influencing factor for the experienced pain (p=0.0016). Furthermore, the analysis showed a significant negative correlation between maternal age and anxiety. That applies for trait anxiety (p=0.0001) as well as for state anxiety (p=0.0001). The older the woman, the less anxious the reported feeling was in both groups. The main indication for undergoing CVS was abnormal ultrasound results (45%), and the main reason for undergoing AC was maternal age (58%). Conclusion Procedure-related pain intensity is highly dependent on the degree of anxiety before the invasive procedure. In addition, the indication has a significant impact on the emerging anxiety and consequential pain experiences. These influencing factors should therefore be considered during counseling

  15. Effect of solvent on proton location and dynamic behavior in short intramolecular hydrogen bonds studied by molecular dynamics simulations and NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

    Mori, Yukie, E-mail: mori.yukie@ocha.ac.jp; Masuda, Yuichi

    2015-09-08

    Highlights: • MD simulations were performed to study dynamics of strong hydrogen bonds. • Nuclear magnetic relaxation times of proton were measured in solution. • The hydrogen bond of dibenzoylmethane enol is asymmetric in methanol solution. • Formation or breakage of intermolecular hydrogen bonds can trigger proton transfer. • Dimethylsulfoxide may form a bifurcated hydrogen bond with a hydrogen-bonded system. - Abstract: Hydrogen phthalate anion has a short strong O–H–O hydrogen bond (H-bond). According to previous experimental studies, the H-bond is asymmetric and two tautomers are interconverted in aqueous solutions. In the present study, the effects of polar solvents on the H-bond in a zwitterionic hydrogen phthalate derivative 1 were investigated by quantum mechanics/molecular mechanics molecular dynamics (MD) simulations. The analyses of the trajectories for the methanol solution showed that the H-bonding proton tends to be located closer to the carboxylate group that forms fewer intermolecular H-bonds, than to the other carboxylate group and that the intramolecular proton transfer in 1 is triggered by the breakage and/or formation of an intermolecular H-bond. The enol form of dibenzoylmethane (2) also has a short H-bond, and the OH bond is reported to be rather long (>1.1 Å) in the crystal. In the present study, the effects of the solvent on the H-bond in 2 were investigated by molecular orbital (MO) calculations, MD simulations and nuclear magnetic resonance (NMR) spectroscopy. Density functional theory (DFT) calculations for 2 in vacuum indicated that the barrier height for the intramolecular proton transfer is almost the same as the zero-point energy of the vibrational ground state, resulting in broad distribution of the proton density along the H-bond, owing to the nuclear quantum effect. The OH distances were determined in CCl{sub 4}, acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the {sup 17

  16. Multispin correlations and pseudo-thermalization of the transient density matrix in solid-state NMR: free induction decay and magic echo

    Science.gov (United States)

    Morgan, Steven W.; Oganesyan, Vadim; Boutis, Gregory S.

    2013-01-01

    Quantum unitary evolution typically leads to thermalization of generic interacting many-body systems. There are very few known general methods for reversing this process, and we focus on the magic echo, a radio-frequency pulse sequence known to approximately “rewind” the time evolution of dipolar coupled homonuclear spin systems in a large magnetic field. By combining analytic, numerical, and experimental results we systematically investigate factors leading to the degradation of magic echoes, as observed in reduced revival of mean transverse magnetization. Going beyond the conventional analysis based on mean magnetization we use a phase encoding technique to measure the growth of spin correlations in the density matrix at different points in time following magic echoes of varied durations and compare the results to those obtained during a free induction decay (FID). While considerable differences are documented at short times, the long-time behavior of the density matrix appears to be remarkably universal among the types of initial states considered – simple low order multispin correlations are observed to decay exponentially at the same rate, seeding the onset of increasingly complex high order correlations. This manifestly athermal process is constrained by conservation of the second moment of the spectrum of the density matrix and proceeds indefinitely, assuming unitary dynamics. PMID:23710125

  17. Applied NMR spectroscopy for chemists and life scientists

    CERN Document Server

    Zerbe, Oliver

    2013-01-01

    From complex structure elucidation to biomolecular interactions - this applicationoriented textbook covers both theory and practice of modern NMR applications. Part one sets the stage with a general description of NMR introducing important parameters such as the chemical shift and scalar or dipolar couplings. Part two describes the theory behind NMR, providing a profound understanding of the involved spin physics, deliberately kept shorter than in other NMR textbooks, and without a rigorous mathematical treatment of all the physico-chemical computations. Part three discusses technical and practical aspects of how to use NMR. Important phenomena such as relaxation, exchange, or the nuclear Overhauser effects and the methods of modern NMR spectroscopy including multidimensional experiments, solid state NMR, and the measurement of molecular interactions are the subject of part four. The final part explains the use of NMR for the structure determination of selected classes of complex biomolecules, from steroids t...

  18. Overview of Neutron Beta Correlation Parameter Analysis from the UCNA Experiment

    Science.gov (United States)

    Sun, Xuan; UCNA Collaboration

    2017-01-01

    The UCNA experiment, operated at the Ultracold Neutron Facility at the Los Alamos Neutron Science Center, uses ultracold neutrons (UCN) to measure the free-neutron β-decay correlation parameter, A, between the neutron spin direction and β momentum direction. Measurements of A presently provide the most precise value of gA /gV , the ratio of the axial-vector and vector coupling constants of the nucleon weak interaction. The UCNA experiment has previously analyzed and reported on a measurement of A from a 2010 dataset. Additional datasets were also taken in 2011-2012 and 2012-2013. Improvements in energy calibrations, polarimetry, and statistics are expected to provide a more precise measurement of A from the later datasets. We provide a review of the experimental apparatus and give an updated overview on the state of the 2011-2012 and 2012-2013 dataset analysis with respect to the A measurement.

  19. Interfacial Ca2+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced 43Ca NMR spectroscopy

    Science.gov (United States)

    Lee, Daniel; Leroy, César; Crevant, Charlène; Bonhomme-Coury, Laure; Babonneau, Florence; Laurencin, Danielle; Bonhomme, Christian; de Paëpe, Gaël

    2017-01-01

    The interfaces within bones, teeth and other hybrid biomaterials are of paramount importance but remain particularly difficult to characterize at the molecular level because both sensitive and selective techniques are mandatory. Here, it is demonstrated that unprecedented insights into calcium environments, for example the differentiation of surface and core species of hydroxyapatite nanoparticles, can be obtained using solid-state NMR, when combined with dynamic nuclear polarization. Although calcium represents an ideal NMR target here (and de facto for a large variety of calcium-derived materials), its stable NMR-active isotope, calcium-43, is a highly unreceptive probe. Using the sensitivity gains from dynamic nuclear polarization, not only could calcium-43 NMR spectra be obtained easily, but natural isotopic abundance 2D correlation experiments could be recorded for calcium-43 in short experimental time. This opens perspectives for the detailed study of interfaces in nanostructured materials of the highest biological interest as well as calcium-based nanosystems in general.

  20. Communication: Localized molecular orbital analysis of the effect of electron correlation on the anomalous isotope effect in the NMR spin-spin coupling constant in methane

    Energy Technology Data Exchange (ETDEWEB)

    Zarycz, M. Natalia C., E-mail: mnzarycz@gmail.com; Provasi, Patricio F., E-mail: patricio@unne.edu.ar [Department of Physics, University of Northeastern - CONICET, Av. Libertad 5500, Corrientes W3404AAS (Argentina); Sauer, Stephan P. A., E-mail: sauer@kiku.dk [Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø (Denmark)

    2014-10-21

    We discuss the effect of electron correlation on the unexpected differential sensitivity (UDS) in the {sup 1}J(C–H) coupling constant of CH{sub 4} using a decomposition into contributions from localized molecular orbitals and compare with the {sup 1}J(N–H) coupling constant in NH{sub 3}. In particular, we discuss the well known fact that uncorrelated coupled Hartree-Fock (CHF) calculations are not able to reproduce the UDS in methane. For this purpose we have implemented for the first time a localized molecular orbital analysis for the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes—SOPPA(CCSD) in the DALTON program. Comparing the changes in the localized orbital contributions at the correlated SOPPA and SOPPA(CCSD) levels and at the uncorrelated CHF level, we find that the latter overestimates the effect of stretching the bond between the coupled atoms on the contribution to the coupling from the localized bonding orbital between these atoms. This disturbs the subtle balance between the molecular orbital contributions, which lead to the UDS in methane.

  1. CPMG relaxation dispersion NMR experiments measuring glycine {sup 1}H{sup {alpha}} and {sup 13}C{sup {alpha}} chemical shifts in the 'invisible' excited states of proteins

    Energy Technology Data Exchange (ETDEWEB)

    Vallurupalli, Pramodh; Hansen, D. Flemming; Lundstroem, Patrik; Kay, Lewis E. [University of Toronto, Departments of Molecular Genetics, Biochemistry and Chemistry (Canada)], E-mail: kay@pound.med.utoronto.ca

    2009-09-15

    Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion NMR experiments are extremely powerful for characterizing millisecond time-scale conformational exchange processes in biomolecules. A large number of such CPMG experiments have now emerged for measuring protein backbone chemical shifts of sparsely populated (>0.5%), excited state conformers that cannot be directly detected in NMR spectra and that are invisible to most other biophysical methods as well. A notable deficiency is, however, the absence of CPMG experiments for measurement of {sup 1}H{sup {alpha}} and {sup 13}C{sup {alpha}} chemical shifts of glycine residues in the excited state that reflects the fact that in this case the {sup 1}H{sup {alpha}}, {sup 13}C{sup {alpha}} spins form a three-spin system that is more complex than the AX {sup 1}H{sup {alpha}}-{sup 13}C{sup {alpha}} spin systems in the other amino acids. Here pulse sequences for recording {sup 1}H{sup {alpha}} and {sup 13}C{sup {alpha}} CPMG relaxation dispersion profiles derived from glycine residues are presented that provide information from which {sup 1}H{sup {alpha}}, {sup 13}C{sup {alpha}} chemical shifts can be obtained. The utility of these experiments is demonstrated by an application to a mutant of T4 lysozyme that undergoes a millisecond time-scale exchange process facilitating the binding of hydrophobic ligands to an internal cavity in the protein.

  2. Proton and deuterium NMR experiments in zero field. [Perdeuterated p-demethoxybenzene, perdeuterated malonic acid, diethyl terephthalate-d4, nonadecane-2,2'-D2, sodium propionate-D2

    Energy Technology Data Exchange (ETDEWEB)

    Millar, J.M.

    1986-02-01

    High field solid-state NMR lineshapes suffer from inhomogeneous broadening since resonance frequencies are a function of molecular orientation. Time domain zero field NMR is a two-dimensional field-cycling technique which removes this broadening by probing the evolution of the spin system under zero applied field. The simplest version, the sudden transition experiment, induces zero field evolution by the sudden removal of the applied magnetic field. Theory and experimental results of this experiment and several variations using pulsed dc magnetic fuelds to initiate zero field evolution are presented. In particular, the pulsed indirect detection method allows detection of the zero field spectrum of one nuclear spin species via another (usually protons) by utilizing the level crossings which occur upon adiabatic demagnetization to zero field. Experimental examples of proton/deuteron systems are presented which demonstrate the method results in enhanced sensitivity relative to that obtained in sudden transition experiments performed directly on deuterium. High resolution /sup 2/H NQR spectra of a series of benzoic acid derivatives are obtained using the sudden transition and indirect detection methods. Librational oscillations in the water molecules of barium chlorate monohydrate are studied using proton and deuterium ZF experiments. 177 refs., 88 figs., 2 tabs.

  3. Intraclass Correlations and Covariate Outcome Correlations for Planning Two-and Three-Level Cluster-Randomized Experiments in Education

    Science.gov (United States)

    Hedges, Larry V.; Hedberg, E. C.

    2013-01-01

    Background: Cluster-randomized experiments that assign intact groups such as schools or school districts to treatment conditions are increasingly common in educational research. Such experiments are inherently multilevel designs whose sensitivity (statistical power and precision of estimates) depends on the variance decomposition across levels.…

  4. Intraclass Correlations and Covariate Outcome Correlations for Planning 2 and 3 Level Cluster Randomized Experiments in Education

    Science.gov (United States)

    Hedges, Larry V.; Hedberg, Eric C.

    2013-01-01

    Background: Cluster randomized experiments that assign intact groups such as schools or school districts to treatment conditions are increasingly common in educational research. Such experiments are inherently multilevel designs whose sensitivity (statistical power and precision of estimates) depends on the variance decomposition across levels.…

  5. Solid State NMR Studies of Energy Conversion and Storage Materials

    Science.gov (United States)

    Jankuru Hennadige, Sohan Roshel De Silva

    NMR (Nuclear magnetic resonance) spectroscopy is utilized to study energy conversion and storage materials. Different types of NMR techniques including Magic Angle Spinning, Cross-polarization and relaxation measurement experiments were employed. Four different projects are discussed in this dissertation. First, three types of CFx battery materials were investigated. Electrochemical studies have demonstrated different electrochemical performances by one type, delivering superior performance over the other two. 13C and 19F MAS NMR techniques are employed to identify the atomic/molecular structural factors that might account for differences in electrochemical performance among different types. Next as the second project, layered polymer dielectrics were investigated by NMR. Previous studies have shown that thin film capacitors are improved by using alternate layers of two polymers with complementary properties: one with a high breakdown strength and one with high dielectric constant as opposed to monolithic layers. 13C to 1H cross-polarization techniques were used to investigate any inter-layer properties that may cause the increase in the dielectric strength. The third project was to study two types of thermoelectric materials. These samples were made of heavily doped phosphorous and boron in silicon by two different methods: ball-milled and annealed. These samples were investigated by NMR to determine the degree of disorder and obtain insight into the doping efficiency. The last ongoing project is on a lithium-ion battery system. The nature of passivating layers or the solid electrolyte interphase (SEI) formed on the electrodes surface is important because of the direct correlation between the SEI and the battery life time/durability. Multinuclear (7Li, 19F, 31P) techniques are employed to identify the composition of the SEI formation of both positive and negative electrodes.

  6. Investigation of zinc alkali pyrophosphate glasses. Part II: Local and medium range orders analysed by 1D/2D NMR

    Energy Technology Data Exchange (ETDEWEB)

    Rajbhandari, P. [UCCS UMR-CNRS 8181, Université de Lille1, Villeneuve d' Ascq (France); Chen, Y. [LASIR UMR-CNRS 8516, Université de Lille1, Villeneuve d' Ascq (France); Doumert, B. [IMMCL CNRS-FR2638, Université de Lille1, Villeneuve d' Ascq (France); Montagne, L. [UCCS UMR-CNRS 8181, Université de Lille1, Villeneuve d' Ascq (France); Tricot, G., E-mail: gregory.tricot@univ-lille1.fr [UCCS UMR-CNRS 8181, Université de Lille1, Villeneuve d' Ascq (France); LASIR UMR-CNRS 8516, Université de Lille1, Villeneuve d' Ascq (France)

    2015-04-01

    The structure of the (66-x)ZnO-xNa{sub 2}O-33.4P{sub 2}O{sub 5} composition line, selected for the development of low-Tg and stable glasses, has been investigated by 1D/2D NMR spectroscopy. If standard 1D {sup 31}P MAS-NMR experiments give access to the Q{sup n} speciation and show the presence of Q{sup 0}, Q{sup 1} and Q{sup 2} sites within the glass structure, application of the homonuclear through-space correlation technique ({sup 31}P DQ-SQ) allows for a more accurate description of the phosphate units. Clear distinction between the Q{sup 1} sites involved in dimmers or in longer chains has been derived from 2D NMR correlation maps and leads to the re-assignment of Q{sup 1} into Q{sup 1,1} and Q{sup 1,2} species. {sup 23}Na and {sup 23}Na({sup 31}P) REDOR MAS-NMR experiments have been used to analyse the Na{sup +} ions distribution and its interaction with the phosphate network. {sup 67}Zn static NMR experiments, performed at very high field, were carried out and suggest a constant Zn{sup 2+} coordination state all along the composition line. The results have been used to discuss the impact of the Zn{sup 2+}/Na{sup +} ratio on the extent of disorder within the glass network expressed in terms of Q{sup n} dismutation equilibrium constant and phosphate chain length distribution. - Highlights: • Structure of zinc alkali pyrophosphate glasses have been analysed by 1D/2D NMR. • 2D {sup 31}P experiments allow to separate Q{sup 1,1} and Q{sup 1,2} species. • {sup 67}Zn static NMR shows a constant signal all along the composition line.

  7. NMR reaction monitoring in flow synthesis

    Directory of Open Access Journals (Sweden)

    M. Victoria Gomez

    2017-02-01

    Full Text Available Recent advances in the use of flow chemistry with in-line and on-line analysis by NMR are presented. The use of macro- and microreactors, coupled with standard and custom made NMR probes involving microcoils, incorporated into high resolution and benchtop NMR instruments is reviewed. Some recent selected applications have been collected, including synthetic applications, the determination of the kinetic and thermodynamic parameters and reaction optimization, even in single experiments and on the μL scale. Finally, software that allows automatic reaction monitoring and optimization is discussed.

  8. Toward Structural Correctness: Aquatolide and the Importance of 1D Proton NMR FID Archiving.

    Science.gov (United States)

    Pauli, Guido F; Niemitz, Matthias; Bisson, Jonathan; Lodewyk, Michael W; Soldi, Cristian; Shaw, Jared T; Tantillo, Dean J; Saya, Jordy M; Vos, Klaas; Kleinnijenhuis, Roel A; Hiemstra, Henk; Chen, Shao-Nong; McAlpine, James B; Lankin, David C; Friesen, J Brent

    2016-02-05

    The revision of the structure of the sesquiterpene aquatolide from a bicyclo[2.2.0]hexane to a bicyclo[2.1.1]hexane structure using compelling NMR data, X-ray crystallography, and the recent confirmation via full synthesis exemplify that the achievement of "structural correctness" depends on the completeness of the experimental evidence. Archived FIDs and newly acquired aquatolide spectra demonstrate that archiving and rigorous interpretation of 1D (1)H NMR data may enhance the reproducibility of (bio)chemical research and curb the growing trend of structural misassignments. Despite being the most accessible NMR experiment, 1D (1)H spectra encode a wealth of information about bonds and molecular geometry that may be fully mined by (1)H iterative full spin analysis (HiFSA). Fully characterized 1D (1)H spectra are unideterminant for a given structure. The corresponding FIDs may be readily submitted with publications and collected in databases. Proton NMR spectra are indispensable for structural characterization even in conjunction with 2D data. Quantum interaction and linkage tables (QuILTs) are introduced for a more intuitive visualization of 1D J-coupling relationships, NOESY correlations, and heteronuclear experiments. Overall, this study represents a significant contribution to best practices in NMR-based structural analysis and dereplication.

  9. 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.

  10. Recent progress in heteronuclear long-range NMR of complex carbohydrates: 3D H2BC and clean HMBC

    DEFF Research Database (Denmark)

    Meier, Sebastian; Petersen, Bent O.; Duus, Jens Øllgaard

    2009-01-01

    carbohydrates whose structure has been determined by NMR, not least due to the enhanced resolution offered by the third dimension in 3D H2BC and the improved spectral quality due to artifact suppression in clean HMBC. Hence these new experiments set the scene to take advantage of the sensitivity boost achieved...... by the latest generation of cold probes for NMR structure determination of even larger and more complex carbohydrates in solution.......The new NMR experiments 3D H2BC and clean HMBC are explored for challenging applications to a complex carbohydrate at natural abundance of 13C. The 3D H2BC experiment is crucial for sequential assignment as it yields heteronuclear one- and two-bond together with COSY correlations for the 1H spins...

  11. The flexibility of SIMPSON and SIMMOL for numerical simulations in solid-and liquid-state NMR spectroscopy

    CERN Document Server

    Vosegaard, T; Nielsen, N C

    2002-01-01

    Addressing the need for numerical simulations in the design and interpretation of advanced solid- and liquid-state NMR experiments, we present a number of novel features for numerical simulations based on the SIMPSON and SIMMOL open source software packages. Major attention is devoted to the flexibility of these Tcl-interfaced programs for numerical simulation of NMR experiments being complicated by demands for efficient powder averaging, large spin systems, and multiple-pulse rf irradiation. These features are exemplified by fast simulation of second-order quadrupolar powder patterns using crystallite interpolation, analysis of rotary resonance triple-quantum excitation for quadrupolar nuclei, iterative fitting of MQ-MAS spectra by combination of SIMIPSON and MINUIT, simulation of multiple-dimensional PISEMA-type correlation experiments for macroscopically oriented membrane proteins, simulation of Hartman-Hahn polarization transfers in liquid-state NMR, and visualization of the spin evolution under complex c...

  12. Applications of NMR spectroscopy to systems biochemistry.

    Science.gov (United States)

    Fan, Teresa W-M; Lane, Andrew N

    2016-02-01

    The past decades of advancements in NMR have made it a very powerful tool for metabolic research. Despite its limitations in sensitivity relative to mass spectrometric techniques, NMR has a number of unparalleled advantages for metabolic studies, most notably the rigor and versatility in structure elucidation, isotope-filtered selection of molecules, and analysis of positional isotopomer distributions in complex mixtures afforded by multinuclear and multidimensional experiments. In addition, NMR has the capacity for spatially selective in vivo imaging and dynamical analysis of metabolism in tissues of living organisms. In conjunction with the use of stable isotope tracers, NMR is a method of choice for exploring the dynamics and compartmentation of metabolic pathways and networks, for which our current understanding is grossly insufficient. In this review, we describe how various direct and isotope-edited 1D and 2D NMR methods can be employed to profile metabolites and their isotopomer distributions by stable isotope-resolved metabolomic (SIRM) analysis. We also highlight the importance of sample preparation methods including rapid cryoquenching, efficient extraction, and chemoselective derivatization to facilitate robust and reproducible NMR-based metabolomic analysis. We further illustrate how NMR has been applied in vitro, ex vivo, or in vivo in various stable isotope tracer-based metabolic studies, to gain systematic and novel metabolic insights in different biological systems, including human subjects. The pathway and network knowledge generated from NMR- and MS-based tracing of isotopically enriched substrates will be invaluable for directing functional analysis of other 'omics data to achieve understanding of regulation of biochemical systems, as demonstrated in a case study. Future developments in NMR technologies and reagents to enhance both detection sensitivity and resolution should further empower NMR in systems biochemical research.

  13. Measurements of Long-range Electronic Correlations During Femtosecond Diffraction Experiments Performed on Nanocrystals of Buckminsterfullerene.

    Science.gov (United States)

    Ryan, Rebecca A; Williams, Sophie; Martin, Andrew V; Dilanian, Ruben A; Darmanin, Connie; Putkunz, Corey T; Wood, David; Streltsov, Victor A; Jones, Michael W M; Gaffney, Naylyn; Hofmann, Felix; Williams, Garth J; Boutet, Sebastien; Messerschmidt, Marc; Seibert, M Marvin; Curwood, Evan K; Balaur, Eugeniu; Peele, Andrew G; Nugent, Keith A; Quiney, Harry M; Abbey, Brian

    2017-08-22

    The precise details of the interaction of intense X-ray pulses with matter are a topic of intense interest to researchers attempting to interpret the results of femtosecond X-ray free electron laser (XFEL) experiments. An increasing number of experimental observations have shown that although nuclear motion can be negligible, given a short enough incident pulse duration, electronic motion cannot be ignored. The current and widely accepted models assume that although electrons undergo dynamics driven by interaction with the pulse, their motion could largely be considered 'random'. This would then allow the supposedly incoherent contribution from the electronic motion to be treated as a continuous background signal and thus ignored. The original aim of our experiment was to precisely measure the change in intensity of individual Bragg peaks, due to X-ray induced electronic damage in a model system, crystalline C60. Contrary to this expectation, we observed that at the highest X-ray intensities, the electron dynamics in C60 were in fact highly correlated, and over sufficiently long distances that the positions of the Bragg reflections are significantly altered. This paper describes in detail the methods and protocols used for these experiments, which were conducted both at the Linac Coherent Light Source (LCLS) and the Australian Synchrotron (AS) as well as the crystallographic approaches used to analyse the data.

  14. 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....

  15. Application of chemometrics to low-field H-1 NMR relaxation data of intact fish flesh

    DEFF Research Database (Denmark)

    Jepsen, Signe Munk; Pedersen, H.T.; Engelsen, S.B.

    1999-01-01

    and subsequently analysed for oil or water content by standard chemical methods. In a second experiment, 58 differently thawed cod (Gadus morhua) samples were measured by NMR and subsequently analysed for water-holding capacity. Correlations between chemical data and NMR data were evaluated using partial least...... squares (PLS) regression on complete relaxation curves and compared with conventional regression models on exponential fitting parameters. Predictions on an independent test set were superior for the PLS regression models, with optimal prediction errors of 12 g kg(-1), 6 g kg(-1) and 3.9% for oil...... and water content in fresh salmon flesh and water-holding capacity in thawed cod flesh respectively. Thus rapid, non-invasive low- field NMR can be used to simultaneously determine both oil and water content of fish flesh. Furthermore, it can predict water- holding capacity of cod flesh, with an R-2 of 0...

  16. Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

    Energy Technology Data Exchange (ETDEWEB)

    Vivas-Reyes, R.; Aria, A. [Universidad de Cartagena, Cartagena (Colombia). Facultad de Ciencias Naturales y Exactas. Grupo de Quimica Cuantica y Computacional]. E-mail: rvivasr@unicartagena.edu.co

    2008-07-01

    Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetra coordinated Sn compounds of the CH{sub 3}SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental {sup 119}Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH{sub 3}, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-3 1 1 + + G basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms. (author)

  17. Non-Constant Learning Rates in Retrospective Experience Curve Analyses and their Correlation to Deployment Programs

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Max [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Smith, Sarah J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Sohn, Michael D. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-07-16

    A key challenge for policy-makers and technology market forecasters is to estimate future technology costs and in particular the rate of cost reduction versus production volume. A related, critical question is what role should state and federal governments have in advancing energy efficient and renewable energy technologies? This work provides retrospective experience curves and learning rates for several energy-related technologies, each of which have a known history of federal and state deployment programs. We derive learning rates for eight technologies including energy efficient lighting technologies, stationary fuel cell systems, and residential solar photovoltaics, and provide an overview and timeline of historical deployment programs such as state and federal standards and state and national incentive programs for each technology. Piecewise linear regimes are observed in a range of technology experience curves, and public investments or deployment programs are found to be strongly correlated to an increase in learning rate across multiple technologies. A downward bend in the experience curve is found in 5 out of the 8 energy-related technologies presented here (electronic ballasts, magnetic ballasts, compact fluorescent lighting, general service fluorescent lighting, and the installed cost of solar PV). In each of the five downward-bending experience curves, we believe that an increase in the learning rate can be linked to deployment programs to some degree. This work sheds light on the endogenous versus exogenous contributions to technological innovation and highlights the impact of exogenous government sponsored deployment programs. This work can inform future policy investment direction and can shed light on market transformation and technology learning behavior.

  18. Study of correlations between photoproduced pairs of charmed particles at Experiment E831/FOCUS

    Energy Technology Data Exchange (ETDEWEB)

    Castromonte Flores, Cesar Manuel [Brazilian Center for Physics Research, Rio de Janeiro (Brazil)

    2008-08-01

    The authors present the study of the charm-pair correlations produced in photon-nucleon interactions at $\\langle$Eγ$\\rangle$ = 175 GeV/c, by the Fermilab fixed target experiment E831/FOCUS. The E831/FOCUS experiment produced and reconstructed over one million charm particles. This high statistics allows the reconstruction of more than 7000 charm-pair mesons D$\\bar{D}$, 10 times the statistic of former experiments, and also allows to get, for the first time, about 600 totally reconstructed charm-pairs in the DDs and DΛc channels. They were able to study, with some detail, the kinematical correlations between the charm and anticharm particle forming a pair, in the square transverse momentum (pT2), azimuthal angle difference (ΔΦ), rapidity difference (Δy) and the charm-pair mass variables. They observe some correlation for the longitudinal momenta, and a significant correlation for the transverse momenta of the charm and anticharm particles. They compare the experimental distributions with theoretical predictions based on the photon-gluon fusion model (PGF), for the production of c$\\bar{c}$ quarks, and the standard Lund hadronization model. These models are implemented by the PYTHIA Monte Carlo event generator. The PYTHIA program allows the inclusion, in the simulation, of non-perturbative effects that have been shown to be important for charm production. In order to compare data and simulation, they have generated two Monte Carlo samples, the first one set to favor the production of D$\\bar{D}$ pairs (MCDD2), and the second one set to favor the production of DDsand DΛc pairs, where each one uses different functions and parameters values for the theoretical models in the simulation. They observe, for the correlation distributions, that the set of parameters used by the MCDD2 model together with the intrinsic transverse momentum (k$\\perp$) of the partons inside the

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

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Takeshi [Ames Laboratory; Gupta, Shalabh [Ames Laboratory; Caporini, Marc A [Bruker BioSpin Corporation; Pecharsky, Vitalij K [Ames Laboratory; Pruski, Marek [Ames Laboratory

    2014-08-28

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

  20. On the Relationship between Convex Bodies Related to Correlation Experiments with Dichotomic Observables

    CERN Document Server

    Avis, D; Ito, T; Avis, David; Imai, Hiroshi; Ito, Tsuyoshi

    2006-01-01

    In this paper we explore further the connections between convex bodies related to quantum correlation experiments with dichotomic variables and related bodies studied in combinatorial optimization, especially cut polyhedra. Such a relationship was established in Avis, Imai, Ito and Sasaki (2005 J. Phys. A: Math. Gen. 38 10971-87) with respect to Bell inequalities. We show that several well known bodies related to cut polyhedra are equivalent to bodies such as those defined by Tsirelson (1993 Hadronic J. S. 8 329-45) to represent hidden deterministic behaviors, quantum behaviors, and no-signalling behaviors. Among other things, our results allow a unique representation of these bodies, give a necessary condition for vertices of the no-signalling polytope, and give a method for bounding the quantum violation of Bell inequalities by means of a body that contains the set of quantum behaviors. Optimization over this latter body may be performed efficiently by semidefinite programming. In the second part of the pap...

  1. Detection System for Neutron $\\beta$ Decay Correlations in the UCNB and Nab experiments

    CERN Document Server

    Broussard, L J; Adamek, E R; Baeßler, S; Birge, N; Blatnik, M; Bowman, J D; Brandt, A E; Brown, M; Burkhart, J; Callahan, N B; Clayton, S M; Crawford, C; Cude-Woods, C; Currie, S; Dees, E B; Ding, X; Fomin, N; Frlez, E; Fry, J; Gray, F E; Hasan, S; Hickerson, K P; Hoagland, J; Holley, A T; Ito, T M; Klein, A; Li, H; Liu, C -Y; Makela, M F; McGaughey, P L; Mirabal-Martinez, J; Morris, C L; Ortiz, J D; Pattie, R W; Penttilä, S I; Plaster, B; Počanić, D; Ramsey, J C; Salas-Bacci, A; Salvat, D J; Saunders, A; Seestrom, S J; Sjue, S K L; Sprow, A P; Tang, Z; Vogelaar, R B; Vorndick, B; Wang, Z; Wei, W; Wexler, J; Wilburn, W S; Womack, T L; Young, A R

    2016-01-01

    We describe a detection system designed for precise measurements of angular correlations in neutron $\\beta$ decay. The system is based on thick, large area, highly segmented silicon detectors developed in collaboration with Micron Semiconductor, Ltd. The prototype system meets specifications for $\\beta$ electron detection with energy thresholds below 10 keV, energy resolution of $\\sim$3 keV FWHM, and rise time of $\\sim$50 ns with 19 of the 127 detector pixels instrumented. Using ultracold neutrons at the Los Alamos Neutron Science Center, we have demonstrated the coincident detection of $\\beta$ particles and recoil protons from neutron $\\beta$ decay. The fully instrumented detection system will be implemented in the UCNB and Nab experiments, to determine the neutron $\\beta$ decay parameters $B$, $a$, and $b$.

  2. The effect of electron-electron correlation on the attoclock experiment

    CERN Document Server

    Emmanouilidou, A; Hofmann, C; Keller, U; Landsman, A S

    2015-01-01

    We investigate multi-electron effects in strong-field ionization of Helium using a semi-classical model that, unlike other commonly used theoretical approaches, takes into account electron-electron correlation. Our approach has an additional advantage of allowing to selectively switch off different contributions from the parent ion (such as the remaining electron or the nuclear charge) and thereby investigate in detail how the final electron angle in the attoclock experiment is influenced by these contributions. We find that the bound electron exerts a significant effect on the final electron momenta distribution that can, however, be accounted for by an appropriately selected mean field. Our results show excellent agreement with other widely used theoretical models done within a single active electron approximation.

  3. Neural correlate of subjective sensory experience gradually builds up across cortical areas

    Science.gov (United States)

    de Lafuente, Victor; Romo, Ranulfo

    2006-01-01

    When a sensory stimulus is presented, many cortical areas are activated, but how does the representation of a sensory stimulus evolve in time and across cortical areas during a perceptual judgment? We investigated this question by analyzing the responses from single neurons, recorded in several cortical areas of parietal and frontal lobes, while trained monkeys reported the presence or absence of a mechanical vibration of varying amplitude applied to the skin of one fingertip. Here we show that the strength of the covariations between neuronal activity and perceptual judgments progressively increases across cortical areas as the activity is transmitted from the primary somatosensory cortex to the premotor areas of the frontal lobe. This finding suggests that the neuronal correlates of subjective sensory experience gradually build up across somatosensory areas of the parietal lobe and premotor cortices of the frontal lobe. PMID:16924098

  4. Detection system for neutron β decay correlations in the UCNB and Nab experiments

    Science.gov (United States)

    Broussard, L. J.; Zeck, B. A.; Adamek, E. R.; Baeßler, S.; Birge, N.; Blatnik, M.; Bowman, J. D.; Brandt, A. E.; Brown, M.; Burkhart, J.; Callahan, N. B.; Clayton, S. M.; Crawford, C.; Cude-Woods, C.; Currie, S.; Dees, E. B.; Ding, X.; Fomin, N.; Frlez, E.; Fry, J.; Gray, F. E.; Hasan, S.; Hickerson, K. P.; Hoagland, J.; Holley, A. T.; Ito, T. M.; Klein, A.; Li, H.; Liu, C.-Y.; Makela, M. F.; McGaughey, P. L.; Mirabal-Martinez, J.; Morris, C. L.; Ortiz, J. D.; Pattie, R. W.; Penttilä, S. I.; Plaster, B.; Počanić, D.; Ramsey, J. C.; Salas-Bacci, A.; Salvat, D. J.; Saunders, A.; Seestrom, S. J.; Sjue, S. K. L.; Sprow, A. P.; Tang, Z.; Vogelaar, R. B.; Vorndick, B.; Wang, Z.; Wei, W.; Wexler, J.; Wilburn, W. S.; Womack, T. L.; Young, A. R.

    2017-03-01

    We describe a detection system designed for precise measurements of angular correlations in neutron β decay. The system is based on thick, large area, highly segmented silicon detectors developed in collaboration with Micron Semiconductor, Ltd. The prototype system meets specifications for β electron detection with energy thresholds below 10 keV, energy resolution of ∼3 keV FWHM, and rise time of ∼50 ns with 19 of the 127 detector pixels instrumented. Using ultracold neutrons at the Los Alamos Neutron Science Center, we have demonstrated the coincident detection of β particles and recoil protons from neutron β decay. The fully instrumented detection system will be implemented in the UCNB and Nab experiments to determine the neutron β decay parameters B, a, and b.

  5. Reported cystoscopic experience correlates poorly with objective assessment of cystoscopic skills.

    Science.gov (United States)

    Nihira, Mikio A; Drake, Natalie L; Corton, Marlene M; Wai, Clifford Y; Coleman, Robert L; Quiroz, Lieschen H

    2012-01-01

    Although gynecologists perform a large number of surgeries in close proximity to the ureters and the urinary bladder, traditionally, Obstetrics and Gynecology resident physicians are not formally taught to perform cystoscopy. The primary objective was to document resident physicians' performance in diagnostic cystoscopic instrumentation and technique. The secondary objective was to examine if reported prior cystoscopic experience was associated with superior performance. Fifty-one postgraduate year 4 residents with reported experience with cystoscopy were evaluated using an operation-specific checklist and a global ratings scale based on the Objective Structured Assessment of Technical Skill model. Before evaluation, they attended a formal training session in cystoscopy, which included practice on a bench model of a simulated bladder. Forty-three of the 51 residents were able to successfully perform a thorough diagnostic examination immediately after the course. Six of the 8 failures were re-evaluated 2 weeks later and successfully performed a complete examination at that time. Before the course, the residents had performed a mean of 12.2 cystoscopic examinations as the primary surgeon (median, 12; range, 2-33). The number of reported cystoscopic examinations performed before the course did not correlate with the ability to perform a thorough cystoscopic examination (r = -0.109; P = 0.496). For this group of residents, there was poor correlation between the number of reported cystoscopic examinations and the ability to perform diagnostic cystoscopy. Trainees may not be able to determine when they have received enough instruction in hands-on training with models before acquisition of technical skills.

  6. Children's Experience of Posttraumatic Growth: Distinguishing General from Domain-Specific Correlates.

    Directory of Open Access Journals (Sweden)

    Odilia M Laceulle

    Full Text Available Although the five domains of posttraumatic growth (new possibilities, relating to others, personal strength, spiritual change and appreciation of life have been studied extensively in adults, little is known about these domains and their correlates in children. We aimed to examine whether demographic and/or social characteristics are related to children's reports of overall posttraumatic growth and of growth in specific domains. In a general population study, children aged 8-12 years who had been exposed to adverse events (N = 1290 filled out questionnaires on their experiences, demographic characteristics (gender, age, time lag since event, stress reactions, peer support, religiosity and posttraumatic growth. All demographic and social characteristics were related to overall posttraumatic growth, except time lag. Associations varied across the five domains with the strongest effects being found for stress reactions and religiosity. A higher level of stress reactions was related to more growth in all domains (general effect, whereas religious children experienced more spiritual growth than non-religious children without differences on other domains (domain specific effect. Other effects were small, and some did not remain significant after Bonferroni corrections. These findings suggest the presence of both general and domain-specific correlates of child posttraumatic growth. Although effects were generally small, the current findings show the need to differentiate between the domains of posttraumatic growth in both further research and clinical practice. This will allow a better understanding of the mechanisms of posttraumatic growth in children as well as more tailored assessment and intervention.

  7. Children's Experience of Posttraumatic Growth: Distinguishing General from Domain-Specific Correlates.

    Science.gov (United States)

    Laceulle, Odilia M; Kleber, Rolf J; Alisic, Eva

    2015-01-01

    Although the five domains of posttraumatic growth (new possibilities, relating to others, personal strength, spiritual change and appreciation of life) have been studied extensively in adults, little is known about these domains and their correlates in children. We aimed to examine whether demographic and/or social characteristics are related to children's reports of overall posttraumatic growth and of growth in specific domains. In a general population study, children aged 8-12 years who had been exposed to adverse events (N = 1290) filled out questionnaires on their experiences, demographic characteristics (gender, age, time lag since event), stress reactions, peer support, religiosity and posttraumatic growth. All demographic and social characteristics were related to overall posttraumatic growth, except time lag. Associations varied across the five domains with the strongest effects being found for stress reactions and religiosity. A higher level of stress reactions was related to more growth in all domains (general effect), whereas religious children experienced more spiritual growth than non-religious children without differences on other domains (domain specific effect). Other effects were small, and some did not remain significant after Bonferroni corrections. These findings suggest the presence of both general and domain-specific correlates of child posttraumatic growth. Although effects were generally small, the current findings show the need to differentiate between the domains of posttraumatic growth in both further research and clinical practice. This will allow a better understanding of the mechanisms of posttraumatic growth in children as well as more tailored assessment and intervention.

  8. Spin–spin coupling in the HD molecule determined from {sup 1}H and {sup 2}H NMR experiments in the gas-phase

    Energy Technology Data Exchange (ETDEWEB)

    Garbacz, Piotr, E-mail: pgarbacz@chem.uw.edu.pl

    2014-10-31

    Highlights: • The spin–spin coupling constant of the HD molecule is equal to 43.136(7) Hz at 300 K. • Peak-to-peak separations between HD multiplet peaks, J{sub eff}, are smaller than J (D, H). • Nuclear relaxation and intermolecular interactions have an influence on J{sub eff}. • J{sub eff} determined from the {sup 1}H NMR spectrum is smaller than from the {sup 2}H NMR spectrum. - Abstract: The indirect spin–spin coupling of hydrogen deuteride, J(D, H), was determined from a series of {sup 1}H and {sup 2}H NMR spectra acquired at various densities of gaseous solvents (He, Ar, CO{sub 2}, and N{sub 2}O). The analysis of these spectra shows that accurate determination of J(D, H) from this experimental data requires careful examination of the effects of nuclear relaxation and of HD–solvent gas interactions on hydrogen deuteride line shapes. Particularly, it was found that the first-order corrections of the peak-to-peak separations between HD multiplet peaks due to weak van der Waals interactions are proportional to solvent gas density, while these corrections for nuclear relaxation of the proton and the deuteron are proportional to the second power of the inverse of the gas density. Analysis of the data indicates that J(D, H), obtained by correcting for the effects of nuclear relaxation and intermolecular interactions, is 43.136(7) Hz at 300 K.

  9. Properties of the static NMR response of a confined thin nematic film of 5CB-d2 under crossed electric and magnetic fields: theory and experiments.

    Science.gov (United States)

    Véron, A; Sugimura, A; Luckhurst, G R; Martins, A F

    2012-11-01

    This work describes an investigation of the static (or quasistatic) nuclear magnetic resonance (NMR) response in a nematic liquid crystal confined between two planar conducting plates and subject to a magnetic field and an electric field produced by a difference of voltage applied on the plates. Deuterium NMR spectroscopy of 4-pentyl-d(2)-4'-cyanobiphenyl (5CB-d(2)) under these conditions has revealed a voltage dependent inhomogeneous director distribution for a particular narrow range of voltages and for a fixed magnetic field (that of the spectrometer). In the ideal setup the two plates are assumed to be rigorously parallel, so that a difference of voltage applied on the plates leads to a constant electric field normal to them. When the magnetic field is parallel to the plates (orthogonal geometry) there exists a threshold value of the electric field for which the effect of both fields exactly compensate; moreover, for stronger electric field the director aligns with the electric field while for weaker electric field the director aligns with the magnetic field. If there is a lack of parallelism between the two plates, the electric field becomes inhomogeneous so that it may be larger than the threshold value in some region of the sample and smaller in the remaining part of the sample. In that case the director will adopt essentially two orientations within the sample, namely, parallel or perpendicular to the magnetic field, and the position of the frontier between the two domains depends on the voltage. This feature is clearly shown by deuterium NMR spectra that exhibit a transfer of intensity between two quadrupolar doublets with increase in the applied voltage. The coexistence of two director populations occurs for a range of voltages that depends on the degree of nonparallelism; accordingly, an estimation of this range by NMR yields an experimental estimation of the lack of parallelism. A tiny tilt of the magnetic field (nonorthogonal geometry) entrains a

  10. Solution state structure determination of silicate oligomers by 29SI NMR spectroscopy and molecular modeling.

    Science.gov (United States)

    Cho, Herman; Felmy, Andrew R; Craciun, Raluca; Keenum, J Patrick; Shah, Neil; Dixon, David A

    2006-02-22

    Evidence for nine new solution state silicate oligomers has been discovered by (29)Si NMR homonuclear correlation experiments of (29)Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the (29)Si-(29)Si two-bond scalar couplings that are necessary for the observation of internuclear correlations in 2-D experiments. The proposed assignments are validated by comparisons of experimental and simulated cross-peaks obtained with high digital resolution. The internuclear connectivity indicated by the NMR data suggests that several of these oligomers can have multiple stereoisomers, including conformers and/or diastereomers. The stabilities of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations.

  11. How We Experience Being Alone: Age Differences in Affective and Biological Correlates of Momentary Solitude.

    Science.gov (United States)

    Pauly, Theresa; Lay, Jennifer C; Nater, Urs M; Scott, Stacey B; Hoppmann, Christiane A

    2017-01-01

    Spending time alone constitutes a ubiquitous part of our everyday lives. As we get older, alone time increases. Less is known, however, about age differences in the experience of spending time alone (momentary solitude). We examined time-varying associations between momentary solitude, affect quality, and two hypothalamic-pituitary-adrenal axis activity markers [salivary cortisol; dehydroepiandrosterone sulfate (DHEAs)] to better understand the affective and biological correlates of momentary solitude across the adult life span. A total of 185 adults aged 20-81 years (mean age = 49 years, 51% female, 74% Caucasian) completed questionnaires on momentary solitude (alone vs. not alone) and current affect on a handheld device, and provided concurrent saliva samples up to seven times a day for 10 consecutive days. Data were analyzed using multilevel models, controlling for the overall amount of time participants spent alone during the study (overall solitude). Greater overall solitude was associated with decreased average high arousal positive affect and increased average cortisol and DHEAs levels. Momentary solitude was associated with reduced high arousal positive affect, increased low arousal positive affect, and increased low arousal negative affect. Age by momentary solitude interactions indicate that greater age was associated with increased high arousal positive affect and reduced low arousal negative affect during momentary solitude. Furthermore, momentary solitude was associated with increased cortisol and DHEAs. With greater age, the association between momentary solitude and cortisol weakened. Consistent with the negative connotations to loneliness and objective social isolation, greater overall solitude was associated with negative affective and biological correlates. Spending a large overall amount of time alone in old age might thus have negative ramifications for health and well-being. Momentary solitude, in contrast, can be a double-edged sword as

  12. NMR study of magnetism and superparamagnetism

    Science.gov (United States)

    Yuan, Shaojie

    The research described in this dissertation is concerned with two different types of magnetic materials. Both types of systems involve competing interactions between transition metal ions. New approaches involving magnetic resonance in the large hyperfine fields at nuclear sites have been developed. The interactions responsible for the properties that have been investigated in the materials studied are geometric frustration in an insulator and ferromagnetic and antiferromagnetic interactions in a metal alloy. Further details are given below. The extended kagome frustrated system YBaCo4O7 has 2D kagome and triangular lattices of Co ions stacked along the c-axis. Antiferromagnetic (AF) ordering accompanied by a structural transition has been reported in the literature. From a zero field (ZF) NMR single crystal rotation experiment, we have obtained the Co spin configurations for both the kagome and triangular layers. A 'spin-flop' configuration between the spins on the kagome layer and the spins on the triangular layer is indicated by our results. Our NMR findings are compared with neutron scattering results for this intriguing frustrated AF spin system. The non-stoichiometric oxygenated sister compound YBaCo4O7.1 has application potential for oxygen storage. While, its' magnetic properties are quite different from those of the stoichiometric compound, in spite of their similar structures of alternating kagome and triangular Co layers. Various techniques, including ZF NMR have been used to investigate the spin dynamics and spin configuration in a single crystal of YBaCo4O7.1. A magnetic transition at 80 K is observed, which is interpreted as the freezing out of spins in the triangular layers. At low temperatures (below 50 K), the spin dynamics persists and a fraction of spins in the kagome layers form a viscous spin liquid. Below 10 K, a glass-like spin structure forms and a large distribution of spin correlation times are suggested by nuclear spin lattice relaxation

  13. Complete NMR analysis of oxytocin in phosphate buffer.

    Science.gov (United States)

    Ohno, Akiko; Kawasaki, Nana; Fukuhara, Kiyoshi; Okuda, Haruhiro; Yamaguchi, Teruhide

    2010-02-01

    Complete NMR analysis of oxytocin (OXT) in phosphate buffer was elucidated by one-dimensional (1D)- and two-dimensional (2D)-NMR techniques, which involve the assignment of peptide amide NH protons and carbamoyl NH(2) protons. The (1)H-(15)N correlation of seven amide NH protons and three carbamoyl NH(2) protons were also shown by HSQC NMR of OXT without (15)N enrichment.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. On the structure of the Nx phase of symmetric dimers: inferences from NMR.

    Science.gov (United States)

    Hoffmann, Anke; Vanakaras, Alexandros G; Kohlmeier, Alexandra; Mehl, Georg H; Photinos, Demetri J

    2015-02-07

    NMR measurements on a selectively deuterated liquid crystal dimer CB-C9-CB, exhibiting two nematic phases, show that the molecules in the lower temperature nematic phase, N(X), experience a chiral environment and are ordered about a uniformly oriented director throughout the macroscopic sample. The results are contrasted with previous interpretations that suggested a twist-bend spatial variation of the director. A structural picture is proposed wherein the molecules are packed into highly correlated chiral assemblies.

  1. Introduction to NMR Quantum Information Processing

    CERN Document Server

    Laflamme, R; Cory, D G; Fortunato, E M; Havel, T F; Miquel, C; Martínez, R; Negrevergne, C; Ortiz, G; Pravia, M A; Sharf, Y; Sinha, S; Somma, R D; Viola, L

    2002-01-01

    After a general introduction to nuclear magnetic resonance (NMR), we give the basics of implementing quantum algorithms. We describe how qubits are realized and controlled with RF pulses, their internal interactions, and gradient fields. A peculiarity of NMR is that the internal interactions (given by the internal Hamiltonian) are always on. We discuss how they can be effectively turned off with the help of a standard NMR method called ``refocusing''. Liquid state NMR experiments are done at room temperature, leading to an extremely mixed (that is, nearly random) initial state. Despite this high degree of randomness, it is possible to investigate QIP because the relaxation time (the time scale over which useful signal from a computation is lost) is sufficiently long. We explain how this feature leads to the crucial ability of simulating a pure (non-random) state by using ``pseudopure'' states. We discuss how the ``answer'' provided by a computation is obtained by measurement and how this measurement differs f...

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

    Science.gov (United States)

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

    2007-06-01

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

  3. Global Indicators Analysis and Consultancy Experience Insights into Correlation between Entrepreneurial Activities and Business Environment

    Directory of Open Access Journals (Sweden)

    Jovan Krivokapić

    2015-02-01

    Full Text Available Many researches and practical experiences clearly indicate the existence of a strong relationship between entrepreneurial activities and the business environment in which these activities are initiated. Although this topic has been quite ignored until the late twentieth century, a lot of studies and consulting practice have contributed to the fact that there are now a number of theories concerning mentioned correlation. These theories aim to offer a model that would provide better utilization of the possibilities from the business environment which could be very important for the development from both macroeconomic and microeconomic aspects. An increasing number of articles on this topic says enough about its importance, and numerous researches by many reputable globally recognized institutions go in favor of this claim. There are many indicators that observe the economic situation in a country or a region from different aspects, so the analyses of these indicators make it possible to determine the specific relationships between entrepreneurial activities and the local and the global business environment. Given the complexity of these relations, the impact cannot be observed partially, without taking into consideration other important factors, but more detailed analyses, however, result in some useful conclusions, which in the proper context can have a positive impact on many economic factors. It is very important to emphasize the fact that the correlation between the business environment and entrepreneurial activities is bidirectional, since this influence is mutual, so that changes in one of these factors can and usually cause some modifications in the other. Frequent series of such iterations actually lead to changes in the business environment, while entrepreneurial activity changes its shape and affects the economy of a country or a region, which is of particular importance for its competitiveness in the era of globalization.

  4. Spin Choreography: Basic Steps in High Resolution NMR (by Ray Freeman)

    Science.gov (United States)

    Minch, Michael J.

    1998-02-01

    There are three orientations that NMR courses may take. The traditional molecular structure course focuses on the interpretation of spectra and the use of chemical shifts, coupling constants, and nuclear Overhauser effects (NOE) to sort out subtle details of structure and stereochemistry. Courses can also focus on the fundamental quantum mechanics of observable NMR parameters and processes such a spin-spin splitting and relaxation. More recently there are courses devoted to the manipulation of nuclear spins and the basic steps of one- and two-dimensional NMR experiments. Freeman's book is directed towards the latter audience. Modern NMR methods offer a myriad ways to extract information about molecular structure and motion by observing the behavior of nuclear spins under a variety of conditions. In Freeman's words: "We can lead the spins through an intricate dance, carefully programmed in advance, to enhance, simplify, correlate, decouple, edit or assign NMR spectra." This is a carefully written, well-illustrated account of how this dance is choreographed by pulse programming, double resonance, and gradient effects. Although well written, this book is not an easy read; every word counts. It is recommended for graduate courses that emphasize the fundamentals of magnetic resonance. It is not a text on interpretation of spectra.

  5. Milli-tesla NMR and spectrophotometry of liquids hyperpolarized by dissolution dynamic nuclear polarization

    Science.gov (United States)

    Zhu, Yue; Chen, Chia-Hsiu; Wilson, Zechariah; Savukov, Igor; Hilty, Christian

    2016-09-01

    Hyperpolarization methods offer a unique means of improving low signal strength obtained in low-field NMR. Here, simultaneous measurements of NMR at a field of 0.7 mT and laser optical absorption from samples hyperpolarized by dissolution dynamic nuclear polarization (D-DNP) are reported. The NMR measurement field closely corresponds to a typical field encountered during sample injection in a D-DNP experiment. The optical spectroscopy allows determination of the concentration of the free radical required for DNP. Correlation of radical concentration to NMR measurement of spin polarization and spin-lattice relaxation time allows determination of relaxivity and can be used for optimization of the D-DNP process. Further, the observation of the nuclear Overhauser effect originating from hyperpolarized spins is demonstrated. Signals from 1H and 19F in a mixture of trifluoroethanol and water are detected in a single spectrum, while different atoms of the same type are distinguished by J-coupling patterns. The resulting signal changes of individual peaks are indicative of molecular contact, suggesting a new application area of hyperpolarized low-field NMR for the determination of intermolecular interactions.

  6. Parsimony and goodness-of-fit in multi-dimensional NMR inversion

    Science.gov (United States)

    Babak, Petro; Kryuchkov, Sergey; Kantzas, Apostolos

    2017-01-01

    Multi-dimensional nuclear magnetic resonance (NMR) experiments are often used for study of molecular structure and dynamics of matter in core analysis and reservoir evaluation. Industrial applications of multi-dimensional NMR involve a high-dimensional measurement dataset with complicated correlation structure and require rapid and stable inversion algorithms from the time domain to the relaxation rate and/or diffusion domains. In practice, applying existing inverse algorithms with a large number of parameter values leads to an infinite number of solutions with a reasonable fit to the NMR data. The interpretation of such variability of multiple solutions and selection of the most appropriate solution could be a very complex problem. In most cases the characteristics of materials have sparse signatures, and investigators would like to distinguish the most significant relaxation and diffusion values of the materials. To produce an easy to interpret and unique NMR distribution with the finite number of the principal parameter values, we introduce a new method for NMR inversion. The method is constructed based on the trade-off between the conventional goodness-of-fit approach to multivariate data and the principle of parsimony guaranteeing inversion with the least number of parameter values. We suggest performing the inversion of NMR data using the forward stepwise regression selection algorithm. To account for the trade-off between goodness-of-fit and parsimony, the objective function is selected based on Akaike Information Criterion (AIC). The performance of the developed multi-dimensional NMR inversion method and its comparison with conventional methods are illustrated using real data for samples with bitumen, water and clay.

  7. Development of an X-ray delay unit for correlation spectroscopy and pump-probe experiments

    Energy Technology Data Exchange (ETDEWEB)

    Roseker, Wojciech

    2008-07-15

    Probing condensed matter on time scales ranging from femtoseconds to nanoseconds will be one of the key topics for future X-ray Free Electron Laser (XFEL) sources. The accessible time windows are, however, compromised by the intrinsic time structure of the sources. One way to overcome this limitation is the usage of a time delay unit. A prototype device capable of splitting an X-ray pulse into two adjustable fractions, delaying one of them with the aim to perform X-ray Photon Correlation Spectroscopy and pump-probe type studies was designed and manufactured. The device utilizes eight perfect crystals in vertical 90 scattering geometry. Its performance has been verified with 8.39 keV and 12.4 keV Xrays at various synchrotron sources. The measured throughput of the device with a Si(333) monochromator at 8.39 keV under ambient conditions is 0.6%. The stability was verified at 12.4 keV and operation without realignment and feedback was possible for more than 30 minutes. Time delays up to 2.95 ns have been achieved. The highest resolution achieved in an experiment was 15.4 ps, a value entirely determined by the diagnostics system. The influence of the delay unit optics on the coherence properties of the beam was investigated by means of Fraunhofer diffraction and static speckle analysis. The obtained high fringe visibility and contrast values larger than 23% indicate the feasibility of performing coherence based experiments with the delay line. (orig.)

  8. What can Lattice QCD theorists learn from NMR spectroscopists?

    CERN Document Server

    Fleming, George T

    2004-01-01

    Euclidean-time hadron correlation functions computed in Lattice QCD (LQCD) are modeled by a sum of decaying exponentials, reminiscent of the exponentially damped sinusoid models of free induction decay (FID) in Nuclear Magnetic Resonance (NMR) spectroscopy. We present our initial progress in studying how data modeling techniques commonly used in NMR perform when applied to LQCD data.

  9. What can Lattice QCD theorists learn from NMR spectroscopists?

    Energy Technology Data Exchange (ETDEWEB)

    George Fleming

    2003-06-01

    Euclidean-time hadron correlation functions computed in Lattice QCD (LQCD) are modeled by a sum of decaying exponentials, reminiscent of the exponentially damped sinusoid models of free induction decay (FID) in Nuclear Magnetic Resonance (NMR) spectroscopy. We present our initial progress in studying how data modeling techniques commonly used in NMR perform when applied to LQCD data.

  10. Racemization Energy of 3,2'-Tetramethylene-2-phenyl-6-(pyrid-2''-yl)pyridine Estimated by Temperature Variation {sup 1}H NMR Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Motiur Rahman, A. F. M. [King Saud Univ., Riyadh (Saudi Arabia); Cha, Hyochang; Kwak, Kyungsook; Lee, Eungseok; Jahng, Yurngdong [Yeungnam Univ., Gyeongsan (Korea, Republic of)

    2013-02-15

    In conclusion, the racemization energy for the two conformational enantiomers of 3,2'-tetramethylene-2-phenyl-6-(pyrid-2''-yl)pyridine was estimated by temperature variation {sup 1}H NMR method to give 23 kcal/mole. Studies on the conformation of annulated bi-aryls have long been pursued extensively due to interest in the chirality and spectroscopic properties of conformationally restricted bi-aryls and their possible use in the determination of the absolute configuration of atropisomeric biaryls. One of the most extensively studied systems is 2,2'-polymethylenebi-phenyls (1), of which the chirality depends on the biphenyl unit as the stereogenic element.

  11. Entanglement witness derived from NMR superdense coding

    Energy Technology Data Exchange (ETDEWEB)

    Rahimi, Robabeh [Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan); Takeda, Kazuyuki [Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan); Ozawa, Masanao [Graduate School of Information Sciences, Tohoku University, Aoba-ku, Sendai 980-8579 (Japan); Kitagawa, Masahiro [Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)

    2006-03-03

    It is shown that superdense coding (SDC) experiments by means of nuclear magnetic resonance (NMR) can show non-classical efficiency gain over classical communication only for nuclear spin polarization beyond a certain threshold, and this threshold coincides with that for non-separability of the density matrix. It is also claimed that transfer of two-bit information mediated by a single qubit in the previous NMR SDC experiments with low nuclear spin polarization is not ascribed to the non-classical effect induced by entanglement, but merely to a statistical effect in an ensemble system having a large number of molecules. Towards experimental detection of entanglement, a new class of entanglement witnesses is proposed, which is based on the measurement of nuclear spin magnetizations in the Bell basis and is suitable for actual NMR experiments.

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

    Science.gov (United States)

    Mills, Nancy S.

    1998-06-01

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

  13. Structural and spectroscopic (UV-Vis, IR, Raman, and NMR) characteristics of anisaldehydes that are flavoring food additives: A density functional study in comparison with experiments

    Science.gov (United States)

    Altun, Ahmet; Swesi, O. A. A.; Alhatab, B. S. S.

    2017-01-01

    The molecular structures, vibrational spectra (IR and Raman), electronic spectra (UV-Vis and DOS), and NMR spectra (13C and 1H) of p-anisaldehyde, m-anisaldehyde, and o-anisaldehyde have been studied by using the B3LYP density functional and the 6-311++G** basis set. While p-anisaldehyde has been found to contain two stable conformers at room temperature, m-anisaldehyde and o-anisaldehyde contain four stable conformers. In agreement with the calculated ground-state energetics and small transition barriers, the comparison of the experimental and calculated spectra of the anisaldehydes indicates equilibrium between all conformers at room temperature. However, the two conformers of o-anisaldehyde, in which the methoxy group lies out of the ring plane, are too rare at the equilibrium. The equilibrium conditions of the conformers of the anisaldehyde isomers have been shown readily accessible through UV-Vis and 13C NMR spectral studies but requiring very detailed vibrational analyses. The effect of the solvent has been found to red-shift the electronic absorption bands and to make the anisaldehydes more reactive and soft. Molecular electrostatic potential maps of the anisaldehydes show that their oxygen atoms are the sites for nucleophilic reactivity. Compared with the most sophisticated NBO method, ESP charges have been found mostly reliable while Mulliken charges fail badly with the present large 6-311++G** basis set. The present calculations reproduce not only the experimental spectral characteristics of the anisaldehydes but also reveal their several structural features.

  14. MCNPX Monte Carlo burnup simulations of the isotope correlation experiments in the NPP Obrigheim

    Energy Technology Data Exchange (ETDEWEB)

    Cao Yan, E-mail: ycao@anl.go [Nuclear Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Gohar, Yousry [Nuclear Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Broeders, Cornelis H.M. [Forschungszentrum Karlsruhe, Institute for Neutron Physics and Reactor Technology, P.O. Box 3640, 76021 Karlsruhe (Germany)

    2010-10-15

    This paper describes the simulation work of the Isotope Correlation Experiment (ICE) using the MCNPX Monte Carlo computer code package. The Monte Carlo simulation results are compared with the ICE-Experimental measurements for burnup up to 30 GWD/t. The comparison shows the good capabilities of the MCNPX computer code package for predicting the depletion of the uranium fuel and the buildup of the plutonium isotopes in a PWR thermal reactor. The Monte Carlo simulation results show also good agreements with the experimental data for calculating several long-lived and stable fission products. However, for the americium and curium actinides, it is difficult to judge the predication capabilities for these actinides due to the large uncertainties in the ICE-Experimental data. In the MCNPX numerical simulations, a pin cell model is utilized to simulate the fuel lattice of the nuclear power reactor. Temperature dependent libraries based on JEFF3.1 nuclear data files are utilized for the calculations. In addition, temperature dependent libraries based ENDF/B-VII nuclear data files are utilized and the obtained results are very close to the JEFF3.1 results, except for {approx}10% differences in the prediction of the minor actinide isotopes buildup.

  15. A position-sensitive twin ionization chamber for fission fragment and prompt neutron correlation experiments

    Energy Technology Data Exchange (ETDEWEB)

    Göök, A.; Geerts, W.; Hambsch, F.-J.; Oberstedt, S.; Vidali, M. [European Commission, Joint Research Centre, Institute for Reference Materials and Measurements, Retieseweg 111, B-2440 Geel (Belgium); Zeynalov, Sh. [Joint Institute for Nuclear Research, Joliot-Curie 6, 141980 Dubna, Mosow region (Russian Federation)

    2016-09-11

    A twin position-sensitive Frisch grid ionization chamber, intended as a fission fragment detector in experiments to study prompt fission neutron correlations with fission fragment properties, is presented. Fission fragment mass and energies are determined by means of the double kinetic energy technique, based on conservation of mass and linear momentum. The position sensitivity is achieved by replacing each anode plate in the standard twin ionization chamber by a wire plane and a strip anode, both readout by means of resistive charge division. This provides information about the fission axis orientation, which is necessary to reconstruct the neutron emission process in the fully accelerated fragment rest-frame. The energy resolution compared to the standard twin ionization chamber is found not to be affected by the modification. The angular resolution of the detector relative to an arbitrarily oriented axis is better than 7° FWHM. Results on prompt fission neutron angular distributions in {sup 235}U(n,f) obtained with the detector in combination with an array of neutron scintillation detectors is presented as a proof of principle.

  16. A position-sensitive twin ionization chamber for fission fragment and prompt neutron correlation experiments

    Science.gov (United States)

    Göök, A.; Geerts, W.; Hambsch, F.-J.; Oberstedt, S.; Vidali, M.; Zeynalov, Sh.

    2016-09-01

    A twin position-sensitive Frisch grid ionization chamber, intended as a fission fragment detector in experiments to study prompt fission neutron correlations with fission fragment properties, is presented. Fission fragment mass and energies are determined by means of the double kinetic energy technique, based on conservation of mass and linear momentum. The position sensitivity is achieved by replacing each anode plate in the standard twin ionization chamber by a wire plane and a strip anode, both readout by means of resistive charge division. This provides information about the fission axis orientation, which is necessary to reconstruct the neutron emission process in the fully accelerated fragment rest-frame. The energy resolution compared to the standard twin ionization chamber is found not to be affected by the modification. The angular resolution of the detector relative to an arbitrarily oriented axis is better than 7° FWHM. Results on prompt fission neutron angular distributions in 235U(n,f) obtained with the detector in combination with an array of neutron scintillation detectors is presented as a proof of principle.

  17. p-adic probability prediction of correlations between particles in the two-slit and neutron interferometry experiments

    CERN Document Server

    Khrennikov, Andrei

    2009-01-01

    We start from Feynman`s idea to use negative probabilities to describe the two slit experiment and other quantum interfernce experiments. Formally by using negative probability distributions we can explain the results of the two slit experiment on the basis of the pure corpuscular picture of quantum mechnanics. However, negative probabilities are absurd objects in the framework of the standard Kolmogorov theory of probability. We present a large class of non-Kolmogorovean probability models where negative probabilities are well defined on the frequency basis. These are models with probabilities which belong to the so-called field of $p$-adic numbers. However, these models are characterized by correlations between trails. Therefore, we predict correlations between particles in interference experiments. In fact, our predictions are similar to the predictions of the so-called nonergodic interpretation of quantum mechanics, which was proposed by V. Buonomano. We propose the concrete experiments (in particular, in...

  18. NMR crystallography of enzyme active sites: probing chemically detailed, three-dimensional structure in tryptophan synthase.

    Science.gov (United States)

    Mueller, Leonard J; Dunn, Michael F

    2013-09-17

    NMR crystallography--the synergistic combination of X-ray diffraction, solid-state NMR spectroscopy, and computational chemistry--offers unprecedented insight into three-dimensional, chemically detailed structure. Initially, researchers used NMR crystallography to refine diffraction data from organic and inorganic solids. Now we are applying this technique to explore active sites in biomolecules, where it reveals chemically rich detail concerning the interactions between enzyme site residues and the reacting substrate. Researchers cannot achieve this level of detail from X-ray, NMR,or computational methodologies in isolation. For example, typical X-ray crystal structures (1.5-2.5 Å resolution) of enzyme-bound intermediates identify possible hydrogen-bonding interactions between site residues and substrate but do not directly identify the protonation states. Solid-state NMR can provide chemical shifts for selected atoms of enzyme-substrate complexes, but without a larger structural framework in which to interpret them only empirical correlations with local chemical structure are possible. Ab initio calculations and molecular mechanics can build models for enzymatic processes, but they rely on researcher-specified chemical details. Together, however, X-ray diffraction, solid-state NMR spectroscopy, and computational chemistry can provide consistent and testable models for structure and function of enzyme active sites: X-ray crystallography provides a coarse framework upon which scientists can develop models of the active site using computational chemistry; they can then distinguish these models by comparing calculated NMR chemical shifts with the results of solid-state NMR spectroscopy experiments. Conceptually, each technique is a puzzle piece offering a generous view of the big picture. Only when correctly pieced together, however, can they reveal the big picture at the highest possible resolution. In this Account, we detail our first steps in the development of

  19. Symptoms of acute myocardial infarction: A correlational study of the discrepancy between patients' expectations and experiences.

    Science.gov (United States)

    Abed, Mona A; Ali, Raeda M Abu; Abu Ras, Motaz M; Hamdallah, Faten O; Khalil, Amani A; Moser, Debra K

    2015-10-01

    Patients' responses to acute myocardial infarction symptoms are affected by symptom incongruence, which is the difference between the symptoms they expect to experience and the symptoms they actually experienced during an acute myocardial infarction. To examine the relationship of patients' demographics, clinical characteristics and sources of information about acute myocardial infarction with their symptom expectations, actual experiences and symptom incongruence. Descriptive correlational study. Patients were recruited from ten hospitals in the two most populated cities in Jordan (Amman and Al Zarqa). Jordanian patients with acute myocardial infarction were recruited. Inclusion criteria were age 18 years or older, diagnosis of acute myocardial infarction, oriented, mentally competent and fluent in Arabic. Exclusion criteria were experiencing acute myocardial infarction during a hospitalization or having severe psychiatric illnesses. The Morgan Incongruence of Heart Attack Symptoms Index was used to quantify symptom incongruence and identify patients' expected and experienced acute myocardial infarction symptoms. Patients' information sources about acute myocardial infarction and demographic and clinical characteristics were collected by interview and medical chart review. Patients (N=299) were mostly males (80%) and married (92%). The average age was 56±12.3 years. Patients expected a limited number of acute myocardial infarction symptoms and these expectations were largely confined to typical symptoms and matched their experiences. Patients who were female, elderly, nonsmokers, poorly educated, with low income, and those who were normolipidemic, had no personal or family cardiac history, and were informed about acute myocardial infarction by relatives expected fewer symptoms (mostly typical and atypical) than their counterparts. Elderly patients and those with hyperlipidemia experienced fewer typical symptoms than their counterparts. Patients with ST

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

    Science.gov (United States)

    2017-01-01

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

  1. Group Chemical Changes and Physical Property Correlations in Refining of Lube Base Stocks. Ir and Nmr Spectroscopy Corrélations entre les propriétés physiques et les changements de composition chimique au cours du raffinage des huiles de base. Spectrométrie infra rouge et résonance magnétique nucléaire

    OpenAIRE

    Singh H.; Gulati I. B.

    2006-01-01

    Changes occurring in the chemical composition of lubricating oil base stocks with different degreeand typeof refining have been investigated by IR and NMR spectroscopy. Significant conclusions about the chemical composition have been reached through the study of structural parameters. Correlations between molecular parameters such as aromaticity , average number of carbon atoms per alkyl substituentand the Viscosity Indexof base oils are reported. The term degree of refininghas been assigned ...

  2. 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...

  3. 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.

  4. 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

  5. Spin-density correlations in the dynamic spin-fluctuation theory: Comparison with polarized neutron scattering experiments

    Energy Technology Data Exchange (ETDEWEB)

    Melnikov, N.B., E-mail: melnikov@cs.msu.su [Lomonosov Moscow State University, Moscow 119991 (Russian Federation); Reser, B.I., E-mail: reser@imp.uran.ru [Miheev Institute of Metal Physics, Ural Branch of Russian Academy of Sciences, Ekaterinburg 620990 (Russian Federation); Paradezhenko, G.V., E-mail: gparadezhenko@cs.msu.su [Lomonosov Moscow State University, Moscow 119991 (Russian Federation)

    2016-08-01

    To study the spin-density correlations in the ferromagnetic metals above the Curie temperature, we relate the spin correlator and neutron scattering cross-section. In the dynamic spin-fluctuation theory, we obtain explicit expressions for the effective and local magnetic moments and spatial spin-density correlator. Our theoretical results are demonstrated by the example of bcc Fe. The effective and local moments are found in good agreement with results of polarized neutron scattering experiment over a wide temperature range. The calculated short-range order is small (up to 4 Å) and slowly decreases with temperature.

  6. Adiabatic Low-Pass J Filters for Artifact Suppression in Heteronuclear NMR

    DEFF Research Database (Denmark)

    Meier, Sebastian; Benie, Andrew J; Duus, Jens Øllgaard

    2009-01-01

    NMR artifact purging: Modern NMR experiments depend on efficient coherence transfer pathways for their sensitivity and on suppression of undesired pathways leading to artifacts for their spectral clarity. A novel robust adiabatic element suppresses hard-to-get-at artifacts.......NMR artifact purging: Modern NMR experiments depend on efficient coherence transfer pathways for their sensitivity and on suppression of undesired pathways leading to artifacts for their spectral clarity. A novel robust adiabatic element suppresses hard-to-get-at artifacts....

  7. Electrophysiological correlates of associative learning in smokers: a higher-order conditioning experiment

    Directory of Open Access Journals (Sweden)

    Littel Marianne

    2012-01-01

    Full Text Available Abstract Background Classical conditioning has been suggested to play an important role in the development, maintenance, and relapse of tobacco smoking. Several studies have shown that initially neutral stimuli that are directly paired with smoking are able to elicit conditioned responses. However, there have been few human studies that demonstrate the contribution of higher-order conditioning to smoking addiction, although it is assumed that higher-order conditioning predominates learning in the outside world. In the present study a higher-order conditioning task was designed in which brain responses of smokers and non-smokers were conditioned by pairing smoking-related and neutral stimuli (CS1smoke and CS1neutral with two geometrical figures (CS2smoke and CS2neutral. ERPs were recorded to all CSs. Results Data showed that the geometrical figure that was paired with smoking stimuli elicited significantly larger P2 and P3 waves than the geometrical figure that was paired with neutral stimuli. During the first half of the experiment this effect was only present in smokers whereas non-smokers displayed no significant differences between both stimuli, indicating that neutral cues paired with motivationally relevant smoking-related stimuli gain more motivational significance even though they were never paired directly with smoking. These conclusions are underscored by self-reported evidence of enhanced second-order conditioning in smokers. Conclusions It can be concluded that smokers show associative learning for higher-order smoking-related stimuli. The present study directly shows the contribution of higher-order conditioning to smoking addiction and is the first to reveal its electrophysiological correlates. Although results are preliminary, they may help in understanding the etiology of smoking addiction and its persistence.

  8. Event-related potential correlates of paranormal ideation and unusual experiences.

    Science.gov (United States)

    Sumich, Alex; Kumari, Veena; Gordon, Evian; Tunstall, Nigel; Brammer, Michael

    2008-01-01

    Separate dimensions of schizotypy have been differentially associated with electrophysiological measures of brain function, and further shown to be modified by sex/gender. We investigated event-related potential (ERP) correlates of two subdimensions of positive schizotypy, paranormal ideation (PI) and unusual experiences (UEs). Seventy-two individuals with no psychiatric diagnosis (men=36) completed self-report measures of UE and PI and performed an auditory oddball task. Average scores for N100, N200 and P300 amplitudes were calculated for left and right anterior, central and posterior electrode sites. Multiple linear regression was used to examine the relationships between the measures of schizotypy and ERPs across the entire sample, as well as separately according to sex. PI was inversely associated with P300 amplitude at left-central sites across the entire sample, and at right-anterior electrodes in women only. Right-anterior P300 and right-posterior N100 amplitudes were negatively associated with UE in women only. Across the entire sample, UE was negatively associated with left-central N100 amplitude, and positively associated with left-anterior N200 amplitude. These results provide support from electrophysiological measures for the fractionation of the positive dimension of schizotypy into subdimensions of PI and UE, and lend indirect support to dimensional or quasidimensional conceptions of psychosis. More specifically, they suggest that PI may be associated with alteration in contextual updating processes, and that UE may reflect altered sensory/early-attention (N100) mechanisms. The sex differences observed are consistent with those previously observed in individuals with schizophrenia.

  9. Regulatory Experience with In Vivo In Vitro Correlations (IVIVC) in New Drug Applications.

    Science.gov (United States)

    Suarez-Sharp, Sandra; Li, Min; Duan, John; Shah, Heta; Seo, Paul

    2016-11-01

    In the past two decades, in vitro in vivo correlation (IVIVC) has been considered an important tool for supporting biowaivers, setting dissolution acceptance criteria, and more recently in the Quality by Design (QbD) framework promoting the establishment of clinically meaningful drug product specifications using dissolution as the endpoint. Based on our review experience at the FDA, for the purposes of this article, we analyzed the current state of regulatory submissions containing IVIVC approaches and discussed the successes and failures from the perspectives of study design to methodology. In the past decade, the overall acceptance rate of the IVIVC submissions is about 40%. Moreover, the number of IVIVC studies seen in the submissions per year is not increasing. Establishing clinically meaningful drug product specifications through the linkages between the identified critical quality attributes and in vivo performance is key for developing a quality drug product. To achieve this goal, there is an imminent need for addressing the issues behind a low success rate in IVIVC development. The results from the current analysis revealed that special considerations should be taken in areas such as (1) selection of appropriate number/kind of formulations for IVIVC development/validation, (2) construction of exploratory plots to guide model building and selection, (3) investigation of the reasons of inconclusive predictability, (4) improvement on the quality and richness of the data, and (5) avoidance of over parameterization. The development and incorporation of biopredictive dissolution methods and the use of non-conventional approaches, including mechanistic/physiologically based approaches, should be explored to increase the likelihood of IVIVC success.

  10. Molecular characterization and quantification using state of the art solid-state adiabatic TOBSY NMR in burn trauma.

    Science.gov (United States)

    Righi, Valeria; Andronesi, Ovidiu; Mintzopoulos, Dionyssios; Tzika, A Aria

    2009-12-01

    We describe a novel solid-state nuclear magnetic resonance (NMR) method that maximizes the advantages of high-resolution magic-angle-spinning (HRMAS), relative conventional liquid-state NMR approaches, when applied to intact biopsies of skeletal muscle specimens collected from burn trauma patients. This novel method, termed optimized adiabatic TOtal through Bond correlation SpectroscopY (TOBSY) solid-state NMR pulse sequence for two-dimensional (2D) 1H-1H homonuclear scalar-coupling longitudinal isotropic mixing, was demonstrated to provide a 40-60% improvement in signal-to-noise ratio (SNR) relative to its liquid-state analogue TOCSY (TOtal Correlation SpectroscopY). Using 1- and 2-dimensional HRMAS NMR experiments, we identified several metabolites in burned tissues. Quantification of metabolites in burned tissues showed increased levels of lipid compounds, intracellular metabolites (e.g., taurine and phosphocreatine) and substantially decreased water-soluble metabolites (e.g., glutathione, carnosine, glucose, glutamine/glutamate and alanine). These findings demonstrate that HRMAS NMR Spectroscopy using TOBSY is a feasible technique that reveals new insights into the pathophysiology of burn trauma. Moreover, this method has applications that facilitate the development of novel therapeutic strategies.

  11. Practical aspects of NMR signal assignment in larger and challenging proteins

    Science.gov (United States)

    Frueh, Dominique P.

    2014-01-01

    NMR has matured into a technique routinely employed for studying proteins in near physiological conditions. However, applications to larger proteins are impeded by the complexity of the various correlation maps necessary to assign NMR signals. This article reviews the data analysis techniques traditionally employed for resonance assignment and describes alternative protocols necessary for overcoming challenges in large protein spectra. In particular, simultaneous analysis of multiple spectra may help overcome ambiguities or may reveal correlations in an indirect manner. Similarly, visualization of orthogonal planes in a multidimensional spectrum can provide alternative assignment procedures. We describe examples of such strategies for assignment of backbone, methyl, and nOe resonances. We describe experimental aspects of data acquisition for the related experiments and provide guidelines for preliminary studies. Focus is placed on large folded monomeric proteins and examples are provided for 37, 48, 53, and 81 kDa proteins. PMID:24534088

  12. A Study of Quantum Error Correction by Geometric Algebra and Liquid-State NMR Spectroscopy

    CERN Document Server

    Sharf, Y; Somaroo, S S; Havel, T F; Knill, E H; Laflamme, R; Sharf, Yehuda; Cory, David G.; Somaroo, Shyamal S.; Havel, Timothy F.; Knill, Emanuel; Laflamme, Raymond

    2000-01-01

    Quantum error correcting codes enable the information contained in a quantum state to be protected from decoherence due to external perturbations. Applied to NMR, quantum coding does not alter normal relaxation, but rather converts the state of a ``data'' spin into multiple quantum coherences involving additional ancilla spins. These multiple quantum coherences relax at differing rates, thus permitting the original state of the data to be approximately reconstructed by mixing them together in an appropriate fashion. This paper describes the operation of a simple, three-bit quantum code in the product operator formalism, and uses geometric algebra methods to obtain the error-corrected decay curve in the presence of arbitrary correlations in the external random fields. These predictions are confirmed in both the totally correlated and uncorrelated cases by liquid-state NMR experiments on 13C-labeled alanine, using gradient-diffusion methods to implement these idealized decoherence models. Quantum error correcti...

  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. Automated analysis of protein NMR assignments using methods from artificial intelligence.

    Science.gov (United States)

    Zimmerman, D E; Kulikowski, C A; Huang, Y; Feng, W; Tashiro, M; Shimotakahara, S; Chien, C; Powers, R; Montelione, G T

    1997-06-20

    An expert system for determining resonance assignments from NMR spectra of proteins is described. Given the amino acid sequence, a two-dimensional 15N-1H heteronuclear correlation spectrum and seven to eight three-dimensional triple-resonance NMR spectra for seven proteins, AUTOASSIGN obtained an average of 98% of sequence-specific spin-system assignments with an error rate of less than 0.5%. Execution times on a Sparc 10 workstation varied from 16 seconds for smaller proteins with simple spectra to one to nine minutes for medium size proteins exhibiting numerous extra spin systems attributed to conformational isomerization. AUTOASSIGN combines symbolic constraint satisfaction methods with a domain-specific knowledge base to exploit the logical structure of the sequential assignment problem, the specific features of the various NMR experiments, and the expected chemical shift frequencies of different amino acids. The current implementation specializes in the analysis of data derived from the most sensitive of the currently available triple-resonance experiments. Potential extensions of the system for analysis of additional types of protein NMR data are also discussed.

  15. 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

  16. Petrophysical properties of greensand as predicted from NMR measurements

    DEFF Research Database (Denmark)

    Hossain, Zakir; Grattoni, Carlos A.; Solymar, Mikael

    2011-01-01

    ABSTRACT: Nuclear magnetic resonance (NMR) is a useful tool in reservoir evaluation. The objective of this study is to predict petrophysical properties from NMR T2 distributions. A series of laboratory experiments including core analysis, capillary pressure measurements, NMR T2 measurements...... and image analysis were carried out on sixteen greensand samples from two formations in the Nini field of the North Sea. Hermod Formation is weakly cemented, whereas Ty Formation is characterized by microcrystalline quartz cement. The surface area measured by the BET method and the NMR derived surface...... with macro-pores. Permeability may be predicted from NMR by using Kozeny's equation when surface relaxivity is known. Capillary pressure drainage curves may be predicted from NMR T2 distribution when pore size distribution within a sample is homogeneous....

  17. NMR Based Quantum Information Processing Achievements and Prospects

    CERN Document Server

    Cory, D G; Knill, E H; Viola, L; Havel, T F; Boulant, N; Boutis, G; Fortunato, E M; Lloyd, S; Martínez, R; Negrevergne, C; Pravia, M A; Sharf, Y; Teklemariam, G; Weinstein, Yu S; Zurek, W H

    2000-01-01

    Nuclear magnetic resonance (NMR) provides an experimental setting to explore physical implementations of quantum information processing (QIP). Here we introduce the basic background for understanding applications of NMR to QIP and explain their current successes, limitations and potential. NMR spectroscopy is well known for its wealth of diverse coherent manipulations of spin dynamics. Ideas and instrumentation from liquid state NMR spectroscopy have been used to experiment with QIP. This approach has carried the field to a complexity of about 10 qubits, a small number for quantum computation but large enough for observing and better understanding the complexity of the quantum world. While liquid state NMR is the only present-day technology about to reach this number of qubits, further increases in complexity will require new methods. We sketch one direction leading towards a scalable quantum computer using spin 1/2 particles. The next step of which is a solid state NMR-based QIP capable of reaching 10-30 qub...

  18. Bringing NMR and IR Spectroscopy to High Schools

    Science.gov (United States)

    Bonjour, Jessica L.; Hass, Alisa L.; Pollock, David W.; Huebner, Aaron; Frost, John A.

    2017-01-01

    Development of benchtop, portable Fourier transform nuclear magnetic resonance (NMR) and infrared (IR) spectrometers has opened up opportunities for creating university-high school partnerships that provide high school students with hands-on experience with NMR and IR instruments. With recent changes to the international baccalaureate chemistry…

  19. Bringing NMR and IR Spectroscopy to High Schools

    Science.gov (United States)

    Bonjour, Jessica L.; Hass, Alisa L.; Pollock, David W.; Huebner, Aaron; Frost, John A.

    2017-01-01

    Development of benchtop, portable Fourier transform nuclear magnetic resonance (NMR) and infrared (IR) spectrometers has opened up opportunities for creating university-high school partnerships that provide high school students with hands-on experience with NMR and IR instruments. With recent changes to the international baccalaureate chemistry…

  20. Realization of quantum discrete Fourier transform with NMR

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The pulse sequences of the logic operations used in quantum discrete Fourier transform are designed for the experiment of nuclear magnetic resonance(NMR), and 2-qubit discrete Fourier transforms are implemented experimentally with NMR. The experimental errors are examined and methods for reducing the errors are proposed.

  1. Peer Evaluation in a Clinical Clerkship: Students' Attitudes, Experiences, and Correlations with Traditional Assessments

    Science.gov (United States)

    Levine, Ruth E.; Kelly, P. Adam; Karakoc, Tayfun; Haidet, Paul

    2007-01-01

    Objective: The authors performed this study to determine whether clerkship peer evaluations, initiated as part of our "team-based learning" curriculum in 2002, correlated with other student performance measures, and to determine what qualities students rate in their peer evaluations. Method: The authors correlated peer evaluation scores with other…

  2. A possible correlation between EGRET Sources and an Air-Borne experiment

    OpenAIRE

    Enomoto, Ryoji

    1995-01-01

    In 1989, an air-borne experiments (VEGA experiment) aiming at the detection of a few 10 GeV $\\gamma$-ray were carried out. In these experiments, nine point-source candidates along the Galactic plane were reported. In these candidates, the five of five highest significance candidates positionally coincide with the EGRET galactic plane sources.

  3. Cross-Modal Interactions in the Experience of Musical Performances: Physiological Correlates

    Science.gov (United States)

    Chapados, Catherine; Levitin, Daniel J.

    2008-01-01

    This experiment was conducted to investigate cross-modal interactions in the emotional experience of music listeners. Previous research showed that visual information present in a musical performance is rich in expressive content, and moderates the subjective emotional experience of a participant listening and/or observing musical stimuli [Vines,…

  4. Cross-Modal Interactions in the Experience of Musical Performances: Physiological Correlates

    Science.gov (United States)

    Chapados, Catherine; Levitin, Daniel J.

    2008-01-01

    This experiment was conducted to investigate cross-modal interactions in the emotional experience of music listeners. Previous research showed that visual information present in a musical performance is rich in expressive content, and moderates the subjective emotional experience of a participant listening and/or observing musical stimuli [Vines,…

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

    Science.gov (United States)

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

    2009-03-02

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

  6. Resonance assignment for a particularly challenging protein based on systematic unlabeling of amino acids to complement incomplete NMR data sets

    Energy Technology Data Exchange (ETDEWEB)

    Bellstedt, Peter, E-mail: pbell@fli-leibniz.de; Seiboth, Thomas; Haefner, Sabine; Kutscha, Henriette; Ramachandran, Ramadurai; Goerlach, Matthias [Leibniz Institute for Age Research, Fritz Lipmann Institute, Biomolecular NMR Spectroscopy (Germany)

    2013-09-15

    NMR-based structure determination of a protein requires the assignment of resonances as indispensable first step. Even though heteronuclear through-bond correlation methods are available for that purpose, challenging situations arise in cases where the protein in question only yields samples of limited concentration and/or stability. Here we present a strategy based upon specific individual unlabeling of all 20 standard amino acids to complement standard NMR experiments and to achieve unambiguous backbone assignments for the fast precipitating 23 kDa catalytic domain of human aprataxin of which only incomplete standard NMR data sets could be obtained. Together with the validation of this approach utilizing the protein GB1 as a model, a comprehensive insight into metabolic interconversion ('scrambling') of NH and CO groups in a standard Escherichia coli expression host is provided.

  7. Employing NMR Spectroscopy To Evaluate Transmission of Electronic Effects in 4-Substituted Chalcones

    Science.gov (United States)

    Wachter-Jurcsak, Nanette; Zamani, Hossein

    1999-05-01

    Described is an organic synthesis experiment that demonstrates the electronic transmission by substituents. The effect of substitution at the para-position of the styryl ring of 1,3-diphenyl-2-propenones (chalcones) by typical electron-donating or -accepting groups can be observed by proton and carbon-13 NMR spectroscopy. A linear correlation is observed when the differences in chemical shift measurements for H are plotted against the corresponding Hammett substituent constant values. Good correlation between carbon-13 chemical shifts of the alpha carbon are also observed. The syntheses of the 4-substituted chalcones is presented as well as a brief discussion of the theory.

  8. Three-Pion HBT Correlations in Relativistic Heavy-Ion Collisions from the STAR Experiment

    CERN Document Server

    Adams, J; Ahammed, Z; Allgower, C; Amonett, J; Anderson, B D; Anderson, M; Arkhipkin, D; Averichev, G S; Balewski, J T; Barannikova, O Yu; Barnby, L S; Baudot, J; Bekele, S; Belaga, V V; Bellwied, R; Berger, J; Bichsel, H; Billmeier, A; Bland, L C; Blyth, C O; Bonner, B E; Botje, M; Boucham, A; Brandin, A; Bravar, A; Cadman, R V; Cai, X Z; Caines, H; Calderón de la Barca-Sanchez, M; Cardenas, A; Carroll, J; Castillo, J; Castro, M; Cebra, D; Chaloupka, P; Chattopadhyay, S; Chen, Y; Chernenko, S P; Cherney, M; Chikanian, A; Choi, B; Christie, W; Coffin, J P; Cormier, T M; Mora-Corral, M J; Cramer, J G; Crawford, H J; Derevshchikov, A A; Didenko, L; Dietel, T; Draper, J E; Dunin, V B; Dunlop, J C; Eckardt, V; Efimov, L G; Emelianov, V; Engelage, J; Eppley, G; Erazmus, B; Fachini, P; Faine, V; Faivre, J; Fatemi, R; Filimonov, K; Finch, E; Fisyak, Yu; Flierl, D; Foley, K J; Fu, J; Gagliardi, C A; Gagunashvili, N D; Gans, J; Gaudichet, L; Germain, M; Geurts, F J M; Ghazikhanian, V; Grachov, O A; Guedon, M; Guertin, S M; Gushin, E; Gutíerrez, T D; Hallman, T J; Hardtke, D; Harris, J W; Heinz, M; Henry, T W; Heppelmann, S; Herston, T; Hippolyte, B; Hirsch, A; Hjort, E; Hoffmann, G W; Horsley, M; Huang, H Z; Humanic, T J; Igo, G; Ishihara, A; Jacobs, P; Jacobs, W W; Janik, M; Johnson, I; Jones, P G; Judd, E G; Kabana, S; Kaneta, M; Kaplan, M; Keane, D; Kiryluk, J; Kisiel, A; Klay, J; Klein, S R; Klyachko, A; Kollegger, T; Konstantinov, A S; Kopytine, M; Kotchenda, L; Kovalenko, A D; Krämer, M; Kravtsov, P; Krüger, K; Kuhn, C; Kulikov, A I; Kunde, G J; Kunz, C L; Kutuev, R K; Kuznetsov, A A; Lamont, M A C; Landgraf, J M; Lange, S; Lansdell, C P; Lasiuk, B; Laue, F; Lauret, J; Lebedev, A; Lednicky, R; Leontiev, V M; Le Vine, M J; Li, Q; Lindenbaum, S J; Lisa, M A; Liu, F; Liu, L; Liu, Z; Liu, Q J; Ljubicic, T; Llope, W J; Long, H; Longacre, R S; López-Noriega, M; Love, W A; Ludlam, Thomas W; Lynn, D; Ma, J; Ma, Y G; Magestro, D; Majka, R; Margetis, S; Markert, C; Martin, L; Marx, J; Matis, H S; Matulenko, Yu A; McShane, T S; Meissner, F; Melnik, Yu M; Meshchanin, A P; Messer, M; Miller, M L; Milosevich, Z; Minaev, N G; Mitchell, J; Molnár, L; Moore, C F; Morozov, V; De Moura, M M; Munhoz, M G; Nelson, J M; Nevski, P; Nikitin, V A; Nogach, L V; Norman, B; Nurushev, S B; Odyniec, Grazyna Janina; Ogawa, A; Okorokov, V; Oldenburg, M; Olson, D; Paic, G; Pandey, S U; Panebratsev, Yu A; Panitkin, S Y; Pavlinov, A I; Pawlak, T; Perevozchikov, V; Peryt, W; Petrov, V; Picha, R; Planinic, M; Pluta, J; Porile, N; Porter, J; Poskanzer, A M; Potrebenikova, E V; Prindle, D J; Pruneau, C A; Putschke, J; Rai, G; Rakness, G; Ravel, O; Ray, R L; Razin, S V; Reichhold, D M; Reid, J G; Renault, G; Retière, F; Ridiger, A; Ritter, H G; Roberts, J B; Rogachevski, O V; Romero, J L; Rose, A; Roy, C; Rykov, V L; Sakrejda, I; Salur, S; Sandweiss, J; Savin, I; Schambach, J; Scharenberg, R P; Schmitz, N; Schröder, L S; Schweda, K; Seger, J; Seyboth, P; Shahaliev, E; Shestermanov, K E; Shimansky, S S; Simon, F; Skoro, G P; Smirnov, N; Snellings, R; Sørensen, P; Sowinski, J; Spinka, H M; Srivastava, B; Stephenson, E J; Stock, Reinhard; Stolpovsky, A; Strikhanov, M N; Stringfellow, B C; Struck, C; Suaide, A A P; Sugarbaker, E R; Suire, C; Sumbera, M; Surrow, B; Symons, T J M; Szanto de Toledo, A; Szarwas, P; Tai, A; Takahashi, J; Tang, A H; Thein, D; Thomas, J H; Thompson, M; Timoshenko, S; Tokarev, M; Tonjes, M B; Trainor, T A; Trentalange, S; Tribble, R E; Trofimov, V; Tsai, O; Ullrich, T S; Underwood, D G; Van Buren, G; Van der Molen, A M; Vasilev, A N; Vigdor, S E; Voloshin, S A; Vznuzdaev, M; Wang, F; Wang, Y; Ward, H; Watson, J W; Wells, R; Westfall, G D; Whitten, C; Wieman, H; Willson, R; Wissink, S W; Witt, R; Wood, J; Xu, N; Xu, Z; Yakutin, A E; Yamamoto, E; Yang, J; Yepes, P; Yurevich, V I; Zanevsky, Yu V; Zborovský, I; Zhang, H; Zhang, W M; Zoulkarneev, R; Zoulkarneeva, Y; Zubarev, A N

    2003-01-01

    Data from the first physics run at the Relativistic Heavy-Ion Collider at Brookhaven National Laboratory, Au+Au collisions at $sqrt{s_{NN}}=130$ GeV, have been analyzed by the STAR Collaboration using three-pion correlations with charged pions to study whether pions are emitted independently at freezeout. We have made a high-statistics measurement of the three-pion correlation function and calculated the normalized three-particle correlator to obtain a quantitative measurement of the degree of chaoticity of the pion source. It is found that the degree of chaoticity seems to increase with increasing particle multiplicity.

  9. NMR analog of the quantum disentanglement eraser.

    Science.gov (United States)

    Teklemariam, G; Fortunato, E M; Pravia, M A; Havel, T F; Cory, D G

    2001-06-25

    We report the implementation of a three-spin quantum disentanglement eraser on a liquid-state NMR quantum information processor. A key feature of this experiment was its use of pulsed magnetic field gradients to mimic projective measurements. This ability is an important step towards the development of an experimentally controllable system which can simulate any quantum dynamics, both coherent and decoherent.

  10. Ca. Nitrososphaera and Bradyrhizobium are inversely correlated and related to agricultural practices in long-term field experiments

    Directory of Open Access Journals (Sweden)

    Kateryna eZhalnina

    2013-05-01

    Full Text Available Agricultural land management, such as fertilization, liming, and tillage affects soil properties, including pH, organic matter content, nitrification rates, and the microbial community. Three different study sites were used to identify microorganisms that correlate with agricultural land use and to determine which factors regulate the relative abundance of the microbial signatures of the agricultural land-use. The three sites included in this study are the Broadbalk Experiment at Rothamsted Research, UK, the Everglades Agricultural Area, Florida, USA and the Kellogg Biological Station, Michigan, USA. The effects of agricultural management on the abundance and diversity of bacteria and archaea were determined using high throughput, barcoded 16S rRNA sequencing. In addition, the relative abundance of these organisms was correlated with soil features. Two groups of microorganisms involved in nitrogen cycle were highly correlated with land use at all three sites. The ammonia oxidizing-archaea, dominated by Ca. Nitrososphaera, were positively correlated with agriculture while a ubiquitous group of soil bacteria closely related to the diazotrophic symbiont, Bradyrhizobium, was negatively correlated with agricultural management. Analysis of successional plots showed that the abundance of ammonia oxidizing-archaea declined and the abundance of bradyrhizobia increased with time away from agriculture. This observation suggests that the effect of agriculture on the relative abundance of these genera is reversible. Soil pH and NH3 concentrations were positively correlated with archaeal abundance but negatively correlated with the abundance of Bradyrhizobium. The high correlations of Ca. Nitrososphaera and Bradyrhizobium abundances with agricultural management at three long-term experiments with different edaphoclimatic conditions allowed us to suggest these two genera as signature microorganisms for agricultural land use.

  11. Modeling of critical experiments and its impact on integral covariance matrices and correlation coefficients

    CERN Document Server

    Peters, Elisabeth; Stuke, Maik

    2016-01-01

    In this manuscript we study the modeling of experimental data and its impact on the resulting integral experimental covariance and correlation matrices. By investigating a set of three low enriched and water moderated UO2 fuel rod arrays we found that modeling the same set of data with different, yet reasonable assumptions concerning the fuel rod composition and its geometric properties leads to significantly different covariance matrices or correlation coefficients. Following a Monte Carlo sampling approach, we show for nine different modeling assumptions the corresponding correlation coefficients and sensitivity profiles for each pair of the effective neutron multiplication factor keff. Within the 95% confidence interval the correlation coefficients vary from 0 to 1, depending on the modeling assumptions. Our findings show that the choice of modeling can have a huge impact on integral experimental covariance matrices. When the latter are used in a validation procedure to derive a bias, this procedure can be...

  12. What Is The Sensation Seeker? Personality Trait And Experience Correlates Of The Sensation-Seeking Scales

    Science.gov (United States)

    Zuckerman, Marvin; And Others

    1972-01-01

    The correlations of the Sensation Seeking Scale with Personality scales indicate that the general sensation seeking trait is related to an uninhibited, nonconforming, inpulsive, dominant type of extraversion, but not particularly related to the socialization type of extraversion. (Author)

  13. Experience drives the development of movement-cognition correlations in a butterfly

    Directory of Open Access Journals (Sweden)

    Emilie eSnell-Rood

    2015-03-01

    Full Text Available Correlations between behavioral traits are widespread, but the developmental genetic architecture of such correlations is poorly characterized. Understanding the developmental mechanisms that lead to correlations between behaviors has implications for predicting how changing environments might alter the strength, direction and persistence of these associations. Here we test the idea that genetic variation in one behavioral trait can drive the development of traits related to a second behavior, resulting in correlations between them.. We focus on correlations between movement and aspects of cognition, in particular accuracy of decision making and neural investment. Such syndromes have been seen across a variety of systems, from insects to birds, but the direction of the correlation often varies. We use cabbage white butterflies as a system because they are easy to rear in large numbers and show ample genetic variation in both movement and learning, facilitating a split-sibling design. We test the prediction that variation in established proxies for movement at emergence will be correlated with the development of cognitive traits later in life (in siblings. Our results suggest that genotypes (full-sibling groups that emerge with more elongate wings explore their environment more rapidly. In addition, genotypes that emerge with relatively smaller thoraxes are more likely to learn to search for atypical host plants and subsequently develop larger brains and brain regions. Taken together, genotypes that invest less in flight are slower, better learners and develop larger brains. These data are consistent with the idea that movement can drive the development of other behavioral traits, resulting in the emergence of correlated behaviors.

  14. Investigating albendazole desmotropes by solid-state NMR spectroscopy.

    Science.gov (United States)

    Chattah, Ana K; Zhang, Rongchun; Mroue, Kamal H; Pfund, Laura Y; Longhi, Marcela R; Ramamoorthy, Ayyalusamy; Garnero, Claudia

    2015-03-02

    Characterization of the molecular structure and physicochemical solid-state properties of the solid forms of pharmaceutical compounds is a key requirement for successful commercialization as potential active ingredients in drug products. These properties can ultimately have a critical effect on the solubility and bioavailability of the final drug product. Here, the desmotropy of Albendazole forms I and II was investigated at the atomic level. Ultrafast magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectroscopy, together with powder X-ray diffraction, thermal analysis, and Fourier transform infrared spectroscopy, were performed on polycrystalline samples of the two solids in order to fully characterize and distinguish the two forms. High-resolution one-dimensional (1)H, (13)C, and (15)N together with two-dimensional (1)H/(1)H single quantum-single quantum, (1)H/(1)H single quantum-double quantum, and (1)H/(13)C chemical shift correlation solid-state NMR experiments under MAS conditions were extensively used to decipher the intramolecular and intermolecular hydrogen bonding interactions present in both solid forms. These experiments enabled the unequivocal identification of the tautomers of each desmotrope. Our results also revealed that both solid forms may be described as dimeric structures, with different intermolecular hydrogen bonds connecting the tautomers in each dimer.

  15. NMR with Hyperpolarised Protons in Metals

    Energy Technology Data Exchange (ETDEWEB)

    Engelbertz, A., E-mail: engelbert@iskp.uni-bonn.de; Anbalagan, P.; Bommas, C.; Eversheim, P.-D.; Hartman, D. T.; Maier, K. [University of Bonn, Helmholtz- Institut fuer Strahlen und Kernphysik (Germany)

    2004-12-15

    Proton pulse NMR, established as a versatile method in Solid State Physics, Chemistry, Biology and Medical Science, requires on the order of 10{sup 18} nuclei to detect an electromagnetic signal in a free induction decay (FID). The main cause for this small sensitivity is the low polarisation in the order of a few ppm due to the Boltzmann distribution in the magnetic field. Thus, NMR experiments on hydrogen are limited to metals with extremely high hydrogen solubility like Pd near room temperature. Using a polarised proton beam, a NMR signal is possible with as few as 10{sup 13} implanted nuclei. For the first time spin-spin and spin-lattice relaxation times were measured in Au and W with this technique at the Bonn cyclotron.

  16. 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.

  17. Magic angle spinning NMR of paramagnetic proteins.

    Science.gov (United States)

    Knight, Michael J; Felli, Isabella C; Pierattelli, Roberta; Emsley, Lyndon; Pintacuda, Guido

    2013-09-17

    Metal ions are ubiquitous in biochemical and cellular processes. Since many metal ions are paramagnetic due to the presence of unpaired electrons, paramagnetic molecules are an important class of targets for research in structural biology and related fields. Today, NMR spectroscopy plays a central role in the investigation of the structure and chemical properties of paramagnetic metalloproteins, linking the observed paramagnetic phenomena directly to electronic and molecular structure. A major step forward in the study of proteins by solid-state NMR came with the advent of ultrafast magic angle spinning (MAS) and the ability to use (1)H detection. Combined, these techniques have allowed investigators to observe nuclei that previously were invisible in highly paramagnetic metalloproteins. In addition, these techniques have enabled quantitative site-specific measurement of a variety of long-range paramagnetic effects. Instead of limiting solid-state NMR studies of biological systems, paramagnetism provides an information-rich phenomenon that can be exploited in these studies. This Account emphasizes state-of-the-art methods and applications of solid-state NMR in paramagnetic systems in biological chemistry. In particular, we discuss the use of ultrafast MAS and (1)H-detection in perdeuterated paramagnetic metalloproteins. Current methodology allows us to determine the structure and dynamics of metalloenzymes, and, as an example, we describe solid-state NMR studies of microcrystalline superoxide dismutase, a 32 kDa dimer. Data were acquired with remarkably short times, and these experiments required only a few milligrams of sample.

  18. Experience of application of clamp-on cross-correlation flow meter in nuclear industry

    Energy Technology Data Exchange (ETDEWEB)

    Gurevich, Y. [Daystar Technology Inc., Ontario (Canada); Ton, V.; Kotenyov, S.; Zhao, C. [Ontario Power Generation, Ontario (Canada); Sharp, B.; Lopez, A. [Advanced Measurements and Analysis Group Inc., Ontario (Canada)

    2010-07-01

    The cross-correlation clamp-on flow meter, CROSSFLOW, developed and manufactured by AMAG, has been used over the world for over 15 years for flow measurements in various systems in nuclear and fossil power plants. Prior that, OPG has used similar technology in Canadian nuclear power plants since 1980-ies. Two recent examples of the application of the clamp-on cross-correlation technology are presented in this paper. In first example OPG meter was used to verify accuracy of ASME nozzles installed in condensate flow lines. In second example AMAG meter was used to measure Diesel Cooling Water (DCW). (author)

  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. Insight into Hydrogen Bonding of Uranyl Hydroxide Layers and Capsules by Use of 1H Magic-Angle Spinning NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Alam, Todd M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Organic Material Science; Liao, Zuolei [Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry and Materials; Nyman, May [Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry and Materials; Yates, Jonathan [Univ. of Oxford (United Kingdom). Dept. of Materials

    2016-04-27

    In this paper, solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO2(OH)2] (α-UOH) and hydrated uranyl hydroxide [(UO2)4O(OH)6·5H2O (metaschoepite). For the metaschoepite material, proton resonances of the μ2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H–1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Finally, these NMR correlations allowed characterization of local hydrogen-bond environments in uranyl U24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.

  3. Ground-Laboratory to In-Space Atomic Oxygen Correlation for the Polymer Erosion and Contamination Experiment (PEACE) Polymers

    Science.gov (United States)

    Stambler, Arielle H.; Inoshita, Karen E.; Roberts, Lily M.; Barbagallo, Claire E.; deGroh, Kim K.; Banks, Bruce A.

    2011-01-01

    The Materials International Space Station Experiment 2 (MISSE 2) Polymer Erosion and Contamination Experiment (PEACE) polymers were exposed to the environment of low Earth orbit (LEO) for 3.95 years from 2001 to 2005. There were 41 different PEACE polymers, which were flown on the exterior of the International Space Station (ISS) in order to determine their atomic oxygen erosion yields. In LEO, atomic oxygen is an environmental durability threat, particularly for long duration mission exposures. Although spaceflight experiments, such as the MISSE 2 PEACE experiment, are ideal for determining LEO environmental durability of spacecraft materials, ground-laboratory testing is often relied upon for durability evaluation and prediction. Unfortunately, significant differences exist between LEO atomic oxygen exposure and atomic oxygen exposure in ground-laboratory facilities. These differences include variations in species, energies, thermal exposures and radiation exposures, all of which may result in different reactions and erosion rates. In an effort to improve the accuracy of ground-based durability testing, ground-laboratory to in-space atomic oxygen correlation experiments have been conducted. In these tests, the atomic oxygen erosion yields of the PEACE polymers were determined relative to Kapton H using a radio-frequency (RF) plasma asher (operated on air). The asher erosion yields were compared to the MISSE 2 PEACE erosion yields to determine the correlation between erosion rates in the two environments. This paper provides a summary of the MISSE 2 PEACE experiment; it reviews the specific polymers tested as well as the techniques used to determine erosion yield in the asher, and it provides a correlation between the space and ground laboratory erosion yield values. Using the PEACE polymers asher to in-space erosion yield ratios will allow more accurate in-space materials performance predictions to be made based on plasma asher durability evaluation.

  4. Incorporation of FT-NMR into Research Infrastructure and Chemistry Curriculum at Bowie State University

    Science.gov (United States)

    2014-01-09

    data. The library of easily used 1D and 2D experiments includes, COSY, DEPT, HETCOR, T1, T2, and kinetics. ii. NUTS (Acorn NMR Inc.) - A NMR data...HBCU) - Incorporation of FT- NMR into Research Infrastructure and Chemistry Curriculum at Bowie State University ALAN ANDERSON BOWIE STATE...Award# FA9550-12-1-0448 (HBCU) Incorporation of FT- NMR into Research Infrastructure and Chemistry Curriculum at

  5. Correlating Neutrino Flux and Staff Presence in the Super-Kamiokande-I Experiment

    CERN Document Server

    Bergman, L E

    2005-01-01

    A search for a non-random co-variation between the Neutrino Flux and Staff Presence was undertaken, using the 5-day period version of the SK-I data taken from May 31st, 1996 to July 15th, 2001. For weekdays for the whole 1996-2001 period, a significant correlation between the Neutrino Flux and Staff Presence was found for each of the two midnight hours, i.e. across all weekdays for each of the two hours between 23:00-1:00. A significant correlation was also found across all weekdays and all hours for the whole year of 1998. It is not clear why this particular year should have been different from the other calendar years of 1996-2001. More specifically, significant correlations were also found for each of its hours around noon, i.e. across all weekdays for each of the hours between 10:00-16:00, for the year of 1998. An attempt was made to interpret why significant correlations were found only for midnight hours and hours around noon, but not for any other hours: when the sun-earth axis and the staff-detector a...

  6. Children's experience of posttraumatic growth : Distinguishing general from domain-specific correlates

    NARCIS (Netherlands)

    Laceulle, O.M.; Kleber, R.J.; Alisic, E.

    2015-01-01

    Although the five domains of posttraumatic growth (new possibilities, relating to others, personal strength, spiritual change and appreciation of life) have been studied extensively in adults, little is known about these domains and their correlates in children. We aimed to examine whether demograph

  7. Children's Experience of Posttraumatic Growth : Distinguishing General from Domain-Specific Correlates

    NARCIS (Netherlands)

    Laceulle, Odilia M; Kleber, Rolf J; Alisic, Eva

    2015-01-01

    Although the five domains of posttraumatic growth (new possibilities, relating to others, personal strength, spiritual change and appreciation of life) have been studied extensively in adults, little is known about these domains and their correlates in children. We aimed to examine whether demograph

  8. Modern solid-state NMR on functional polymers; Moderne Festkoerper-NMR an Funktionspolymeren

    Energy Technology Data Exchange (ETDEWEB)

    Wang, M.

    2004-07-01

    In this thesis the microscopic structures of natural caoutchouc, on silicic acid plugged polydimethylsiloxane (PDMS), and polyamide-clay-nanocomposite are studied. For natural caoutchouc it is shown how the network density can be characterized by the study of the dipole-dipole couplings between protons and carbon by means of the heteronuclear double-quantum NMR method and further double-resonance experiments. In PDMS homo- and heteronuclear multi-quantum NMR, spin-diffusion, relaxometry, and double-resonance experiments are used for the study of the dependence of the molecular motion on external influences. Finally the structural change of polyamides by addition of clay particles is studied.

  9. Non-destructive characterization of materials by single-sided NMR

    Energy Technology Data Exchange (ETDEWEB)

    Goga, Nicolae-Octavian

    2007-08-20

    The experiments conducted in this work demonstrate the efficiency and sensitivity of single-sided NMR for investigating macromolecular materials on large time and length scales. Elastomers can readily be characterized by unilateral NMR of protons in terms of a variety of parameters, which correlate with the overall molecular mobility. In this way information about the cross-link density, state of cure and strain, the effects of aging and product heterogeneity can obtained. For these purposes, the NMR-MOUSE was used to optimize product development and to monitor product and production quality on-line. The sensor is also suitable for nondestructive probing of the mechanical deformation in cross-linked elastomers. A special magnet design that fits a stress-strain device has been used for complementary investigation of a series of different rubber stripes during mechanical testing. The profile NMR-MOUSE was found to be a unique tool for the characterization of changes induced by the UV irradiation in natural rubber. The aging profiles were interpreted for the first time based on a novel model in which the radiation absorption coefficient depends on the depth in the sample. (orig.)

  10. 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.

  11. Correlates and consequences of parent-teen incongruence in reports of teens' sexual experience.

    Science.gov (United States)

    Mollborn, Stefanie; Everett, Bethany

    2010-07-01

    Using the National Longitudinal Study of Adolescent Health, factors associated with incongruence between parents' and adolescents' reports of teens' sexual experience were investigated, and the consequences of inaccurate parental knowledge for adolescents' subsequent sexual behaviors were explored. Most parents of virgins accurately reported teens' lack of experience, but most parents of teens who had had sex provided inaccurate reports. Binary logistic regression analyses showed that many adolescent-, parent-, and family-level factors predicted the accuracy of parents' reports. Parents' accurate knowledge of their teens' sexual experience was not found to be consistently beneficial for teens' subsequent sexual outcomes. Rather, parents' expectations about teens' sexual experience created a self-fulfilling prophecy, with teens' subsequent sexual outcomes conforming to parents' expectations. These findings suggest that research on parent-teen communication about sex needs to consider the expectations being expressed, as well as the information being exchanged.

  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. Irrelevance of Bell's Theorem for experiments involving correlations in space and time: a specific loophole-free computer-example

    CERN Document Server

    De Raedt, Hans; Hess, Karl

    2016-01-01

    John Bell is generally credited to have accomplished the remarkable "proof" that any theory of physics, which is both Einstein-local and "realistic" (counterfactually definite), results in a strong upper bound to the correlations that are measured in space and time. He thus predicts that Einstein-Podolsky-Rosen experiments cannot violate Bell- type inequalities. We present a counterexample to this claim, based on discrete-event computer simulations. Our model-results fully agree with the predictions of quantum theory for Einstein-Podolsky-Rosen-Bohm experiments and are free of the detection- or a coincidence-loophole.

  14. Determination of the Rotational Barrier for Kinetically Stable Conformational Isomers via NMR and 2D TLC: An Introductory Organic Chemistry Experiment

    Science.gov (United States)

    Rushton, Gregory T.; Burns, William G.; Lavin, Judi M.; Chong, Yong S.; Pellechia, Perry; Shimizu, Ken D.

    2007-01-01

    An experiment to determine the rotational barrier about a C[subscript aryl]-N[subscript imide] single bond that is suitable for first-semester organic chemistry students is presented. The investigation begins with the one-step synthesis of a N,N'-diaryl naphthalene diimide, which exists as two room temperature-stable atropisomers (syn and anti).…

  15. Determination of Unknown Concentrations of Sodium Acetate Using the Method of Standard Addition and Proton NMR: An Experiment for the Undergraduate Analytical Chemistry Laboratory

    Science.gov (United States)

    Rajabzadeh, Massy

    2012-01-01

    In this experiment, students learn how to find the unknown concentration of sodium acetate using both the graphical treatment of standard addition and the standard addition equation. In the graphical treatment of standard addition, the peak area of the methyl peak in each of the sodium acetate standard solutions is found by integration using…

  16. Determination of Unknown Concentrations of Sodium Acetate Using the Method of Standard Addition and Proton NMR: An Experiment for the Undergraduate Analytical Chemistry Laboratory

    Science.gov (United States)

    Rajabzadeh, Massy

    2012-01-01

    In this experiment, students learn how to find the unknown concentration of sodium acetate using both the graphical treatment of standard addition and the standard addition equation. In the graphical treatment of standard addition, the peak area of the methyl peak in each of the sodium acetate standard solutions is found by integration using…

  17. Observation of 1H-13C and 1H-1H proximities in a paramagnetic solid by NMR at high magnetic field under ultra-fast MAS

    Science.gov (United States)

    Li, Shenhui; Trébosc, Julien; Lafon, Olivier; Zhou, Lei; Shen, Ming; Pourpoint, Frédérique; Amoureux, Jean-Paul; Deng, Feng

    2015-02-01

    The assignment of NMR signals in paramagnetic solids is often challenging since: (i) the large paramagnetic shifts often mask the diamagnetic shifts specific to the local chemical environment, and (ii) the hyperfine interactions with unpaired electrons broaden the NMR spectra and decrease the coherence lifetime, thus reducing the efficiency of usual homo- and hetero-nuclear NMR correlation experiments. Here we show that the assignment of 1H and 13C signals in isotopically unmodified paramagnetic compounds with moderate hyperfine interactions can be facilitated by the use of two two-dimensional (2D) experiments: (i) 1H-13C correlations with 1H detection and (ii) 1H-1H double-quantum ↔ single-quantum correlations. These methods are experimentally demonstrated on isotopically unmodified copper (II) complex of L-alanine at high magnetic field (18.8 T) and ultra-fast Magic Angle Spinning (MAS) frequency of 62.5 kHz. Compared to 13C detection, we show that 1H detection leads to a 3-fold enhancement in sensitivity for 1H-13C 2D correlation experiments. By combining 1H-13C and 1H-1H 2D correlation experiments with the analysis of 13C longitudinal relaxation times, we have been able to assign the 1H and 13C signals of each L-alanine ligand.

  18. 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.

  19. 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.

  20. Metabolic pathway visualization in living yeast by DNP-NMR.

    Science.gov (United States)

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

    2011-10-01

    Central carbon metabolism of living Saccharomyces cerevisiae is visualized by DNP-NMR. Experiments are conducted as real time assays that detect metabolic bottlenecks, pathway use, reversibility of reactions and reaction mechanisms in vivo with subsecond time resolution.

  1. Angular Correlations Between Fragment Spin and Prompt Neutron Evaporation in Spontaneous Fission of 252Cf: CORA-Demon Experiment

    Science.gov (United States)

    Prokhorova, E.; Gönnenwein, F.; Kopatch, Yu.; Mutterer, M.; Hanappe, F.; Kinnard, V.; Stuttgé, L.; Dorvaux, O.; Wollersheim, H.-J.

    2007-05-01

    A novel method to search for the anisotropic emission of prompt neutrons in the center-of-mass system of fission fragments is presented. The anisotropy is conjectured to be due to the large spins of fission fragments are known to carry. Triple neutron- neutron-fragment correlations in spontaneous fission of 252Cf were investigated in an exploratory experiment dubbed CORA-DEMON experiment. Fission fragments were intercepted in a double ionization chamber while neutrons were spotted in 2 two-dimensional cylindrical walls of Demon detectors with the target on the vertical cylinder axis. A new method of analysis of triple angular correlations between 2 neutrons and a fission fragment was applied. Preliminary results are reported.

  2. BOOK REVIEW: NMR Imaging of Materials

    Science.gov (United States)

    Blümich, Bernhard

    2003-09-01

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

  3. OPENCORE NMR: open-source core modules for implementing an integrated FPGA-based NMR spectrometer.

    Science.gov (United States)

    Takeda, Kazuyuki

    2008-06-01

    A tool kit for implementing an integrated FPGA-based NMR spectrometer [K. Takeda, A highly integrated FPGA-based nuclear magnetic resonance spectrometer, Rev. Sci. Instrum. 78 (2007) 033103], referred to as the OPENCORE NMR spectrometer, is open to public. The system is composed of an FPGA chip and several peripheral boards for USB communication, direct-digital synthesis (DDS), RF transmission, signal acquisition, etc. Inside the FPGA chip have been implemented a number of digital modules including three pulse programmers, the digital part of DDS, a digital quadrature demodulator, dual digital low-pass filters, and a PC interface. These FPGA core modules are written in VHDL, and their source codes are available on our website. This work aims at providing sufficient information with which one can, given some facility in circuit board manufacturing, reproduce the OPENCORE NMR spectrometer presented here. Also, the users are encouraged to modify the design of spectrometer according to their own specific needs. A home-built NMR spectrometer can serve complementary roles to a sophisticated commercial spectrometer, should one comes across such new ideas that require heavy modification to hardware inside the spectrometer. This work can lower the barrier of building a handmade NMR spectrometer in the laboratory, and promote novel and exciting NMR experiments.

  4. Structural investigations on betacyanin pigments by LC NMR and 2D NMR spectroscopy.

    Science.gov (United States)

    Stintzing, Florian C; Conrad, Jürgen; Klaiber, Iris; Beifuss, Uwe; Carle, Reinhold

    2004-02-01

    Four betacyanin pigments were analysed by LC NMR and subjected to extensive NMR characterisation after isolation. Previously, low pH values were applied for NMR investigations of betalains resulting in rapid degradation of the purified substances thus preventing extensive NMR studies. Consequently, up to now only one single (13)C NMR spectrum of a betalain pigment, namely that of neobetanin (=14,15-dehydrobetanin), was available. Because of its sufficient stability under highly acidic conditions otherwise detrimental for betacyanins, this pigment remained an exemption. Since betalains are most stable in the pH range of 5-7, a new solvent system has been developed allowing improved data acquisition through improved pigment stability at near neutral pH. Thus, not only (1)H, but for the first time also partial (13)C data of betanin, isobetanin, phyllocactin and hylocerenin isolated from red-purple pitaya [Hylocereus polyrhizus (Weber) Britton & Rose, Cactaceae] could be indirectly obtained by gHSQC- and gHMQC-NMR experiments.

  5. Spectral evolution of gamma-ray bursts detected by the SIGNE experiment. 1: Correlation between intensity and spectral hardness

    Science.gov (United States)

    Kargatis, Vincent E.; Liang, Edison P.; Hurley, Kevin C.; Barat, C.; Eveno, E.; Niel, M.

    1994-01-01

    We study the continuum spectral evolution of 16 gamma-ray bursts detected by the Franco-Soviet SIGNE experiment in 1981-1982 by fitting time resolved (0.5 s) spectra in count space with simple thermal bremsstrahlung and synchrotron models. We find that there is no single characteristic of spectral evolution: we see hard-to-soft, soft-to-hard, luminosity-hardness tracking, and chaotic evolution. We perform correlation studies between instantaneous burst intensity and spectral temperature for seven bursts. While we basically confirm the existence of a correlation between these variables as originally claimed by Golenetskii et al. (1983) we find higher values and a broader range of correlation indices.

  6. PROTON - LAMBDA CORRELATIONS IN AU-AU COLLISIONS AT SQUARE ROOT NN = 200 GEV FROM THE STAR EXPERIMENT.

    Energy Technology Data Exchange (ETDEWEB)

    RENAULT,G.; (THE STAR COLLABORATION)

    2004-03-15

    The space-time evolution of the source of particles formed in the collision of nuclei can be studied through particle correlations. The STAR experiment is dedicated to study ultra-relativistic heavy ions collisions and allows to measure non-identical strange particle correlations. The source size can be extracted by studying p - {Lambda}, {bar p} - {bar {Lambda}}, {bar p} - {Lambda} and p - {bar {Lambda}} correlation functions. Strong interaction potential has been studied for these systems using an analytical model. Final State Interaction (FSI) parameters have been determined and has shown a significant annihilation process present in {bar p} - {Lambda} and p - {bar {Lambda}} systems not present in p - {Lambda} and {bar p} - {bar {Lambda}}.

  7. PROTON - LAMBDA CORRELATIONS IN AU-AU COLLISIONS AT SQUARE ROOT NN = 200 GEV FROM THE STAR EXPERIMENT.

    Energy Technology Data Exchange (ETDEWEB)

    RENAULT,G.; (THE STAR COLLABORATION)

    2004-03-15

    The space-time evolution of the source of particles formed in the collision of nuclei can be studied through particle correlations. The STAR experiment is dedicated to study ultra-relativistic heavy ions collisions and allows to measure non-identical strange particle correlations. The source size can be extracted by studying p - {Lambda}, {bar p} - {bar {Lambda}}, {bar p} - {Lambda} and p - {bar {Lambda}} correlation functions. Strong interaction potential has been studied for these systems using an analytical model. Final State Interaction (FSI) parameters have been determined and has shown a significant annihilation process present in {bar p} - {Lambda} and p - {bar {Lambda}} systems not present in p - {Lambda} and {bar p} - {bar {Lambda}}.

  8. Correlated fluorine diffusion and ionic conduction in the nanocrystalline F(-) solid electrolyte Ba(0.6)La(0.4)F(2.4)-(19)F T1(ρ) NMR relaxation vs. conductivity measurements.

    Science.gov (United States)

    Preishuber-Pflügl, F; Bottke, P; Pregartner, V; Bitschnau, B; Wilkening, M

    2014-05-28

    Chemical reactions induced by mechanical treatment may give access to new compounds whose properties are governed by chemical metastability, defects introduced and the size effects present. Their interplay may lead to nanocrystalline ceramics with enhanced transport properties being useful to act as solid electrolytes. Here, the introduction of large amounts of La into the cubic structure of BaF2 served as such an example. The ion transport properties in terms of dc-conductivity values of the F(-) anion conductor Ba1-xLaxF2+x (here with x = 0.4) considerably exceed those of pure, nanocrystalline BaF2. So far, there is only little knowledge about activation energies and jump rates of the elementary hopping processes. Here, we took advantage of both impedance spectroscopy and (19)F NMR relaxometry to get to the bottom of ion jump diffusion proceeding on short-range and long-range length scales in Ba0.6La0.4F2.4. While macroscopic transport is governed by an activation energy of 0.55 to 0.59 eV, the elementary steps of hopping seen by NMR are characterised by much smaller activation energies. Fortunately, we were able to deduce an F(-) self-diffusion coefficient by the application of spin-locking NMR relaxometry.

  9. The effect of ionic correlations on radiative properties in the solar interior and terrestrial experiments

    CERN Document Server

    Krief, Menahem; Feigel, Alexander; Gazit, Doron

    2016-01-01

    Intending to solve the decade old problem of solar opacity, we report substantial photoabsorption increase due to the effect of ion-ion correlation which was not heretofore considered. By performing detailed opacity calculations of the solar mixture, we find that taking into account the ionic structure results in a $ \\sim 10\\% $ increase in the Rosseland opacity near the convection zone, which mimics the missing opacity profile required by helioseismology and neutrino observations. These results point out the correlation effect as a major source for the missing opacity and call for a detailed characterization of its uncertainties. We also report a $ \\sim15\\% $ increase in the Rosseland opacity for iron monochromatic opacity which was recently measured at the Sandia Z facility, where the temperature reached that prevailing in the convection zone while the density is $ 2.5 $ times lower. Finally, we propose a method to measure opacities at solar temperatures and densities that were never reached in the past via...

  10. The phototoxicity of polycyclic aromatic hydrocarbons: a theoretical study of excited states and correlation to experiment.

    Science.gov (United States)

    Betowski, Leon D; Enlow, Mark; Riddick, Lee

    2002-06-01

    Investigators using models to determine the phototoxic effects of sunlight on polycyclic aromatic hydrocarbons (PAHs) have invoked the excited states of the molecule as important in elucidating the mechanism of these reactions. Energies of actual excited states were calculated for ten PAHs by several ab initio methods. The main method used for these calculations was the Configuration Interaction approach, modeling excited states as combinations of single substitutions out of the Hartree-Fock ground state. These calculations correlate well with both experimentally measured singlet and triplet state energies and also previous HOMO-LUMO gap energies that approximate the singlet state energies. The excited state calculations then correlate well with general models of photo-induced toxicity based for the PAHs.

  11. Correlation-induced network oscillations of pyramidal cells in the weakly electric fish - theory and experiment

    Science.gov (United States)

    Lindner, Benjamin; Doiron, Brent; Longtin, Andre; Maler, Leonard; Bastian, Joseph

    2004-03-01

    The spiking activity of pyramidal cells in the weakly electric fish is studied. It is experimentally shown that the oscillatory spiking activity of these cells increases with the spatial correlations of external stochastic input. A model network of integrate-and-fire (IF) neurons with delayed inhibitory feedback reproduces this effect. Moreover, a novel analytical approach for stochastic neuron models with weak feedback is presented that leads to a simple expression for the power spectrum of the spike train of a single neuron. The analytical results agree well with simulation results of the leaky IF neurons; they also show the same qualitative features as the experimental spectra and are helpful in understanding the deeper origin of the correlation-induced oscillations.

  12. Good Old Gamers, Good Drivers: Results from a correlational experiment among older drivers

    Directory of Open Access Journals (Sweden)

    Suchada Vichitvanichphong

    2016-03-01

    Full Text Available In many situations, driving is essential for senior citizens to maintain their independent lifestyle. A systematic literature review was conducted that summarized the age-related physical, visual and cognitive functional declines and their associated risk to driving. Based on these findings, we explored whether the skills required in playing Xbox Kinect video games were correlated with measures of driving performance among older drivers. Fifty-two participants, 65 years of age or older (Mean = 72; SD = 3.84; range 65 – 85 years; 29 males who have access to a car and drive frequently were invited to play Just dance, Table Tennis (ping pong, Bowling, and Dr Kawashima’s Brain Training Exercises on an Xbox Kinect 360. Participants also completed a 25-minute on-road driving task along a predetermined route to assess and identify critical driving errors using a similar instrument as that used by a driving license tester. Bivariate correlation examined the relationship between game scores and these objective driving skills. There was a significant correlation between the Xbox Kinect video games and on-road driving scores (r = 0.861, p <0.001, indicating that ‘good gamers are good drivers’. This was correlation was significant for the males (r = 0.864, p <0.001 as well as for the females (r = 0.878, p <0.001. We suggest that performance on Xbox games may be a suitable, cost-effective and less-risky indicator of on-road driving skills for older drivers, particularly in jurisdictions in which mandatory testing of older citizens has been introduced or is being considered as a requirement in the driver licensing process.

  13. Fluid-Rock Characterization and Interactions in NMR Well Logging

    Energy Technology Data Exchange (ETDEWEB)

    George J. Hirasaki; Kishore K. Mohanty

    2005-09-05

    The objective of this report is to characterize the fluid properties and fluid-rock interactions that are needed for formation evaluation by NMR well logging. The advances made in the understanding of NMR fluid properties are summarized in a chapter written for an AAPG book on NMR well logging. This includes live oils, viscous oils, natural gas mixtures, and the relation between relaxation time and diffusivity. Oil based drilling fluids can have an adverse effect on NMR well logging if it alters the wettability of the formation. The effect of various surfactants on wettability and surface relaxivity are evaluated for silica sand. The relation between the relaxation time and diffusivity distinguishes the response of brine, oil, and gas in a NMR well log. A new NMR pulse sequence in the presence of a field gradient and a new inversion technique enables the T{sub 2} and diffusivity distributions to be displayed as a two-dimensional map. The objectives of pore morphology and rock characterization are to identify vug connectivity by using X-ray CT scan, and to improve NMR permeability correlation. Improved estimation of permeability from NMR response is possible by using estimated tortuosity as a parameter to interpolate between two existing permeability models.

  14. Correlated two-particle diffusion in dense colloidal suspensions at early times: Theory and comparison to experiment.

    Science.gov (United States)

    Dell, Zachary E; Tsang, Boyce; Jiang, Lingxiang; Granick, Steve; Schweizer, Kenneth S

    2015-11-01

    The spatially resolved diffusive dynamic cross correlations of a pair of colloids in dense quasi-two-dimensional monolayers of identical particles are studied experimentally and theoretically at early times where motion is Fickian. In very dense systems where strong oscillatory equilibrium packing correlations are present, we find an exponential decay of the dynamic cross correlations on small and intermediate length scales. At large separations where structure becomes random, an apparent power law decay with an exponent of approximately -2.2 is observed. For a moderately dense suspension where local structural correlations are essentially absent, this same apparent power law decay is observed over all probed interparticle separations. A microscopic nonhydrodynamic theory is constructed for the dynamic cross correlations which is based on interparticle frictional effects and effective structural forces. Hydrodynamics enters only via setting the very short-time single-particle self-diffusion constant. No-adjustable-parameter quantitative predictions of the theory for the dynamic cross correlations are in good agreement with experiment over all length scales. The origin of the long-range apparent power law is the influence of the constraint of fixed interparticle separation on the amplitude of the mean square force exerted on the two tagged particles by the surrounding fluid. The theory is extended to study high-packing-fraction 3D hard sphere fluids. The same pattern of an oscillatory exponential form of the dynamic cross correlation function is predicted in the structural regime, but the long-range tail decays faster than in monolayers with an exponent of -3.

  15. 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

  16. Women Exiting Street-Based Sex Work: Correlations between Ethno-Racial Identity, Number of Children, and Violent Experiences.

    Science.gov (United States)

    Hankel, Jennifer; Dewey, Susan; Martinez, Nina

    2016-01-01

    Through this article the authors examine data collected from 126 women seeking services at a transitional housing facility, primarily for women leaving street-based prostitution. Descriptive statistics on the women's ethno-racial identity, numbers of children, and experiences with violence are presented and analyzed to determine correlations and implications for social service providers working with this unique population of women. Nearly half of respondents are women of color, a majority have given birth to at least one child, and more than half are in a non-commercial intimate partnership, with a significant number reporting extensive experiences with violent trauma and abuse. Results indicate statistically significant differences in women's ethno-racial self-identification and their experiences of sex work and violence, as well as their marital status. Most notably, African-American and Hispanic women face the greatest and most diverse forms of intimate partner violence and negative sex industry experiences, with African-Americans more likely to engage in sex work as minors, be sexually abused as children, work for a pimp, and face physical assault and instances of sex trafficking. Results also support existing research showing correlations between traumatic childhood events and adult substance abuse, sexual assault, and other negative outcomes.

  17. Clusters and Correlates of Experiences with Parents and Peers in Early Adolescence

    Science.gov (United States)

    Kan, Marni L.; McHale, Susan M.

    2007-01-01

    This study used a person-oriented approach to examine links between adolescents' experiences with parents and peers. Cluster analysis classified 361, White, working- and middle-class youth (mean age = 12.16 years) based on mothers' and fathers' reports of parental acceptance and adolescents' reports of perceived peer competence. Three patterns…

  18. Fully automated system for pulsed NMR measurements

    Energy Technology Data Exchange (ETDEWEB)

    Cantor, David Milton

    1977-01-01

    A system is described which places many of the complex, tedious operations for pulsed NMR experiments under computer control. It automatically optimizes the experiment parameters of pulse length and phase, and precision, accuracy, and measurement speed are improved. The hardware interface between the computer and the NMR instrument is described. Design features, justification of the choices made between alternative design strategies, and details of the implementation of design goals are presented. Software features common to all the available experiments are discussed. Optimization of pulse lengths and phases is performed via a sequential search technique called Uniplex. Measurements of the spin-lattice and spin-spin relaxation times and of diffusion constants are automatic. Options for expansion of the system are explored along with some of the limitations of the system.

  19. Engineering out motion: a surface disulfide bond alters the mobility of tryptophan 22 in cytochrome b5 as probed by time-resolved fluorescence and 1H NMR experiments.

    Science.gov (United States)

    Storch, E M; Grinstead, J S; Campbell, A P; Daggett, V; Atkins, W M

    1999-04-20

    In the accompanying paper [Storch et al. (1999) Biochemistry 38, 5054-5064] equilibrium denaturation studies and molecular dynamics (MD) simulations were used to investigate localized dynamics on the surface of cytochrome b5 (cyt b5) that result in the formation of a cleft. In those studies, an S18C:R47C disulfide mutant was engineered to inhibit cleft mobility. Temperature- and urea-induced denaturation studies revealed significant differences in Trp 22 fluorescence between the wild-type and mutant proteins. On the basis of the results, it was proposed that wild type populates a conformational ensemble that is unavailable to the disulfide mutant and is mediated by cleft mobility. As a result, the solvent accessibility of Trp 22 is decreased in S18C:R47C, suggesting that the local environment of this residue is less mobile due to the constraining effects of the disulfide on cleft dynamics. To further probe the structural effects on the local environment of Trp 22 caused by inhibition of cleft formation, we report here the results of steady-state and time-resolved fluorescence quenching, differential phase/modulation fluorescence anisotropy, and 1H NMR studies. In Trp fluorescence experiments, the Stern-Volmer quenching constant increases in wild type versus the oxidized disulfide mutant with increasing temperature. At 50 degrees C, KSV is nearly 1.5-fold greater in wild type compared to the oxidized disulfide mutant. In the reduced disulfide mutant, KSV was the same as wild type. The bimolecular collisional quenching constant, kq, for acrylamide quenching of Trp 22 increases 2.7-fold for wild type and only 1.8-fold for S18C:R47C, upon increasing the temperature from 25 to 50 degrees C. The time-resolved anisotropy decay at 25 degrees C was fit to a double-exponential decay for both the wild type and S18C:R47C. Both proteins exhibited a minor contribution from a low-amplitude fast decay, consistent with local motion of Trp 22. This component was more prevalent in

  20. Quantum mechanical NMR simulation algorithm for protein-size spin systems.

    Science.gov (United States)

    Edwards, Luke J; Savostyanov, D V; Welderufael, Z T; Lee, Donghan; Kuprov, Ilya

    2014-06-01

    Nuclear magnetic resonance spectroscopy is one of the few remaining areas of physical chemistry for which polynomially scaling quantum mechanical simulation methods have not so far been available. In this communication we adapt the restricted state space approximation to protein NMR spectroscopy and illustrate its performance by simulating common 2D and 3D liquid state NMR experiments (including accurate description of relaxation processes using Bloch-Redfield-Wangsness theory) on isotopically enriched human ubiquitin - a protein containing over a thousand nuclear spins forming an irregular polycyclic three-dimensional coupling lattice. The algorithm uses careful tailoring of the density operator space to only include nuclear spin states that are populated to a significant extent. The reduced state space is generated by analysing spin connectivity and decoherence properties: rapidly relaxing states as well as correlations between topologically remote spins are dropped from the basis set.

  1. Moisture dynamics in wall paintings monitored by single-sided NMR.

    Science.gov (United States)

    Oligschläger, D; Waldow, S; Haber, A; Zia, W; Blümich, B

    2015-01-01

    The durability of historic wall paintings is highly dependent on environmental influences such as moisture ingress, salt crystallization and temperature changes. A fundamental understanding of dynamic transport processes in wall paintings is necessary to apply suitable conservation and restoration methods to preserve such objects with high cultural value. Non-invasive, mobile-NMR techniques with single-sided sensors, such as the NMR-MOUSE(®), enable to monitor the moisture content, transport and apparent diffusion constants in wall paintings. We investigated this technique by experiment and modeling to correlate salt crystallization, moisture transport and local diffusion in wall-painting samples. Moreover, the influence of different painting techniques (fresco and secco) and conservation/consolidation methods on moisture transport and diffusion is discussed. The results are compared with results from field measurements on real fresco paintings in Casa del Salone Nero and the Villa of the Papyri, Herculaneum, Italy.

  2. Recent progress in heteronuclear long-range NMR of complex carbohydrates: 3D H2BC and clean HMBC.

    Science.gov (United States)

    Meier, Sebastian; Petersen, Bent O; Duus, Jens Ø; Sørensen, Ole W

    2009-11-02

    The new NMR experiments 3D H2BC and clean HMBC are explored for challenging applications to a complex carbohydrate at natural abundance of (13)C. The 3D H2BC experiment is crucial for sequential assignment as it yields heteronuclear one- and two-bond together with COSY correlations for the (1)H spins, all in a single spectrum with good resolution and non-informative diagonal-type peaks suppressed. Clean HMBC is a remedy for the ubiquitous problem of strong coupling induced one-bond correlation artifacts in HMBC spectra of carbohydrates. Both experiments work well for one of the largest carbohydrates whose structure has been determined by NMR, not least due to the enhanced resolution offered by the third dimension in 3D H2BC and the improved spectral quality due to artifact suppression in clean HMBC. Hence these new experiments set the scene to take advantage of the sensitivity boost achieved by the latest generation of cold probes for NMR structure determination of even larger and more complex carbohydrates in solution.

  3. 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.

  4. 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.

  5. NMR studies of metalloproteins

    OpenAIRE

    Li, H; H. Sun

    2011-01-01

    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...

  6. Enzyme dynamics from NMR spectroscopy.

    Science.gov (United States)

    Palmer, Arthur G

    2015-02-17

    conformational transition in AlkB between an open state, in which the side chains of methionine residues in the active site are disordered, and a closed state, in which these residues are ordered. The open state is highly populated in the AlkB/Zn(II) complex, and the closed state is highly populated in the AlkB/Zn(II)/2OG/substrate complex, in which 2OG is the 2-oxoglutarate cosubstrate and the substrate is a methylated DNA oligonucleotide. The equilibrium is shifted to approximately equal populations of the two conformations in the AlkB/Zn(II)/2OG complex. The conformational shift induced by 2OG ensures that 2OG binds to AlkB/Zn(II) prior to the substrate. In addition, the opening rate of the closed conformation limits premature release of substrate, preventing generation of toxic side products by reaction with water. Closure of active site loop 6 in triosephosphate isomerase is critical for forming the Michaelis complex, but reopening of the loop after the reaction is (partially) rate limiting. NMR spin relaxation and MD simulations of triosephosphate isomerase in complex with glycerol 3-phosphate demonstrate that closure of loop 6 is a highly correlated rigid-body motion. The MD simulations also indicate that motions of Gly173 in the most flexible region of loop 6 contribute to opening of the active site loop for product release. Considered together, these three enzyme systems illustrate the power of NMR spin relaxation investigations in providing global insights into the role of conformational dynamic processes in the mechanisms of enzymes from initial activation to final product release.

  7. Quantum correlations by four-wave-mixing in atomic vapor. Theory and Experiments

    CERN Document Server

    Glorieux, Quentin

    2011-01-01

    We study both theoretically and experimentally the generation of quantum correlations in the continuous variable regime by way of four-wave mixing in a hot atomic vapor. Two theoretical approaches have been developed. On one side, we study the four-wave mixing under the "classical" non-linear optics point of view. In such a way we obtain the evolution equation for an ideal linear amplifier in a {\\chi}^(3) medium. On the other side, we present a microscopic model with 4 levels in the double-{\\Lambda} configuration to calculate the {\\chi}^(3) coefficient in a atomic vapor dressed with a laser. This calculation allows us to derive the spectra of intensity noise for interesting parameters. The experimental part of this work describes the demonstration of this effect on the D1 line of rubidium 85. We present a measurement of relative intensity squeezing as high as -9.2dB below the standard quantum limit, and an original regime where quantum correlations have been measured without amplification.These results have b...

  8. Correlation of FEA Prediction And Experiments On Dual-Phase Steel Automotive Rails

    Science.gov (United States)

    Du, C.; Chen, X. M.; Lim, T.; Chang, T.; Xiao, P.; Liu, S.-D.

    2007-05-01

    The North American Auto/Steel Partnership (A/SP) High-Strength Steel Forming Project Team has been studying the impact of advanced high-strength steels on stamping of structural components. Tooling was built to evaluate the effect of different grades of dual-phase steels on rail type stampings. The formed panels were laser scanned and the amount of springback was measured against the design intention. FEA simulation of the forming process was carried out to validate the numerical modeling techniques in the large and complex dual-phase steel stampings. The materials used in the study were Dual-Phase (DP) Steels DP600, DP780 and DP980. The FEA solver used was LS-Dyna version 971. The simulation results were correlated with the measurement data under various forming conditions including forming methods, trimming, binder and pad pressures. Reasonably good correlations were obtained across different grades of steels in terms of flange opening angles, wall opening angles, twist angles and dimensional deviations.

  9. NMR Hyperpolarization Techniques of Gases.

    Science.gov (United States)

    Barskiy, Danila A; Coffey, Aaron M; Nikolaou, Panayiotis; Mikhaylov, Dmitry M; Goodson, Boyd M; Branca, Rosa T; Lu, George J; Shapiro, Mikhail G; Telkki, Ville-Veikko; Zhivonitko, Vladimir V; Koptyug, Igor V; Salnikov, Oleg G; Kovtunov, Kirill V; Bukhtiyarov, Valerii I; Rosen, Matthew S; Barlow, Michael J; Safavi, Shahideh; Hall, Ian P; Schröder, Leif; Chekmenev, Eduard Y

    2017-01-18

    Nuclear spin polarization can be significantly increased through the process of hyperpolarization, leading to an increase in the sensitivity of nuclear magnetic resonance (NMR) experiments by 4-8 orders of magnitude. Hyperpolarized gases, unlike liquids and solids, can often be readily separated and purified from the compounds used to mediate the hyperpolarization processes. These pure hyperpolarized gases enabled many novel MRI applications including the visualization of void spaces, imaging of lung function, and remote detection. Additionally, hyperpolarized gases can be dissolved in liquids and can be used as sensitive molecular probes and reporters. This Minireview covers the fundamentals of the preparation of hyperpolarized gases and focuses on selected applications of interest to biomedicine and materials science. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Distinguishing Cause from Correlation in Tokamak Experiments to Trigger Edge Localised Plasma Instabilities

    CERN Document Server

    Webster, A J

    2014-01-01

    The generic question is considered: How can we determine the probability of an otherwise quasirandom event, having been triggered by an external influence? A specific problem is the quantification of the success of techniques to trigger, and hence control, edge-localised plasma instabilities (ELMs) in magnetically confined fusion (MCF) experiments. The development of such techniques is essential to ensure tolerable heat loads on components in large MCF fusion devices, and is necessary for their development into economically successful power plants. Bayesian probability theory is used to rigorously formulate the problem and to provide a formal solution. Accurate but pragmatic methods are developed to estimate triggering probabilities, and are illustrated with experimental data. These allow results from experiments to be quantitatively assessed, and rigorously quantified conclusions to be formed.

  11. Hydration dynamics of the collagen triple helix by NMR.

    Science.gov (United States)

    Melacini, G; Bonvin, A M; Goodman, M; Boelens, R; Kaptein, R

    2000-07-28

    The hydration of the collagen-like Ac-(Gly-Pro-Hyp)(6)-NH(2) triple-helical peptide in solution was investigated using an integrated set of high-resolution NMR hydration experiments, including different recently developed exchange-network editing methods. This approach was designed to explore the hydration dynamics in the proximity of labile groups, such as the hydroxyproline hydroxyl group, and revealed that the first shell of hydration in collagen-like triple helices is kinetically labile with upper limits for water molecule residence times in the nanosecond to sub-nanosecond range. This result is consistent with a "hopping" hydration model in which solvent molecules are exchanged in and out of solvation sites at a rate that is not directly correlated to the degree of site localization. The hopping model thus reconciles the dynamic view of hydration revealed by NMR with the previously suggested partially ordered semi-clathrate-like cylinder of hydration. In addition, the nanosecond to sub-nanosecond upper limits for water molecule residence times imply that hydration-dehydration events are not likely to be the rate-limiting step for triple helix self-recognition, complementing previous investigations on water dynamics in collagen fibers. This study has also revealed labile proton features expected to facilitate the characterization of the structure and folding of triple helices in collagen peptides.

  12. Anomalous echo: Exploring abnormal experience correlates of emotional motor resonance in Schizophrenia Spectrum.

    Science.gov (United States)

    Sestito, Mariateresa; Raballo, Andrea; Umiltà, Maria Alessandra; Amore, Mario; Maggini, Carlo; Gallese, Vittorio

    2015-09-30

    Anomalous experiences such as Basic Symptoms (BS) are considered the first subjective manifestation of the neurobiological substrate of schizophrenia. The purpose of this study was to explore whether a low or high emotional motor resonance occurring in Schizophrenia Spectrum (SzSp) patients was related to patients׳ clinical features and to their anomalous subjective experiences as indexed by the Bonn Scale for the Assessment of Basic Symptoms (BSABS). To this aim, we employed a validated paradigm sensitive in evoking a congruent facial mimicry (measured by means of facial electromyographic activity, EMG) through multimodal positive and negative emotional stimuli presentation. Results showed that SzSp patients more resonating with negative emotional stimuli (i.e. Externalizers) had significantly higher scores in BSABS Cluster 3 (Vulnerability) and more psychotic episodes than Internalizers patients. On the other hand, SzSp patients more resonating with positive emotional stimuli (i.e. Externalizers) scored higher in BSABS Cluster 5 (Interpersonal irritation) than Internalizers. Drawing upon a phenomenological-based perspective, we attempted to shed new light on the abnormal experiences characterizing schizophrenia, explaining them in terms of a disruption of the normal self-perception conveyed by the basic, low-level emotional motor mechanisms.

  13. EEG gamma coherence and other correlates of subjective reports during ayahuasca experiences.

    Science.gov (United States)

    Stuckey, David E; Lawson, Robert; Luna, Luis Eduardo

    2005-06-01

    The current study examined QEEG power and coherence of ayahuasca experiences with two experienced participants in a Brazilian jungle setting. An exploratory case series design was adopted for naturalistic field research. EEGs recorded during visual imagery was compared to eyes-closed baselines. The most important findings were increases in global EEG coherence in the 36-44 Hz and 50-64 Hz frequency bands for both subjects. Widely distributed cortical hyper-coherence seems reasonable given the intense synesthesia during ayahuasca experiences. Other findings include increased modal EEG alpha frequency and global power decreases across the cortex in most frequency bands, which concur with the EEG of psychedelics literature. Exploratory analysis revealed the usefulness of analyzing single Hz bins over the standard wide-band analysis. The discovery-oriented naturalistic approach developed for this study resulted in potentially important findings. We believe that finding increases in global gamma coherence during peak psychedelic experiences might contribute to the discussion of binding theory. Also, in light of recent research with gamma coherence during advanced meditative conditions, our findings might further the comparison of shamanic psychedelic practices with meditation.

  14. Indirect spin-spin coupling constants in CH{sub 4}, SiH{sub 4} and GeH{sub 4} - Gas-phase NMR experiment and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Antusek, Andrej [Slovak University of Technology in Bratislava, Faculty of Materials Science and Technology in Trnava, Paulinska 16, 917 24 Trnava (Slovakia); Department of Chemistry, Nicolaus Copernicus University, Gagarina 7, PL 87-100 Torun (Poland); Kedziera, Dariusz [Department of Chemistry, Nicolaus Copernicus University, Gagarina 7, PL 87-100 Torun (Poland); Jackowski, Karol [Laboratory of NMR Spectroscopy, Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Jaszunski, Michal [Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01224 Warsaw (Poland)], E-mail: michaljz@icho.edu.pl; Makulski, Wlodzimierz [Laboratory of NMR Spectroscopy, Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)

    2008-09-03

    New values of the indirect spin-spin coupling constants in CH{sub 4}, SiH{sub 4} and GeH{sub 4}, derived from experiment and ab initio calculations, are reported. The new experimental values of {sup 1}J(CH), {sup 1}J(SiH) and {sup 1}J(GeH) are obtained from gas-phase NMR spectra. The dependence of the measured one-bond coupling constants on the density is analysed and the results are extrapolated to zero-density point to eliminate the effects due to intermolecular forces. In the calculation of the coupling constants, at the nonrelativistic level coupled cluster singles and doubles (CCSD) perturbation theory is used and the basis set convergence of the results is discussed. The relativistic corrections are estimated from Dirac-Hartree-Fock (DHF) calculations. The final theoretical values are obtained adding available estimates of the vibrational and temperature corrections. The agreement of the calculated and experimental {sup 1}J(XH), X = C, Si, Ge, constants is very satisfying, the differences are approximately 1-3%.

  15. Correlation of Process Data and Electrochemical Noise to Assess Kraft Digester Corrosion: Spring Grove Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Pawel, SJ

    2003-06-18

    Electrochemical noise (ECN) probes were deployed in a carbon steel continuous kraft digester at four locations and at one location in the bottom cone of the associated flash tank. The probes consisted of carbon steel electrodes, representing the vessel construction material, and 309LSi stainless steel overlay electrodes, representing the weld overlay repair in a portion of the vessel. Current and potential noise, the temperature at each probe location, and the value of about 32 process parameters (flow rates, liquor chemistry, etc.) were monitored continuously for a period of almost one year. Historical vessel inspection data and post-test evaluation of the probe components were used to assess/compare ECN corrosion activity with physical changes in wall thickness and corrosion patterns on the digester shell. In addition, attempts were made to correlate ECN activity from each electrode type with process parameters. The results indicate the high general corrosion rates of steel observed just below the extraction screens--on the order of 35 mils/y for the past few years--accelerated further during the period of probe deployment. The maximum wastage of steel (normalized to one full year exposure) was about 85 mils/y at the ring 6N probe just below the extraction screens. Consistent with recent historical observations, the steel corrosion rate at the ring 6S probe--at the same elevation but directly across the digester from ring 6N--was significantly lower at about 50 mils/y. Just prior to probe deployment, the digester shell below the extraction screens was overlaid with 309LSi stainless steel, which was observed to be essentially immune to corrosion at this location. While the ECN probes detected differences in electrochemical behavior between steel probes and between 309LSi probes at rings 6N and 6S, there was only poor quantitative correlation of current sums with actual corrosion rates at these locations. A significant contribution of redox reactions on both steel

  16. 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.

  17. Site-selective Cu deposition on Pt dendrimer-encapsulated nanoparticles: correlation of theory and experiment.

    Science.gov (United States)

    Carino, Emily V; Kim, Hyun You; Henkelman, Graeme; Crooks, Richard M

    2012-03-07

    The voltammetry of Cu underpotential deposition (UPD) onto Pt dendrimer-encapsulated nanoparticles (DENs) containing an average of 147 Pt atoms (Pt(147)) is correlated to density functional theory (DFT) calculations. Specifically, the voltammetric peak positions are in good agreement with the calculated energies for Cu deposition and stripping on the Pt(100) and Pt(111) facets of the DENs. Partial Cu shells on Pt(147) are more stable on the Pt(100) facets, compared to the Pt(111) facets, and therefore, Cu UPD occurs on the 4-fold hollow sites of Pt(100) first. Finally, the structures of Pt DENs having full and partial monolayers of Cu were characterized in situ by X-ray absorption spectroscopy (XAS). The results of XAS studies are also in good agreement with the DFT-optimized models.

  18. Correlation of Process Data and Electrochemical Noise to Assess Kraft Digester Corrosion: Kamloops Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Pawel, SJ

    2002-05-09

    Electrochemical noise (ECN) probes were deployed in a carbon steel continuous kraft digester at five locations roughly equi-spaced from top to bottom of the vessel. Current and potential noise, the temperature at each probe location, and the value of about 60 process parameters (flow rates, liquor chemistry, etc.) were monitored continuously for a period of one year. Historical vessel inspection data, including inspections accomplished immediately prior to and immediately following probe deployment, and post-test evaluation of the probe components were used to assess/compare corrosion indications from the probes with physical changes in wall thickness and corrosion patterns on the digester shell. The results indicate that furnish composition is a significant variable influencing digester corrosion, with increasing amounts of Douglas fir in the nominal furnish correlating directly with increased corrosion activity on the ECN probes. All five probes detected changes in furnish composition approximately simultaneously, indicating rapid chemical communication through the liquor, but the effect was strongest and persisted longest relatively high in the digester. The ECN probes also indicate significant corrosion activity occurred at each probe position during shutdown/restart transients. Little or no correlation between ECN probe corrosion activity and other operational variables was observed. Post-test evaluation of the probes confirmed general corrosion of a magnitude that closely agreed with corrosion current sums calculated for each probe over the exposure period and with historical average corrosion rates for the respective locations. Further, no pitting was observed on any of the electrodes, which is consistent with the ECN data, relevant polarization curves developed for steel in liquor removed from the digester, and the post-test inspection of the digester.

  19. Measuring skin penetration by confocal Raman microscopy (CRM): correlation to results from conventional experiments

    Science.gov (United States)

    Lunter, Dominique; Daniels, Rolf

    2016-03-01

    Confocal Raman microscopy has become an advancing technique in the characterization of drug transport into the skin. In this study the skin penetration of a local anesthetic from a semisolid preparation was investigated. Furthermore, the effect of the chemical enhancers propylene glycol and POE-23-lauryl ether on its penetration was investigated. The results show that confocal Raman microscopy may provide detailed information on the penetration of APIs into the skin and may elucidate their distribution within the skin with high resolution. The results of the CRM analysis are fully in line with those of conventional permeation and penetration experiments.

  20. Thermal mathematical model correlation through genetic algorithms of an experiment conducted on board the International Space Station

    Science.gov (United States)

    Garmendia, Iñaki; Anglada, Eva

    2016-05-01

    Genetic algorithms have been used for matching temperature values generated using thermal mathematical models against actual temperatures measured in thermal testing of spacecrafts and space instruments. Up to now, results for small models have been very encouraging. This work will examine the correlation of a small-medium size model, whose thermal test results were available, by means of genetic algorithms. The thermal mathematical model reviewed herein corresponds to Tribolab, a materials experiment deployed on board the International Space Station and subjected to preflight thermal testing. This paper will also discuss in great detail the influence of both the number of reference temperatures available and the number of thermal parameters included in the correlation, taking into account the presence of heat sources and the maximum range of temperature mismatch. Conclusions and recommendations for the thermal test design will be provided, as well as some indications for future improvements.

  1. Neural correlates of an illusory touch experience investigated with fMRI.

    Science.gov (United States)

    Lloyd, Donna M; McKenzie, Kirsten J; Brown, Richard J; Poliakoff, Ellen

    2011-10-01

    When asked to judge the presence or absence of near-threshold tactile stimuli, participants often report touch experiences when no tactile stimulation has been delivered ('false alarms'). The simultaneous presentation of a light flash during the stimulation period can increase the frequency of touch reports, both when touch is and is not present. Using fMRI, we investigated the BOLD response during both light-present and light-absent false alarms, testing predictions concerning two possible neural mechanisms underlying these illusory touch experiences: activation of a tactile representation in primary somatosensory cortex (SI) and/or activation of a tactile representation in late processing areas outside of sensory-specific cortex, such as medial prefrontal cortex (MPC). Our behavioural results showed that participants made false alarms in light-present and light-absent trials, both of which activated regions of the medial parietal and medial prefrontal cortex including precuneus, posterior cingulate and paracingulate cortex, suggesting the same underlying mechanism. However, only a non-significant increase in SI activity was measured in response to false alarm vs. correct rejection trials. We argue that our results provide evidence for the role of top-down regions in somatic misperception, consistent with findings from studies in humans and non-human primates.

  2. Noninferiority tests based on concordance correlation coefficient for assessment of the agreement for gene expression data from microarray experiments.

    Science.gov (United States)

    Liao, Chen-Tuo; Lin, Chia-Ying; Liu, Jen-Pei

    2007-01-01

    Microarray is one of the breakthrough technologies in the twenty-first century. Despite of its great potential, transition and realization of microarray technology into the clinically useful commercial products have not been as rapid as the technology could promise. One of the primary reasons is lack of agreement and poor reproducibility of the intensity measurements on gene expression obtained from microarray experiments. Current practices often use the testing the hypothesis of zero Pearson correlation coefficient to assess the agreement of gene expression levels between the technical replicates from microarray experiments. However, Pearson correlation coefficient is to evaluate linear association between two variables and fail to take into account changes in accuracy and precision. Hence, it is not appropriate for evaluation of agreement of gene expression levels between technical replicates. Therefore, we propose to use the concordance correlation coefficient to assess agreement of gene expression levels between technical replicates. We also apply the Generalized Pivotal Quantities to obtain the exact confidence interval for concordance coefficient. In addition, based on the concept of noninferiority test, a one-sided (1 - alpha) lower confidence limit for concordance correlation coefficient is employed to test the hypothesis that the agreement of expression levels of the same genes between two technical replicates exceeds some minimal requirement of agreement. We conducted a simulation study, under various combinations of mean differences, variability, and sample size, to empirically compare the performance of different methods for assessment of agreement in terms of coverage probability, expected length, size, and power. Numerical data from published papers illustrate the application of the proposed methods.

  3. HN-NCA heteronuclear TOCSY-NH experiment for {sup 1}H{sup N} and {sup 15}N sequential correlations in ({sup 13}C, {sup 15}N) labelled intrinsically disordered proteins

    Energy Technology Data Exchange (ETDEWEB)

    Wiedemann, Christoph; Goradia, Nishit; Häfner, Sabine [Leibniz Institute for Age Research, Fritz Lipmann Institute, Research Group Biomolecular NMR Spectroscopy (Germany); Herbst, Christian [Ubon Ratchathani University, Department of Physics, Faculty of Science (Thailand); Görlach, Matthias; Ohlenschläger, Oliver; Ramachandran, Ramadurai, E-mail: raman@fli-leibniz.de [Leibniz Institute for Age Research, Fritz Lipmann Institute, Research Group Biomolecular NMR Spectroscopy (Germany)

    2015-10-15

    A simple triple resonance NMR experiment that leads to the correlation of the backbone amide resonances of each amino acid residue ‘i’ with that of residues ‘i−1’ and ‘i+1’ in ({sup 13}C, {sup 15}N) labelled intrinsically disordered proteins (IDPs) is presented. The experimental scheme, {HN-NCA heteronuclear TOCSY-NH}, exploits the favourable relaxation properties of IDPs and the presence of {sup 1}J{sub CαN} and {sup 2}J{sub CαN} couplings to transfer the {sup 15}N{sub x} magnetisation from amino acid residue ‘i’ to adjacent residues via the application of a band-selective {sup 15}N–{sup 13}C{sup α} heteronuclear cross-polarisation sequence of ∼100 ms duration. Employing non-uniform sampling in the indirect dimensions, the efficacy of the approach has been demonstrated by the acquisition of 3D HNN chemical shift correlation spectra of α-synuclein. The experimental performance of the RF pulse sequence has been compared with that of the conventional INEPT-based HN(CA)NH pulse scheme. As the availability of data from both the HCCNH and HNN experiments will make it possible to use the information extracted from one experiment to simplify the analysis of the data of the other and lead to a robust approach for unambiguous backbone and side-chain resonance assignments, a time-saving strategy for the simultaneous collection of HCCNH and HNN data is also described.

  4. NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR.

    Science.gov (United States)

    Schreckenbach, Georg

    2002-12-16

    In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

  5. Search for Sporadic Enhancements of UHECR and Correlations with Cosmic Phenomena in LAAS Experiment

    Science.gov (United States)

    Ochi, N.; Iyono, A.; Konishi, T.; Nakamura, T.; Nakatsuka, T.; Ohara, S.; Ohmori, N.; Okei, K.; Saitoh, K.; Tada, J.; Takahashi, N.; Tsuji, S.; Wada, T.; Yamamoto, I.; Yamashita, Y.; LAAS Group

    2003-07-01

    The Large Area Air Shower (LAAS) group has been collecting extensive air shower (EAS) data by compact EAS arrays simultaneously operating at eleven sites in Japan. Working since 1996, a large number of EAS data have been accumulated and they are analyzed in this report. In order to find out signals from short-lived burst activities in the universe, we insp ect EAS trigger rates of short time windows and search for sporadic excess events in them. Significant events are furthermore employed to explore possible correlations with cosmic phenomena such as gamma-ray bursts, cluster events observed by AGASA and highest energy cosmic rays by AGASA and HiRes. Particularly, our EAS arrays in Okayama area, of which trigger conditions are uniformly set at 2-fold coincidence of adjacent counters since 2002, are expected to be more sensitive to such sporadic phenomena because they can be triggered by lower energy primary particles. The results using all LAAS data will be presented at the conference.

  6. Correlates of perceptual awareness in human primary auditory cortex revealed by an informational masking experiment.

    Science.gov (United States)

    Wiegand, Katrin; Gutschalk, Alexander

    2012-05-15

    The presence of an auditory event may remain undetected in crowded environments, even when it is well above the sensory threshold. This effect, commonly known as informational masking, allows for isolating neural activity related to perceptual awareness, by comparing repetitions of the same physical stimulus where the target is either detected or not. Evidence from magnetoencephalography (MEG) suggests that auditory-cortex activity in the latency range 50-250 ms is closely coupled with perceptual awareness. Here, BOLD fMRI and MEG were combined to investigate at which stage in the auditory cortex neural correlates of conscious auditory perception can be observed. Participants were asked to indicate the perception of a regularly repeating target tone, embedded within a random multi-tone masking background. Results revealed widespread activation within the auditory cortex for detected target tones, which was delayed but otherwise similar to the activation of an unmasked control stimulus. The contrast of detected versus undetected targets revealed activity confined to medial Heschl's gyrus, where the primary auditory cortex is located. These results suggest that activity related to conscious perception involves the primary auditory cortex and is not restricted to activity in secondary areas.

  7. Correlating DFT-calculated energy barriers to experiments in nonheme octahedral Fe(IV)O species.

    Science.gov (United States)

    Cho, Kyung-Bin; Kim, Eun Jeong; Seo, Mi Sook; Shaik, Sason; Nam, Wonwoo

    2012-08-13

    The experimentally measured bimolecular reaction rate constant, k(2), should in principle correlate with the theoretically calculated rate-limiting free energy barrier, ΔG(≠), through the Eyring equation, but it fails quite often to do so due to the inability of current computational methods to account in a precise manner for all the factors contributing to ΔG(≠). This is further aggravated by the exponential sensitivity of the Eyring equation to these factors. We have taken herein a pragmatic approach for C-H activation reactions of 1,4-cyclohexadiene with a variety of octahedral nonheme Fe(IV)O complexes. The approach consists of empirically determining two constants that would aid in predicting experimental k(2) values uniformly from theoretically calculated electronic energy (ΔE(≠)) values. Shown in this study is the predictive power as well as insights into energy relationships in Fe(IV)O C-H activation reactions. We also find that the difference between ΔG(≠) and ΔE(≠) converges at slow reactions, in a manner suggestive of changes in the importance of the triplet spin state weight in the overall reaction.

  8. NMR-Based Diffusion Lattice Imaging

    CERN Document Server

    Laun, Frederik Bernd

    2013-01-01

    Nuclear magnetic resonance (NMR) diffusion experiments are widely employed as they yield information about structures hindering the diffusion process, e.g. about cell membranes. While it has been shown in recent articles, that these experiments can be used to determine the exact shape of closed pores averaged over a volume of interest, it is still an open question how much information can be gained in open systems. In this theoretical work, we show that the full structure information of periodic open systems is accessible. To this end, the so-called 'SEquential Rephasing by Pulsed field-gradient Encoding N Time-intervals' (SERPENT) sequence is used, which employs several diffusion weighting gradient pulses with different amplitudes. The structural information is obtained by an iterative technique relying on a Gaussian envelope model of the diffusion propagator. Two solid matrices that are surrounded by an NMR-visible medium are considered: a hexagonal lattice of cylinders and a cubic lattice of triangles.

  9. Structural Studies of Biological Solids Using NMR

    Science.gov (United States)

    Ramamoorthy, Ayyalusamy

    2011-03-01

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

  10. Reversed-phase liquid chromatography with electrospray mass detection and 1H and 13C NMR characterization of new process-related impurities, including forced degradants of efavirenz: related substances correlated to the synthetic pathway.

    Science.gov (United States)

    Gadapayale, Kamalesh; Kakde, Rajendra; Sarma, V U M

    2015-01-01

    In this study, a stability-indicating reversed-phase liquid chromatographic electrospray mass spectrometric method was developed and validated for the determination of process-related impurities and forced degradants of Efavirenz in bulk drugs. Efavirenz was subjected to acid, alkaline hydrolysis, H2O2 oxidation, photolysis, and thermal stress. Significant degradation was observed during alkaline hydrolysis, and the degradants were isolated on a mass-based purification system and characterized by high-resolution mass spectrometry, positive electrospray ionization tandem mass spectrometry, and (1)H and (13)C NMR spectroscopy. Accurate mass measurement and NMR spectroscopy revealed the possible structure of process-related impurities and degradant under stress conditions. The acceptable separation was accomplished on Waters bondapak C18 column (250 mm × 4.6 mm; 5 μm), using 5 mM ammonium acetate and acetonitrile as a mobile phase in a gradient elution mode at a flow rate of 1.0 mL/min. The eluents were monitored by diode array detector at 247 nm and quantitation limits were obtained in the range of 0.1-2.5 μg/mL for Efavirenz, degradants, and process-related impurities. The liquid chromatography method was validated with respect to accuracy, precision, linearity, robustness, and limits of detection and quantification as per International Conference on Harmonization guidelines. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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.

  12. CORRELATION OF CRISES, CRISIS EXPERIENCES AND ORIENTATION OF TIME PERSPECTIVE AT THE INITIAL STAGE OF TRAINING IN HIGHER EDUCATION INSTITUTION

    Directory of Open Access Journals (Sweden)

    Irina A. Kurus

    2016-01-01

    Full Text Available The purpose of article is identification of an actual problem of psychological science: correlation of crises and a crisis experiences with and orientation of time perspective at the initial stage of training in institution of higher education.Methods. During the research the following psychodiagnostic methods are applied: the questionnaire of crisis experiences for student by V. R. Manukyan; a questionnaire of time perspective by F. Zimbardo in adaptation of A. Syrtsova, E. T. Sokolova, O. V. Mitina (ZTPI.Results and scientific novelty. Data on interrelation of crises and crisis experiences with an orientation of temporary prospect are obtained and analysed on the basis of representative selection of students in Novosibirsk State Medical University. Gender distinctions of crises behaviour of students are shown. It is established that temporary prospects «The negative past» and «The fatalistic present» correlate with all the crisis experiences of students at the initial stage of training in higher education institution. The temporary prospect «Future» has the return correlation with crisis experience «absence of the appreciably attractive purposes in the future», and the interrelation with crises is absent. In this regard the author proposes the correction procedure of psychological escort of first-year students.Practical significance. The research findings can be used by educational psychologists for psychological diagnostics of pupils, to search the reasons of their poor progress, during the developing and correction of programs of psychology and pedagogical escort of first-year students, in particular when writing the program of adaptive training in the centers of psychosocial maintenance of the trainees. Guidelines for a choice of the techniques and methods promoting overcoming of the problems connected with crisis of identity and biographic crises are given.

  13. 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.

  14. 3D Reconstruction of NMR Images

    Directory of Open Access Journals (Sweden)

    Peter Izak

    2007-01-01

    Full Text Available This paper introduces experiment of 3D reconstruction NMR images scanned from magnetic resonance device. There are described methods which can be used for 3D reconstruction magnetic resonance images in biomedical application. The main idea is based on marching cubes algorithm. For this task was chosen sophistication method by program Vision Assistant, which is a part of program LabVIEW.

  15. Transformer-coupled NMR probe

    Science.gov (United States)

    Utsuzawa, Shin; Mandal, Soumyajit; Song, Yi-Qiao

    2012-03-01

    In this study, we propose an NMR probe circuit that uses a transformer with a ferromagnetic core for impedance matching. The ferromagnetic core provides a strong but confined coupling that result in efficient energy transfer between the sample coil and NMR spectrometer, while not disturbing the B1 field generated by the sample coil. We built a transformer-coupled NMR probe and found that it offers comparable performance (loss NQR.

  16. Keeping an Eye on the Conductor: Neural Correlates of Visuo-motor Synchronization and Musical Experience

    Directory of Open Access Journals (Sweden)

    Kentaro eOno

    2015-04-01

    Full Text Available For orchestra musicians, synchronized playing under a conductor’s direction is necessary to achieve optimal performance. Previous studies using simple auditory/visual stimuli have reported cortico-subcortical networks underlying synchronization and that training improves the accuracy of synchronization. However, it is unclear whether people who played regularly under a conductor and non-musicians activate the same networks when synchronizing with a conductor’s gestures. We conducted a functional magnetic resonance imaging (fMRI experiment testing nonmusicians and musicians who regularly play music under a conductor. Participants were required to tap the rhythm they perceived from silent movies displaying either conductor’s gestures or a swinging metronome. Musicians performed tapping under a conductor with more precision than nonmusicians. Results from fMRI measurement showed greater activity in the anterior part of the left superior frontal gyrus (SFG in musicians with more frequent practice under a conductor. Conversely, tapping with the metronome did not show any difference between musicians and nonmusicians, indicating that the expertise effect in tapping under the conductor does not result in a general increase in tapping performance for musicians. These results suggest that orchestra musicians have developed an advanced ability to predict conductor’s next action from the gestures.

  17. Keeping an eye on the conductor: neural correlates of visuo-motor synchronization and musical experience.

    Science.gov (United States)

    Ono, Kentaro; Nakamura, Akinori; Maess, Burkhard

    2015-01-01

    For orchestra musicians, synchronized playing under a conductor's direction is necessary to achieve optimal performance. Previous studies using simple auditory/visual stimuli have reported cortico-subcortical networks underlying synchronization and that training improves the accuracy of synchronization. However, it is unclear whether people who played regularly under a conductor and non-musicians activate the same networks when synchronizing with a conductor's gestures. We conducted a functional magnetic resonance imaging (fMRI) experiment testing nonmusicians and musicians who regularly play music under a conductor. Participants were required to tap the rhythm they perceived from silent movies displaying either conductor's gestures or a swinging metronome. Musicians performed tapping under a conductor with more precision than nonmusicians. Results from fMRI measurement showed greater activity in the anterior part of the left superior frontal gyrus (SFG) in musicians with more frequent practice under a conductor. Conversely, tapping with the metronome did not show any difference between musicians and nonmusicians, indicating that the expertize effect in tapping under the conductor does not result in a general increase in tapping performance for musicians. These results suggest that orchestra musicians have developed an advanced ability to predict conductor's next action from the gestures.

  18. Solid-state NMR structures of integral membrane proteins.

    Science.gov (United States)

    Patching, Simon G

    2015-01-01

    Solid-state NMR is unique for its ability to obtain three-dimensional structures and to measure atomic-resolution structural and dynamic information for membrane proteins in native lipid bilayers. An increasing number and complexity of integral membrane protein structures have been determined by solid-state NMR using two main methods. Oriented sample solid-state NMR uses macroscopically aligned lipid bilayers to obtain orientational restraints that define secondary structure and global fold of embedded peptides and proteins and their orientation and topology in lipid bilayers. Magic angle spinning (MAS) solid-state NMR uses unoriented rapidly spinning samples to obtain distance and torsion angle restraints that define tertiary structure and helix packing arrangements. Details of all current protein structures are described, highlighting developments in experimental strategy and other technological advancements. Some structures originate from combining solid- and solution-state NMR information and some have used solid-state NMR to refine X-ray crystal structures. Solid-state NMR has also validated the structures of proteins determined in different membrane mimetics by solution-state NMR and X-ray crystallography and is therefore complementary to other structural biology techniques. By continuing efforts in identifying membrane protein targets and developing expression, isotope labelling and sample preparation strategies, probe technology, NMR experiments, calculation and modelling methods and combination with other techniques, it should be feasible to determine the structures of many more membrane proteins of biological and biomedical importance using solid-state NMR. This will provide three-dimensional structures and atomic-resolution structural information for characterising ligand and drug interactions, dynamics and molecular mechanisms of membrane proteins under physiological lipid bilayer conditions.

  19. Magic Angle Spinning NMR Metabolomics

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Jian Z.

    2016-05-31

    Nuclear Magnetic Resonance (NMR) spectroscopy is a non-destructive, quantitative, reproducible, untargeted and unbiased method that requires no or minimal sample preparation, and is one of the leading analytical tools for metabonomics research [1-3]. The easy quantification and the no need of prior knowledge about compounds present in a sample associated with NMR are advantageous over other techniques [1,4]. 1H NMR is especially attractive because protons are present in virtually all metabolites and its NMR sensitivity is high, enabling the simultaneous identification and monitoring of a wide range of low molecular weight metabolites.

  20. Evidence for strong electron correlations in graphene molecular fragments: Theory and experiments on two-photon absorptions

    Science.gov (United States)

    Aryanpour, Karan; Roberts, Adam; Sandhu, Arvinder; Shukla, Alok; Mazumdar, Sumit

    2013-03-01

    Historically, the occurrence of the lowest two-photon state below the optical one-photon state in linear polyenes, polyacetylenes and polydiacetylenes provided the strongest evidence for strong electron correlations in these linear π-conjugated systems. We demonstrate similar behavior in several molecular fragments of graphene with D6 h symmetry, theoretically and experimentally. Theoretically, we have calculated one versus two-photon absorptions in coronene, two different hexabenzocoronenes and circumcoronene, within the Pariser-Parr-Pople π-electron Hamiltonian using high order configuration interaction. Experimentally, we have performed z-scan measurements using a white light super-continuum source on coronene and hexa-peri-hexabenzocoronene to determine frequency-dependent two-photon absorption coefficients, for comparison to the ground state absorptions. Excellent agreement between experiment and theory in our work gives strong evidence for significant electron correlations between the π-electrons in the graphene molecular fragments. We particularly benchmark high order electron-hole excitations in graphene fragments as a key element behind the agreement between theory and experiment in this work. We acknowledge NSF-CHE-1151475 grant as our funding source.

  1. New results on fluctuations and correlations from the NA61/SHINE experiment at the CERN SPS arXiv

    CERN Document Server

    Grebieszkow, Katarzyna

    The exploration of the QCD phase diagram is the most important task of present heavy ion experiments. In particular, we want to study the phase transition from hadronic to partonic matter and look for the critical point (CP) of strongly interacting matter. Fluctuations and correlations in kinematic characteristics and particle yields may help to locate the CP (in analogy to enlarged fluctuations due to critical opalescence close to a CP in a liquid/gas transition). The strong interactions program of the NA61/SHINE experiment may allow to discover or rule out the existence of the CP in the Super Proton Synchrotron energy domain. For this purpose we perform a two-dimensional scan by varying the energy ($5.1 < \\sqrt{s_{NN}} < 16.8/17.3$ GeV) and the system size (p+p, p+Pb, Be+Be, Ar+Sc, Xe+La, Pb+Pb) of the collisions. In this report new NA61/SHINE results on fluctuations and correlations in p+p, Be+Be, and Ar+Sc collisions are presented. In particular, results on transverse momentum and multiplicity fluct...

  2. A Quick and Easy Simplification of Benzocaine's NMR Spectrum

    Science.gov (United States)

    Carpenter, Suzanne R.; Wallace, Richard H.

    2006-04-01

    The preparation of benzocaine is a common experiment used in sophomore-level organic chemistry. Its straightforward procedure and predictable good yields make it ideal for the beginning organic student. Analysis of the product via NMR spectroscopy, however, can be confusing to the novice interpreter. An inexpensive, quick, and effective method for simplifying the NMR spectrum is reported. The method results in a spectrum that is cleanly integrated and more easily interpreted.

  3. Analyzing protein-ligand interactions by dynamic NMR spectroscopy.

    Science.gov (United States)

    Mittermaier, Anthony; Meneses, Erick

    2013-01-01

    Nuclear magnetic resonance (NMR) spectroscopy can provide detailed information on protein-ligand interactions that is inaccessible using other biophysical techniques. This chapter focuses on NMR-based approaches for extracting affinity and rate constants for weakly binding transient protein complexes with lifetimes of less than about a second. Several pulse sequences and analytical techniques are discussed, including line-shape simulations, spin-echo relaxation dispersion methods (CPMG), and magnetization exchange (EXSY) experiments.

  4. Correlation of pre-earthquake electromagnetic signals with laboratory and field rock experiments

    Directory of Open Access Journals (Sweden)

    T. Bleier

    2010-09-01

    Full Text Available Analysis of the 2007 M5.4 Alum Rock earthquake near San José California showed that magnetic pulsations were present in large numbers and with significant amplitudes during the 2 week period leading up the event. These pulsations were 1–30 s in duration, had unusual polarities (many with only positive or only negative polarities versus both polarities, and were different than other pulsations observed over 2 years of data in that the pulse sequence was sustained over a 2 week period prior to the quake, and then disappeared shortly after the quake. A search for the underlying physics process that might explain these pulses was was undertaken, and one theory (Freund, 2002 demonstrated that charge carriers were released when various types of rocks were stressed in a laboratory environment. It was also significant that the observed charge carrier generation was transient, and resulted in pulsating current patterns. In an attempt to determine if this phenomenon occurred outside of the laboratory environment, the authors scaled up the physics experiment from a relatively small rock sample in a dry laboratory setting, to a large 7 metric tonne boulder comprised of Yosemite granite. This boulder was located in a natural, humid (above ground setting at Bass Lake, Ca. The boulder was instrumented with two Zonge Engineering, Model ANT4 induction type magnetometers, two Trifield Air Ion Counters, a surface charge detector, a geophone, a Bruker Model EM27 Fourier Transform Infra Red (FTIR spectrometer with Sterling cycle cooler, and various temperature sensors. The boulder was stressed over about 8 h using expanding concrete (Bustartm, until it fractured into three major pieces. The recorded data showed surface charge build up, magnetic pulsations, impulsive air conductivity changes, and acoustical cues starting about 5 h before the boulder actually broke. These magnetic and air conductivity pulse signatures resembled both the laboratory

  5. Use of (113)Cd NMR to probe the native metal binding sites in metalloproteins: an overview.

    Science.gov (United States)

    Armitage, Ian M; Drakenberg, Torbjörn; Reilly, Brian

    2013-01-01

    Our laboratories have actively published in this area for several years and the objective of this chapter is to present as comprehensive an overview as possible. Following a brief review of the basic principles associated with (113)Cd NMR methods, we will present the results from a thorough literature search for (113)Cd chemical shifts from metalloproteins. The updated (113)Cd chemical shift figure in this chapter will further illustrate the excellent correlation of the (113)Cd chemical shift with the nature of the coordinating ligands (N, O, S) and coordination number/geometry, reaffirming how this method can be used not only to identify the nature of the protein ligands in uncharacterized cases but also the dynamics at the metal binding site. Specific examples will be drawn from studies on alkaline phosphatase, Ca(2+) binding proteins, and metallothioneins.In the case of Escherichia coli alkaline phosphatase, a dimeric zinc metalloenzyme where a total of six metal ions (three per monomer) are involved directly or indirectly in providing the enzyme with maximal catalytic activity and structural stability, (113)Cd NMR, in conjunction with (13)C and (31)P NMR methods, were instrumental in separating out the function of each class of metal binding sites. Perhaps most importantly, these studies revealed the chemical basis for negative cooperativity that had been reported for this enzyme under metal deficient conditions. Also noteworthy was the fact that these NMR studies preceded the availability of the X-ray crystal structure.In the case of the calcium binding proteins, we will focus on two proteins: calbindin D(9k) and calmodulin. For calbindin D(9k) and its mutants, (113)Cd NMR has been useful both to follow actual changes in the metal binding sites and the cooperativity in the metal binding. Ligand binding to calmodulin has been studied extensively with (113)Cd NMR showing that the metal binding sites are not directly involved in the ligand binding. The (113)Cd

  6. NMR methods for beer characterization and quality control.

    Science.gov (United States)

    Rodrigues, J E; Gil, A M

    2011-12-01

    The use of high-resolution NMR spectroscopy in the brewing industry is described; most studies having aimed at assessing the composition of beer and its raw materials and correlating it to a variety of quality parameters. First, the application of NMR to the qualitative characterization of beer is reviewed, addressing both targeted and untargeted methods and focusing on both beer extracts and direct beer analysis. A subsequent chapter addresses the NMR studies, which envisage the development of new rapid methods for beer analysis and quality control, such as site-specific natural fractionation-NMR and multivariate data analysis methods for marker search or rapid compound quantification. Finally, possible future perspectives toward a deeper and more complete understanding of beer and its brewing process are discussed. Copyright © 2012 John Wiley & Sons, Ltd.

  7. 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...

  8. Interface Induced Growth and Transformation of Polymer-Conjugated Proto-Crystalline Phases in Aluminosilicate Hybrids: A Multiple-Quantum (23)Na-(23)Na MAS NMR Correlation Spectroscopy Study.

    Science.gov (United States)

    Brus, Jiri; Kobera, Libor; Urbanova, Martina; Doušová, Barbora; Lhotka, Miloslav; Koloušek, David; Kotek, Jiří; Čuba, Pavel; Czernek, Jiri; Dědeček, Jiří

    2016-03-22

    Nanostructured materials typically offer enhanced physicochemical properties because of their large interfacial area. In this contribution, we present a comprehensive structural characterization of aluminosilicate hybrids with polymer-conjugated nanosized zeolites specifically grown at the organic-inorganic interface. The inorganic amorphous Al-O-Si framework is formed by alkali-activated low-temperature transformation of metakaoline, whereas simultaneous copolymerization of organic comonomers creates a secondary epoxide network covalently bound to the aluminosilicate matrix. This secondary epoxide phase not only enhances the mechanical integrity of the resulting hybrids but also introduces additional binding sites accessible for compensating negative charge on the aluminosilicate framework. This way, the polymer network initiates growth and subsequent transformation of protocrystalline short-range ordered zeolite domains that are located at the organic-inorganic interface. By applying an experimental approach based on 2D (23)Na-(23)Na double-quantum (DQ) MAS NMR spectroscopy, we discovered multiple sodium binding sites in these protocrystalline domains, in which immobilized Na(+) ions form pairs or small clusters. It is further demonstrated that these sites, the local geometry of which allows for the pairing of sodium ions, are preferentially occupied by Pb(2+) ions during the ion exchange. The proposed synthesis protocol thus allows for the preparation of a novel type of geopolymer hybrids with polymer-conjugated zeolite phases suitable for capturing and storage of metal cations. The demonstrated (23)Na-(23)Na DQ MAS NMR combined with DFT calculations represents a suitable approach for understanding the role of Na(+) ions in aluminositicate solids and related inorganic-organic hybrids, particularly their specific arrangement and clustering at interfacial areas.

  9. Direct observation of millisecond to second motions in proteins by dipolar CODEX NMR spectroscopy.

    Science.gov (United States)

    Krushelnitsky, Alexey; deAzevedo, Eduardo; Linser, Rasmus; Reif, Bernd; Saalwächter, Kay; Reichert, Detlef

    2009-09-02

    We present a site-resolved study of slow (ms to s) motions in a protein in the solid (microcrystalline) state performed with the use of a modified version of the centerband-only detection of exchange (CODEX) NMR experiment. CODEX was originally based on measuring changes in molecular orientation by means of the chemical shift anisotropy (CSA) tensor, and in our modification, angular reorientations of internuclear vectors are observed. The experiment was applied to the study of slow (15)N-(1)H motions of the SH3 domain of chicken alpha-spectrin. The protein was perdeuterated with partial back-exchange of protons at labile sites. This allowed indirect (proton) detection of (15)N nuclei and thus a significant enhancement of sensitivity. The diluted proton system also made negligible proton-driven spin diffusion between (15)N nuclei, which interferes with the molecular exchange (motion) and hampers the acquisition of dynamic parameters. The experiment has shown that approximately half of the peaks in the 2D (15)N-(1)H correlation spectrum exhibit exchange in a different extent. The correlation time of the slow motion for most peaks is 1 to 3 s. This is the first NMR study of the internal dynamics of proteins in the solid state on the millisecond to second time scale with site-specific spectral resolution that provides both time-scale and geometry information about molecular motions.

  10. 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.

  11. Pulsed-Field NMR Measurements in Porous Media and Biological Systems

    Science.gov (United States)

    Latour, Lawrence Lance

    During the early stages of cerebral ischemia, the diffusion of water in the brain is decreased. The physical change in the tissue that is responsible for the decrease is unknown. Previous investigations have shown that pulsed-field-gradient nuclear magnetic resonance (PFG -NMR) measurements of diffusion in porous media contain information about microstructures. To advance the understanding of the PFG-NMR measurement of water diffusing in heterogeneous media, such as the brain, the studies presented in this dissertation were undertaken. Three groups of experiments are presented. The first set of experiments deals with the type of structural information that is available from PFG-NMR measurements of water diffusing in the pore-space of porous solids. In the second group of experiments, the diffusion of water in packed red blood cells, a model for diffusion in systems with permeable membranes, is studied. The third set of experiments deals with the diffusion of water in the rat brain during focal ischemia and cortical spreading depression. Measurements of time dependant diffusion in porous media indicate that the surface-to-pore-volume ratio and the free diffusion coefficient of the saturating fluid can be extracted from the short-time behavior and that the tortuosity of the pore space can be extracted from the long-time limit. Furthermore, the dynamic probability -of-return-to-the-origin can be obtained directly from the PFG-NMR amplitude. Experiments on packed red blood cells demonstrate that the measured diffusion coefficient is a sensitive function of both membrane permeability and extracellular volume fraction. Results on water diffusion measurements in the ischemic rat brain show the correlation between the region of the brain with decreased diffusion and the subsequently infarcted tissue and demonstrate the ability to predict the tissue salvaged by reperfusion. Also demonstrated is a decrease in diffusion following the transient depolarization of excitable

  12. NMR Studies of 3-Acylcamphor

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    NMR studies of some chiral 3-acyclcamphor were conducted.A complete assignment was given to 3-(4-pyridyl)carbonylcamphor by the 2D NMR technology.Assignments were also given to other b -diketones.The results showed that those 3-acylcamphors exist in the enol forms,while 2-benzoyl menthone exists in diketon form.

  13. Designing of high-resolution photoresists: use of modern NMR techniques for evaluating lithographic performance

    Indian Academy of Sciences (India)

    Debmalya Roy; P K Basu; P Raghunathan; S V Eswaran

    2004-06-01

    Applications of improved 1-D/ 2-D NMR spectroscopic techniques have been reviewed for quantitatively estimating the incorporation of different monomers and degree of linearity in resin microstructure. Comparison of the NMR data with those from lithography leads to a distinct correlation between resin microstructure and lithographic performance. A novel photoresist mechanism is proposed in a positive photoresist; also, using modern NMR techniques, the crosslinking mechanism in a negative photoresist has been studied.

  14. Quantification of pore size distribution using diffusion NMR: experimental design and physical insights.

    Science.gov (United States)

    Katz, Yaniv; Nevo, Uri

    2014-04-28

    Pulsed field gradient (PFG) diffusion NMR experiments are sensitive to restricted diffusion within porous media and can thus reveal essential microstructural information about the confining geometry. Optimal design methods of inverse problems are designed to select preferred experimental settings to improve parameter estimation quality. However, in pore size distribution (PSD) estimation using NMR methods as in other ill-posed problems, optimal design strategies and criteria are scarce. We formulate here a new optimization framework for ill-posed problems. This framework is suitable for optimizing PFG experiments for probing geometries that are solvable by the Multiple Correlation Function approach. The framework is based on a heuristic methodology designed to select experimental sets which balance between lowering the inherent ill-posedness and increasing the NMR signal intensity. This method also selects favorable discrete pore sizes used for PSD estimation. Numerical simulations performed demonstrate that using this framework greatly improves the sensitivity of PFG experimental sets to the pores' sizes. The optimization also sheds light on significant features of the preferred experimental sets. Increasing the gradient strength and varying multiple experimental parameters is found to be preferable for reducing the ill-posedness. We further evaluate the amount of pore size information that can be obtained by wisely selecting the duration of the diffusion and mixing times. Finally, we discuss the ramification of using single PFG or double PFG sequences for PSD estimation. In conclusion, the above optimization method can serve as a useful tool for experimenters interested in quantifying PSDs of different specimens. Moreover, the applicability of the suggested optimization framework extends far beyond the field of PSD estimation in diffusion NMR, and reaches design of sampling schemes of other ill-posed problems.

  15. Structural Biology: Practical NMR Applications

    CERN Document Server

    Teng, Quincy

    2005-01-01

    This textbook begins with an overview of NMR development and applications in biological systems. It describes recent developments in instrument hardware and methodology. Chapters highlight the scope and limitation of NMR methods. While detailed math and quantum mechanics dealing with NMR theory have been addressed in several well-known NMR volumes, chapter two of this volume illustrates the fundamental principles and concepts of NMR spectroscopy in a more descriptive manner. Topics such as instrument setup, data acquisition, and data processing using a variety of offline software are discussed. Chapters further discuss several routine stategies for preparing samples, especially for macromolecules and complexes. The target market for such a volume includes researchers in the field of biochemistry, chemistry, structural biology and biophysics.

  16. Dipeptide Structural Analysis Using Two-Dimensional NMR for the Undergraduate Advanced Laboratory

    Science.gov (United States)

    Gonzalez, Elizabeth; Dolino, Drew; Schwartzenburg, Danielle; Steiger, Michelle A.

    2015-01-01

    A laboratory experiment was developed to introduce students in either an organic chemistry or biochemistry lab course to two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy using simple biomolecules. The goal of this experiment is for students to understand and interpret the information provided by a 2D NMR spectrum. Students are…

  17. Dipeptide Structural Analysis Using Two-Dimensional NMR for the Undergraduate Advanced Laboratory

    Science.gov (United States)

    Gonzalez, Elizabeth; Dolino, Drew; Schwartzenburg, Danielle; Steiger, Michelle A.

    2015-01-01

    A laboratory experiment was developed to introduce students in either an organic chemistry or biochemistry lab course to two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy using simple biomolecules. The goal of this experiment is for students to understand and interpret the information provided by a 2D NMR spectrum. Students are…

  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. Characterisation of hydrogen bonding networks in RNAs via magic angle spinning solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Riedel, Kerstin; Leppert, Joerg; Ohlenschlaeger, Oliver; Goerlach, Matthias; Ramachandran, Ramadurai [Institut fuer Molekulare Biotechnologie, Abteilung Molekulare Biophysik/NMR-Spektroskopie (Germany)], E-mail: raman@imb-jena.de

    2005-04-15

    It is demonstrated that the spatial proximity of {sup 1}H nuclei in hydrogen bonded base-pairs in RNAs can be conveniently mapped via magic angle spinning solid state NMR experiments involving proton spin diffusion driven chemical shift correlation of low gamma nuclei such as the imino and amino nitrogens of nucleic acid bases. As different canonical and non-canonical base-pairing schemes encountered in nucleic acids are characterised by topologically different networks of proton dipolar couplings, different base-pairing schemes lead to characteristic cross-peak intensity patterns in such correlation spectra. The method was employed in a study of a 100 kDa RNA composed of 97 CUG repeats, or (CUG){sub 97} that has been implicated in the neuromuscular disease myotonic dystrophy. {sup 15}N-{sup 15}N chemical shift correlation studies confirm the presence of Watson-Crick GC base pairs in (CUG){sub 97}.

  20. 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.

  1. The effects of prior pain experience on neural correlates of empathy for pain: An fMRI study.

    Science.gov (United States)

    Preis, Mira A; Schmidt-Samoa, Carsten; Dechent, Peter; Kroener-Herwig, Birgit

    2013-03-01

    Neuroimaging studies have revealed partially shared neural substrates for both the actual experience of pain and empathy elicited by the pain of others. We examined whether prior pain exposure increased neural activity in the anterior midcingulate cortex (aMCC) and bilateral anterior insula (AI) as a correlate of empathy for pain. Participants (N=64: 32 women, 32 men) viewed pictures displaying exposure to pressure pain (pain pictures) and pictures without any cue of pain (neutral pictures). Prior to the experiment, half of the participants were exposed to the same pain stimulus as the one seen in the pain pictures (pain exposure condition); the other half had no such experience (touch exposure condition). A balanced sex ratio was kept, to investigate possible sex differences. In the region-of-interest analyses, participants of the pain exposure condition showed decreased activity in the right AI and the aMCC relative to participants of the touch exposure condition. While in men, no differences were found in relation to their exposure condition, women with pain exposure showed decreased activity in the aMCC and additionally, in bilateral AI. Based on the entire sample, whole brain analyses revealed stronger activation in the retrosplenial cortex, dorsomedial prefrontal cortex, and medial prefrontal cortex in the pain exposure condition. In conclusion, prior pain exposure did not increase, but decreased activity in regions regularly associated with empathy for pain. However, pain experience increased activity in regions associated with memory retrieval, perspective taking, and top-down emotion regulation, which might facilitate empathizing with others.

  2. 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.

  3. Prevalence of psychotic-like experiences in young adults with social anxiety disorder and correlation with affective dysregulation.

    Science.gov (United States)

    Armando, Marco; Lin, Ashleigh; Girardi, Paolo; Righetti, Valentino; Dario, Claudia; Saba, Riccardo; Decrescenzo, Franco; Mazzone, Luigi; Vicari, Stefano; Birchwood, Maximillian; Fiori Nastro, Paolo

    2013-12-01

    Social anxiety disorder (SAD) is associated with psychotic-like experiences (PLEs) and is a frequent diagnosis in the prodromal phases of psychosis. We investigated whether psychopathological factors could discriminate which subjects with SAD are more likely to develop PLEs. A sample of 128 young adults with SAD was split into two subsamples according to the presence of clinically relevant PLEs. Correlations between PLEs and other psychopathological markers were explored. The SAD with PLEs group showed higher level of anxiety, depression, and intolerance of uncertainty (IU) compared with the SAD without PLEs group. A limitation of this study is that the cross-sectional design precluded the analysis of causality. In our sample, the presence of PLEs is related to higher levels of depression, anxiety, and IU. The current findings are consistent with hypotheses suggesting that cognitive disturbances, together with social anxiety, may result in PLEs.

  4. Correlation between the adaptive response and individual sensitivity to monoepoxybutene in in vitro experiments on human lymphocytes.

    Science.gov (United States)

    Sasiadek, M; Paprocka-Borowicz, M

    1997-05-23

    Individual variations in the susceptibility to mutagenic/carcinogenic chemicals depend on the activity of xenobiotic metabolizing enzymes and on DNA- and chromosome-damage repair systems. Monoepoxybutene (MEB) is a genotoxic metabolite of 1,3-butadiene (BD), which has been classified as a probable carcinogen in humans. The purpose of the present study was to investigate by in vitro experiments on human whole blood lymphocytes (WBL), whether an individual sensitivity to MEB correlates with the adaptive response to the tested agent. In the analyzed group, 8.3% of blood donors were relatively sensitive to MEB. The comparison of SCE induction in cultures pretreated and not pretreated with an adaptive dose (AD) of MEB showed, that there was an adaptive response to MEB. The adaptive response in the group of relatively sensitive donors was similar to that of the relatively resistant ones. This result suggests that individual sensitivity to the tested agent and adaptive response depend on different biological mechanisms.

  5. Separation of components of a broad 1H-NMR composite signal by means of nutation experiments under low amplitude radiofrequency fields. Application to the water signal in synthetic clays; Developpement et mise en oeuvre d'une nouvelle methode fondee sur le phenomene de nutation pour la decomposition d'un signal composite de resonance magnetique nucleaire. Application au signal 1h de l'eau dans des argiles synthetiques

    Energy Technology Data Exchange (ETDEWEB)

    Trausch, G

    2006-11-15

    Nowadays, geologic nuclear waste storage is envisioned according to a multi-layer model which implies clays. The latter exhibit retention capacities and low permeability to water; that is why they are considered as a good candidate for engineered barriers to radioactive waste disposal. The present work here aims at studying transport phenomena which involve water molecules in three samples of synthetic clays (two of them exhibiting a Pake doublet) by means of Nuclear Magnetic Resonance (NMR). The first chapter describes structural properties of clays and presents the state-of-art of NMR and other experimental techniques used for such systems. The second chapter deals with the interpretation and the simulation of each conventional proton spectrum. These simulations allow us to evidence and to characterize a chemical exchange phenomenon. The third chapter is dedicated to original nutation experiments performed under low radiofrequency field in the case of broad NMR signal. It is shown that this type of NMR experiment can yield the number and the proportion of each species contributing to the whole signal. These results are exploited in the fourth chapter for processing relaxation and diffusion experiments. Finally, the diffusion coefficients obtained by NMR are divided by a factor 4 with respect to pure water while relaxation rates are two orders of magnitude greater. (author)

  6. Fiction feelings in Harry Potter: haemodynamic response in the mid-cingulate cortex correlates with immersive reading experience.

    Science.gov (United States)

    Hsu, Chun-Ting; Conrad, Markus; Jacobs, Arthur M

    2014-12-03

    Immersion in reading, described as a feeling of 'getting lost in a book', is a ubiquitous phenomenon widely appreciated by readers. However, it has been largely ignored in cognitive neuroscience. According to the fiction feeling hypothesis, narratives with emotional contents invite readers more to be empathic with the protagonists and thus engage the affective empathy network of the brain, the anterior insula and mid-cingulate cortex, than do stories with neutral contents. To test the hypothesis, we presented participants with text passages from the Harry Potter series in a functional MRI experiment and collected post-hoc immersion ratings, comparing the neural correlates of passage mean immersion ratings when reading fear-inducing versus neutral contents. Results for the conjunction contrast of baseline brain activity of reading irrespective of emotional content against baseline were in line with previous studies on text comprehension. In line with the fiction feeling hypothesis, immersion ratings were significantly higher for fear-inducing than for neutral passages, and activity in the mid-cingulate cortex correlated more strongly with immersion ratings of fear-inducing than of neutral passages. Descriptions of protagonists' pain or personal distress featured in the fear-inducing passages apparently caused increasing involvement of the core structure of pain and affective empathy the more readers immersed in the text. The predominant locus of effects in the mid-cingulate cortex seems to reflect that the immersive experience was particularly facilitated by the motor component of affective empathy for our stimuli from the Harry Potter series featuring particularly vivid descriptions of the behavioural aspects of emotion.

  7. Movement disorder society unified Parkinson disease rating scale experiences in daily living: longitudinal changes and correlation with other assessments.

    Science.gov (United States)

    Lang, Anthony E; Eberly, Shirley; Goetz, Christopher G; Stebbins, Glenn; Oakes, David; Marek, Ken; Ravina, Bernard; Tanner, Caroline M; Shoulson, Ira

    2013-12-01

    The Movement Disorder Society (MDS) commissioned a revision of the UPDRS with the goals of improving instructions and definitions, more accurately evaluating milder features, and assessing patient-reported outcomes and nonmotor features. To date, no study has evaluated longitudinal changes in components of the MDS-UPDRS over time or correlated these with changes in other scales of various symptoms. We assessed Parts I and II of the MDS-UPDRS (non-Motor and Motor Experiences of Daily Living [nM-EDL, M-EDL]) as well as a number of other scales of motor, cognitive and behavioral function in a large population of patients (n = 383) with early- to mid-stage Parkinson's disease (PD) who had previously participated in a trial of a putative disease-modifying agent. Both parts of a MDS-UPDRS showed significant change over the 3-year follow-up period, with M-EDL scores declining to a greater extent than nM-EDL. Both the scores and their changes over time correlated relatively well with other rating scales of similar disease aspects. Modest correlations with the original version of the UPDRS supported the increased attention to nonmotor symptoms as well as milder levels of severity in the MDS-UPDRS. The M-EDL was much more sensitive to change over time in these early- to mid-stage patients than the original UPDRS Activities of Daily Living (ADL) scale. Finally, we showed no change over time in a small group of individuals with dopamine transporter single-photon emission computed tomography scans without evidence for dopamine deficiency. The nM-EDL and M-EDL components of the MDS-UPDRS provide an effective, relevant measure of change in the broad spectrum of symptoms of PD over the first decade of the disease. © 2013 Movement Disorder Society.

  8. Quantum Correlations in Mixed-State Metrology

    Directory of Open Access Journals (Sweden)

    Kavan Modi

    2011-12-01

    Full Text Available We analyze the effects of quantum correlations, such as entanglement and discord, on the efficiency of phase estimation by studying four quantum circuits that can be readily implemented using NMR techniques. These circuits define a standard strategy of repeated single-qubit measurements, a classical strategy where only classical correlations are allowed, and two quantum strategies where nonclassical correlations are allowed. In addition to counting space (number of qubits and time (number of gates requirements, we introduce mixedness as a key constraint of the experiment. We compare the efficiency of the four strategies as a function of the mixedness parameter. We find that the quantum strategy gives sqrt[N] enhancement over the standard strategy for the same amount of mixedness. This result applies even for highly mixed states that have nonclassical correlations but no entanglement.

  9. NMR and Chemometric Characterization of Vacuum Residues and Vacuum Gas Oils from Crude Oils of Different Origin

    Directory of Open Access Journals (Sweden)

    Jelena Parlov Vuković

    2015-03-01

    Full Text Available NMR spectroscopy in combination with statistical methods was used to study vacuum residues and vacuum gas oils from 32 crude oils of different origin. Two chemometric metodes were applied. Firstly, principal component analysis on complete spectra was used to perform classification of samples and clear distinction between vacuum residues and vacuum light and heavy gas oils were obtained. To quantitatively predict the composition of asphaltenes, principal component regression models using areas of resonance signals spaned by 11 frequency bins of the 1H NMR spectra were build. The first 5 principal components accounted for more than 94 % of variations in the input data set and coefficient of determination for correlation between measured and predicted values was R2 = 0.7421. Although this value is not significant, it shows the underlying linear dependence in the data. Pseudo two-dimensional DOSY NMR experiments were used to assess the composition and structural properties of asphaltenes in a selected crude oil and its vacuum residue on the basis of their different hydrodynamic behavior and translational diffusion coefficients. DOSY spectra showed the presence of several asphaltene aggregates differing in size and interactions they formed. The obtained results have shown that NMR techniques in combination with chemometrics are very useful to analyze vacuum residues and vacuum gas oils. Furthermore, we expect that our ongoing investigation of asphaltenes from crude oils of different origin will elucidate in more details composition, structure and properties of these complex molecular systems.

  10. Interfacial Ca2+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced 43Ca NMR spectroscopy

    Science.gov (United States)

    Lee, Daniel; Leroy, César; Crevant, Charlène; Bonhomme-Coury, Laure; Babonneau, Florence; Laurencin, Danielle; Bonhomme, Christian; De Paëpe, Gaël

    2017-01-01

    The interfaces within bones, teeth and other hybrid biomaterials are of paramount importance but remain particularly difficult to characterize at the molecular level because both sensitive and selective techniques are mandatory. Here, it is demonstrated that unprecedented insights into calcium environments, for example the differentiation of surface and core species of hydroxyapatite nanoparticles, can be obtained using solid-state NMR, when combined with dynamic nuclear polarization. Although calcium represents an ideal NMR target here (and de facto for a large variety of calcium-derived materials), its stable NMR-active isotope, calcium-43, is a highly unreceptive probe. Using the sensitivity gains from dynamic nuclear polarization, not only could calcium-43 NMR spectra be obtained easily, but natural isotopic abundance 2D correlation experiments could be recorded for calcium-43 in short experimental time. This opens perspectives for the detailed study of interfaces in nanostructured materials of the highest biological interest as well as calcium-based nanosystems in general. PMID:28128197

  11. Structural characterization of homogalacturonan by NMR spectroscopy - assignment of reference compounds

    DEFF Research Database (Denmark)

    Petersen, Bent O.; Meier, Sebastian; Duus, Jens Øllgaard;

    2008-01-01

    Complete assignment of 1H and 13C NMR of six hexagalactopyranuronic acids with varying degree and pattern of methyl esterification is reported. The NMR experiments were run at room temperature using approximately 2 mg of sample making this method convenient for studying the structure of homogalac......Complete assignment of 1H and 13C NMR of six hexagalactopyranuronic acids with varying degree and pattern of methyl esterification is reported. The NMR experiments were run at room temperature using approximately 2 mg of sample making this method convenient for studying the structure...

  12. Study of molecular interactions with 13C DNP-NMR.

    Science.gov (United States)

    Lerche, Mathilde H; Meier, Sebastian; Jensen, Pernille R; Baumann, Herbert; Petersen, Bent O; Karlsson, Magnus; Duus, Jens Ø; Ardenkjaer-Larsen, Jan H

    2010-03-01

    NMR spectroscopy is an established, versatile technique for the detection of molecular interactions, even when these interactions are weak. Signal enhancement by several orders of magnitude through dynamic nuclear polarization alleviates several practical limitations of NMR-based interaction studies. This enhanced non-equilibrium polarization contributes sensitivity for the detection of molecular interactions in a single NMR transient. We show that direct (13)C NMR ligand binding studies at natural isotopic abundance of (13)C gets feasible in this way. Resultant screens are easy to interpret and can be performed at (13)C concentrations below muM. In addition to such ligand-detected studies of molecular interaction, ligand binding can be assessed and quantified with enzymatic assays that employ hyperpolarized substrates at varying enzyme inhibitor concentrations. The physical labeling of nuclear spins by hyperpolarization thus provides the opportunity to devise fast novel in vitro experiments with low material requirement and without the need for synthetic modifications of target or ligands.

  13. Observations of Quantum Dynamics by Solution-State NMR Spectroscopy

    CERN Document Server

    Pravia, M A; Weinstein, Yu S; Price, M D; Teklemariam, G; Nelson, R J; Sharf, Y; Somaroo, S S; Tseng, C H; Havel, T F; Cory, D G

    1999-01-01

    NMR is emerging as a valuable testbed for the investigation of foundational questions in quantum mechanics. The present paper outlines the preparation of a class of mixed states, called pseudo-pure states, that emulate pure quantum states in the highly mixed environment typically used to describe solution-state NMR samples. It also describes the NMR observation of spinor behavior in spin 1/2 nuclei, the simulation of wave function collapse using a magnetic field gradient, the creation of entangled (or Bell) pseudo-pure states, and a brief discussion of quantum computing logic gates, including the Quantum Fourier Transform. These experiments show that liquid-state NMR can be used to demonstrate quantum dynamics at a level suitable for laboratory exercises.

  14. Imprinting of idiosyncratic experience in cortical sensory maps: neural substrates of representational remodeling and correlative perceptual changes.

    Science.gov (United States)

    Xerri, Christian

    2008-09-01

    Over the past 30 years, extensive research has been conducted in the field of cortical plasticity, under the impetus of seminal studies showing that the mature brain retains a capacity to reorganize the morphological and functional architecture of its neural circuits in order to adapt to environmental changes and mediate functional recovery following injury. Much effort has been focused on determining how idiosyncratic experience translates into molecular, structural and physiological changes in the sensory and motor representations embedded within cortical networks. The wealth of data generated by a broad spectrum of experimental manipulations has allowed unprecedented progress in our understanding of the physiological processes and neuroplasticity mechanisms underlying cortical representational remodeling. The objective of the present review is to put various facets of cortical map plasticity into perspective so as to examine possible links between changes occurring at multiple scales of the neural organization of the mature brain. The main focus is on neural substrates that mediate the instructive influence of experience and behavioral context on cortical reorganization, and perceptual correlates of representational remodeling.

  15. Direct Numerical Simulation of Fracture Behaviour for Random Short Wood Fibres Reinforced Composites, Comparison with Digital Image Correlation Experiments

    Science.gov (United States)

    Shen, M.; Touchard, F.; Bezine, G.; Brillaud, J.

    2010-06-01

    The work is to predict fracture behaviour of bio-composites from the tensile properties of its components. In this work, we have realized a direct numerical simulation of fracture behaviour for random short spruce fibers reinforced composites. For calculations, wood fibers have been considered as linear elastic bodies, polypropylene matrix as an elastic-plastic material. Then, numerical results have been compared with experimental results that have been obtained by digital image correlation. This comparison indicates that random fiber FE model of random short spruce fibers reinforced composites can be able to fairly reflect the influence of random fibers microstructure in the composite on its fracture behavior. The calculation of both random fiber and homogeneous FE model and their comparison with experiments show that the average values of J-integral in a region in the front of the crack tip from both numerical FE models are in good agreement with the average J value of DIC experiment in the same region when the numerical and experimental CT specimens of the short spruce fiber reinforced composite are subjected to the same extension at their loading point.

  16. Direct Numerical Simulation of Fracture Behaviour for Random Short Wood Fibres Reinforced Composites, Comparison with Digital Image Correlation Experiments

    Directory of Open Access Journals (Sweden)

    Brillaud J.

    2010-06-01

    Full Text Available The work is to predict fracture behaviour of bio-composites from the tensile properties of its components. In this work, we have realized a direct numerical simulation of fracture behaviour for random short spruce fibers reinforced composites. For calculations, wood fibers have been considered as linear elastic bodies, polypropylene matrix as an elastic-plastic material. Then, numerical results have been compared with experimental results that have been obtained by digital image correlation. This comparison indicates that random fiber FE model of random short spruce fibers reinforced composites can be able to fairly reflect the influence of random fibers microstructure in the composite on its fracture behavior. The calculation of both random fiber and homogeneous FE model and their comparison with experiments show that the average values of J-integral in a region in the front of the crack tip from both numerical FE models are in good agreement with the average J value of DIC experiment in the same region when the numerical and experimental CT specimens of the short spruce fiber reinforced composite are subjected to the same extension at their loading point.

  17. High-resolution (19)F MAS NMR spectroscopy: structural disorder and unusual J couplings in a fluorinated hydroxy-silicate.

    Science.gov (United States)

    Griffin, John M; Yates, Jonathan R; Berry, Andrew J; Wimperis, Stephen; Ashbrook, Sharon E

    2010-11-10

    High-resolution (19)F magic angle spinning (MAS) NMR spectroscopy is used to study disorder and bonding in a crystalline solid. (19)F MAS NMR reveals four distinct F sites in a 50% fluorine-substituted deuterated hydrous magnesium silicate (clinohumite, 4Mg(2)SiO(4)·Mg(OD(1-x)F(x))(2) with x = 0.5), indicating extensive structural disorder. The four (19)F peaks can be assigned using density functional theory (DFT) calculations of NMR parameters for a number of structural models with a range of possible local F environments generated by F(-)/OH(-) substitution. These assignments are supported by two-dimensional (19)F double-quantum MAS NMR experiments that correlate F sites based on either spatial proximity (via dipolar couplings) or through-bond connectivity (via scalar, or J, couplings). The observation of (19)F-(19)F J couplings is unexpected as the fluorines coordinate Mg atoms and the Mg-F interaction is normally considered to be ionic in character (i.e., there is no formal F-Mg-F covalent bonding arrangement). However, DFT calculations predict significant (19)F-(19)F J couplings, and these are in good agreement with the splittings observed in a (19)F J-resolved MAS NMR experiment. The existence of these J couplings is discussed in relation to both the nature of bonding in the solid state and the occurrence of so-called "through-space" (19)F-(19)F J couplings in solution. Finally, we note that we have found similar structural disorder and spin-spin interactions in both synthetic and naturally occurring clinohumite samples.

  18. Quantitative strain analysis in analogue modelling experiments: insights from X-ray computed tomography and tomographic image correlation

    Science.gov (United States)

    Adam, J.; Klinkmueller, M.; Schreurs, G.; Wieneke, B.

    2009-04-01

    The combination of scaled analogue modelling experiments, advanced research in analogue material mechanics (Lohrmann et al. 2003, Panien et al. 2006), X-ray computed tomography and new high-resolution deformation monitoring techniques (2D/3D Digital Image Correlation) is a new powerful tool not only to examine the evolution and interaction of faulting in analogue models, but also to evaluate relevant controlling factors such as mechanics, sedimentation, erosion and climate. This is of particular interest for applied problems in the energy sector (e.g., structurally complex reservoirs, LG & CO2 underground storage) because the results are essential for geological and seismic interpretation as well as for more realistically constrained fault/fracture simulations and reservoir characterisation. X-ray computed tomography (CT) analysis has been successfully applied to analogue models since the late 1980s. This technique permits visualisation of the interior of an analogue model without destroying it. Technological improvements have resulted in more powerful X-ray CT scanners that allow periodic acquisition of volumetric data sets thus making it possible to follow the 3-D evolution of the model structures with time (e.g. Schreurs et al., 2002, 2003). Optical strain monitoring (Digital Image Correlation, DIC) in analogue experiments (Adam et al., 2005) represents an important advance in quantitative physical modelling and in helping to understand non-linear rock deformation processes. Optical non-intrusive 2D/3D strain and surface flow analysis by DIC is a new methodology in physical modelling that enables the complete quantification of localised and distributed model deformation. The increase in spatial/temporal strain data resolution of several orders of magnitude makes physical modelling - used for decades to visualize the kinematic processes of geological deformation processes - a unique research tool to determine what fundamental physical processes control tectonic

  19. Quantitative time- and frequency-domain analysis of the two-pulse COSY revamped by asymmetric Z-gradient echo detection NMR experiment: Theoretical and experimental aspects, time-zero data truncation artifacts, and radiation damping.

    Science.gov (United States)

    Kirsch, Stefan; Hull, William E

    2008-07-28

    The two-pulse COSY revamped by asymmetric Z-gradient echo detection (CRAZED) NMR experiment has the basic form 90 degrees -Gdelta-t(rec)-beta-nGdelta-t(rec)-FID, with a phase-encoding gradient pulse G of length delta applied during the evolution time tau for transverse magnetization, readout pulse beta, rephasing gradient nGdelta, and recovery time t(rec) prior to acquisition of the free-induction decay. Based on the classical treatment of the spatially modulated dipolar demagnetizing field and without invoking intermolecular multiple-quantum coherence, a new formulation of the first-order approximation for the theoretical solution of the nonlinear Bloch equations has been developed. The nth-order CRAZED signal can be expressed as a simple product of a scaling function C(n)(beta,tau) and a signal amplitude function A(n)(t), where the domain t begins immediately after the beta pulse. Using a single-quantum coherence model, a generalized rf phase shift function has also been developed, which explains all known phase behavior, including nth-order echo selection by phase cycling. Details of the derivations are provided in two appendices as supplementary material. For n>1, A(n)(t) increases from zero to a maximum value at t=t(max) before decaying and can be expressed as a series of n exponential decays with antisymmetric binomial coefficients. Fourier transform gives an antisymmetric binomial series of Lorentzians, where the composite lineshape exhibits negative wings, zero integral, and a linewidth that decreases with n. Analytical functions are presented for t(max) and A(n)(t(max)) and for estimating the maximal percent error incurred for A(n)(t(max)) when using the first-order model. The preacquisition delay Delta=delta+t(rec) results in the loss of the data points for t=0 to Delta. Conventional Fourier transformation produces time-zero truncation artifacts (reduced negative wing amplitude, nonzero integral, and reduced effective T(2) ( *)), which can be avoided by

  20. The development of solid-state NMR of membrane proteins.

    Science.gov (United States)

    Opella, Stanley J

    Most biological functions are carried out in supramolecular assemblies. As a result of their slow reorientation in solution, these assemblies have been resistant to the widely employed solution NMR approaches. The development of solid-state NMR to first of all overcome the correlation time problem and then obtain informative high-resolution spectra of proteins in supramolecular assemblies, such as virus particles and membranes, is described here. High resolution solid-state NMR is deeply intertwined with the history of NMR, and the seminal paper was published in 1948. Although the general principles were understood by the end of the 1950s, it has taken more than fifty years for instrumentation and experimental methods to become equal to the technical problems presented by the biological assemblies of greatest interest. It is now possible to obtain atomic resolution structures of viral coat proteins in virus particles and membrane proteins in phospholipid bilayers by oriented sample solid-state NMR methods. The development of this aspect of the field of solid-state NMR is summarized in this review article.

  1. nmr spectroscopic study and dft calculations of giao nmr shieldings ...

    African Journals Online (AJOL)

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    various fields of science and industry such as microelectronic and aerospace ... GIAO/DFT (Gauge Including Atomic Orbitals/Density Functional Theory) approach is .... successfully by using NMR and quantum chemical calculations.

  2. Annual reports on NMR spectroscopy

    CERN Document Server

    Webb, Graham A; McCarthy, M J

    1995-01-01

    Over recent years, no other technique has grown to such importance as that of NMR spectroscopy. It is used in all branches of science where precise structural determination is required and where the nature of interactions and reactions in solution is being studied. Annual Reports on NMR Spectroscopy has established itself as a means for the specialist and non-specialist alike to become familiar with new applications of the technique in all branches of chemistry, including biochemistry, and pharmaceutics. This volume focuses on theoretical aspects of NMR nuclear shielding and on applications of

  3. Flow units from integrated WFT and NMR data

    Energy Technology Data Exchange (ETDEWEB)

    Kasap, E.; Altunbay, M.; Georgi, D.

    1997-08-01

    Reliable and continuous permeability profiles are vital as both hard and soft data required for delineating reservoir architecture. They can improve the vertical resolution of seismic data, well-to-well stratigraphic correlations, and kriging between the well locations. In conditional simulations, permeability profiles are imposed as the conditioning data. Variograms, covariance functions and other geostatistical indicators are more reliable when based on good quality permeability data. Nuclear Magnetic Resonance (NMR) logging and Wireline Formation Tests (WFT) separately generate a wealth of information, and their synthesis extends the value of this information further by providing continuous and accurate permeability profiles without increasing the cost. NMR and WFT data present a unique combination because WFTs provide discrete, in situ permeability based on fluid-flow, whilst NMR responds to the fluids in the pore space and yields effective porosity, pore-size distribution, bound and moveable fluid saturations, and permeability. The NMR permeability is derived from the T{sub 2}-distribution data. Several equations have been proposed to transform T{sub 2} data to permeability. Regardless of the transform model used, the NMR-derived permeabilities depend on interpretation parameters that may be rock specific. The objective of this study is to integrate WFT permeabilities with NMR-derived, T{sub 2} distribution-based permeabilities and thereby arrive at core quality, continuously measured permeability profiles. We outlined the procedures to integrate NMR and WFT data and applied the procedure to a field case. Finally, this study advocates the use of hydraulic unit concepts to extend the WFT-NMR derived, core quality permeabilities to uncored intervals or uncored wells.

  4. Characterizations of Some N-Substituted-salicylhydrazide in Mixtures by NMR Diffusion Ordered Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    张芳; 于贤勇; 陈忠; 林深; 刘世雄

    2003-01-01

    Several novel N-substituted-salicylhydrazide ligands, most of which are difficult to be purified or recrystallized so that their chemical configurations can not be confirmed by conventional NMR and/or X-ray diffraction techniques, were synthesized in this experiment, and their chemical configurations in mixture were analyzed and characterized by 2D NMR diffusion ordered spectroscopy (DOSY), a labor-saving virtual separation based on diffusion properties,together with several routine NMR techniques.

  5. NMR methodologies for studying mitochondrial bioenergetics.

    Science.gov (United States)

    Alves, Tiago C; Jarak, Ivana; Carvalho, Rui A

    2012-01-01

    Nuclear magnetic resonance (NMR) spectroscopy is a technique with an increasing importance in the study of metabolic diseases. Its initial important role in the determination of chemical structures (1, 2) has been considerably overcome by its potential for the in vivo study of metabolism (3-5). The main characteristic that makes this technique so attractive is its noninvasiveness. Only nuclei capable of transitioning between energy states, in the presence of an intense and constant magnetic field, are studied. This includes abundant nuclei such as proton ((1)H) and phosphorous ((31)P), as well as stable isotopes such as deuterium ((2)H) and carbon 13 ((13)C). This allows a wide range of applications that vary from the determination of water distribution in tissues (as obtained in a magnetic resonance imaging scan) to the calculation of metabolic fluxes under ex vivo and in vivo conditions without the need to use radioactive tracers or tissue biopsies (as in a magnetic resonance spectroscopy (MRS) scan). In this chapter, some technical aspects of the methodology of an NMR/MRS experiment as well as how it can be used to study mitochondrial bioenergetics are overviewed. Advantages and disadvantages of in vivo MRS versus high-resolution NMR using proton high rotation magic angle spinning (HRMAS) of tissue biopsies and tissue extracts are also discussed.

  6. Earth's field NMR; a surface moisture detector?

    Science.gov (United States)

    Fukushima, Eiichi; Altobelli, Stephen; McDowell, Andrew; Zhang, Tongsheng

    2012-10-01

    Earth's field NMR (EFNMR), being free of magnets, would be an ideal teaching medium as well as a mobile NMR technique except for its weak S/N. The common EFNMR apparatus uses a powerful prepolarization field to enhance the spin magnetization before the experiment. We introduce a coil design geared to larger but manageable samples with sufficient sensitivity without prepolarization to move EFNMR closer to routine use and to provide an inexpensive teaching tool. Our coil consists of parallel wires spread out on a plywood to form a current sheet with the current return wires separated so they will not influence the main part of the coil assembly. The sensitive region is a relatively thin region parallel to the coil and close to it. A single turn of the coil is wound to be topologically equivalent to a figure-8. The two crossing segments in the center of a figure-8 form two of the parallel wires of the flat coil. Thus, a two-turn figure-8 has four crossing wires so its topologically equivalent coil will have four parallel wires with currents in phase. Together with the excellent sensitivity, this coil offers outstanding interference rejection because of the figure-8 geometry. An example of such a coil has 328 parallel wires covering a ˜1 meter square plywood which yields a good NMR signal from 26 liters of water spread out roughly over the area of the coil in less than one minute in a nearby park.

  7. 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...

  8. Determining pore length scales and pore surface relaxivity of rock cores by internal magnetic fields modulation at 2MHz NMR.

    Science.gov (United States)

    Liu, Huabing; Nogueira d'Eurydice, Marcel; Obruchkov, Sergei; Galvosas, Petrik

    2014-09-01

    Pore length scales and pore surface relaxivities of rock cores with different lithologies were studied on a 2MHz Rock Core Analyzer. To determine the pore length scales of the rock cores, the high eigenmodes of spin bearing molecules satisfying the diffusion equation were detected with optimized encoding periods in the presence of internal magnetic fields Bin. The results were confirmed using a 64MHz NMR system, which supports the feasibility of high eigenmode detection at fields as low as 2MHz. Furthermore, this methodology was combined with relaxometry measurements to a two-dimensional experiment, which provides correlation between pore length and relaxation time. This techniques also yields information on the surface relaxivity of the rock cores. The estimated surface relaxivities were then compared to the results using an independent NMR method.

  9. Low-power broadband solid-state MAS NMR of 14N

    Science.gov (United States)

    Pell, Andrew J.; Sanders, Kevin J.; Wegner, Sebastian; Pintacuda, Guido; Grey, Clare P.

    2017-05-01

    We propose two broadband pulse schemes for 14N solid-state magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) that achieves (i) complete population inversion and (ii) efficient excitation of the double-quantum spectrum using low-power single-sideband-selective pulses. We give a comprehensive theoretical description of both schemes using a common framework that is based on the jolting-frame formalism of Caravatti et al. [J. Magn. Reson. 55, 88 (1983)]. This formalism is used to determine for the first time that we can obtain complete population inversion of 14N under low-power conditions, which we do here using single-sideband-selective adiabatic pulses. It is then used to predict that double-quantum coherences can be excited using low-power single-sideband-selective pulses. We then proceed to design a new experimental scheme for double-quantum excitation. The final double-quantum excitation pulse scheme is easily incorporated into other NMR experiments, as demonstrated here for double quantum-single quantum 14N correlation spectroscopy, and 1H-14N dipolar heteronuclear multiple-quantum correlation experiments. These pulses and irradiation schemes are evaluated numerically using simulations on single crystals and full powders, as well as experimentally on ammonium oxalate ((NH4)2C2O4) at moderate MAS and glycine at ultra-fast MAS. The performance of these new NMR methods is found to be very high, with population inversion efficiencies of 100% and double-quantum excitation efficiencies of 30%-50%, which are hitherto unprecedented for the low radiofrequency field amplitudes, up to the spinning frequency, that are used here.

  10. Quantitative NMR spectroscopy for gas analysis for production of primary reference gas mixtures.

    Science.gov (United States)

    Meyer, K; Rademann, K; Panne, U; Maiwald, M

    2017-02-01

    Due to its direct correlation to the number of spins within a sample quantitative NMR spectroscopy (qNMR) is a promising method with absolute comparison abilities in complex systems in technical, as well as metrological applications. Most of the samples studied with qNMR are in liquid state in diluted solutions, while gas-phase applications represent a rarely applied case. Commercially available NMR equipment was used for purity assessment of liquid and liquefied hydrocarbons serving as raw materials for production of primary reference gas standards. Additionally, gas-phase studies were performed within an online NMR flow probe, as well as in a high-pressure NMR setup to check feasibility as verification method for the composition of gas mixtures. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. Reaction monitoring using hyperpolarized NMR with scaling of heteronuclear couplings by optimal tracking

    Science.gov (United States)

    Zhang, Guannan; Schilling, Franz; Glaser, Steffen J.; Hilty, Christian

    2016-11-01

    Off-resonance decoupling using the method of Scaling of Heteronuclear Couplings by Optimal Tracking (SHOT) enables determination of heteronuclear correlations of chemical shifts in single scan NMR spectra. Through modulation of J-coupling evolution by shaped radio frequency pulses, off resonance decoupling using SHOT pulses causes a user-defined dependence of the observed J-splitting, such as the splitting of 13C peaks, on the chemical shift offset of coupled nuclei, such as 1H. Because a decoupling experiment requires only a single scan, this method is suitable for characterizing on-going chemical reactions using hyperpolarization by dissolution dynamic nuclear polarization (D-DNP). We demonstrate the calculation of [13C, 1H] chemical shift correlations of the carbanionic active sites from hyperpolarized styrene polymerized using sodium naphthalene as an initiator. While off resonance decoupling by SHOT pulses does not enhance the resolution in the same way as a 2D NMR spectrum would, the ability to obtain the correlations in single scans makes this method ideal for determination of chemical shifts in on-going reactions on the second time scale. In addition, we present a novel SHOT pulse that allows to scale J-splittings 50% larger than the respective J-coupling constant. This feature can be used to enhance the resolution of the indirectly detected chemical shift and reduce peak overlap, as demonstrated in a model reaction between p-anisaldehyde and isobutylamine. For both pulses, the accuracy is evaluated under changing signal-to-noise ratios (SNR) of the peaks from reactants and reaction products, with an overall standard deviation of chemical shift differences compared to reference spectra of 0.02 ppm when measured on a 400 MHz NMR spectrometer. Notably, the appearance of decoupling side-bands, which scale with peak intensity, appears to be of secondary importance.

  12. β-NMR sample optimization

    CERN Document Server

    Zakoucka, Eva

    2013-01-01

    During my summer student programme I was working on sample optimization for a new β-NMR project at the ISOLDE facility. The β-NMR technique is well-established in solid-state physics and just recently it is being introduced for applications in biochemistry and life sciences. The β-NMR collaboration will be applying for beam time to the INTC committee in September for three nuclei: Cu, Zn and Mg. Sample optimization for Mg was already performed last year during the summer student programme. Therefore sample optimization for Cu and Zn had to be completed as well for the project proposal. My part in the project was to perform thorough literature research on techniques studying Cu and Zn complexes in native conditions, search for relevant binding candidates for Cu and Zn applicable for ß-NMR and eventually evaluate selected binding candidates using UV-VIS spectrometry.

  13. Integrative NMR for biomolecular research.

    Science.gov (United States)

    Lee, Woonghee; Cornilescu, Gabriel; Dashti, Hesam; Eghbalnia, Hamid R; Tonelli, Marco; Westler, William M; Butcher, Samuel E; Henzler-Wildman, Katherine A; Markley, John L

    2016-04-01

    NMR spectroscopy is a powerful technique for determining structural and functional features of biomolecules in physiological solution as well as for observing their intermolecular interactions in real-time. However, complex steps associated with its practice have made the approach daunting for non-specialists. We introduce an NMR platform that makes biomolecular NMR spectroscopy much more accessible by integrating tools, databases, web services, and video tutorials that can be launched by simple installation of NMRFAM software packages or using a cross-platform virtual machine that can be run on any standard laptop or desktop computer. The software package can be downloaded freely from the NMRFAM software download page ( http://pine.nmrfam.wisc.edu/download_packages.html ), and detailed instructions are available from the Integrative NMR Video Tutorial page ( http://pine.nmrfam.wisc.edu/integrative.html ).

  14. Compact orthogonal NMR field sensor

    Science.gov (United States)

    Gerald, II, Rex E.; Rathke, Jerome W [Homer Glen, IL

    2009-02-03

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

  15. Nonuniform sampling and maximum entropy reconstruction in multidimensional NMR.

    Science.gov (United States)

    Hoch, Jeffrey C; Maciejewski, Mark W; Mobli, Mehdi; Schuyler, Adam D; Stern, Alan S

    2014-02-18

    NMR spectroscopy is one of the most powerful and versatile analytic tools available to chemists. The discrete Fourier transform (DFT) played a seminal role in the development of modern NMR, including the multidimensional methods that are essential for characterizing complex biomolecules. However, it suffers from well-known limitations: chiefly the difficulty in obtaining high-resolution spectral estimates from short data records. Because the time required to perform an experiment is proportional to the number of data samples, this problem imposes a sampling burden for multidimensional NMR experiments. At high magnetic field, where spectral dispersion is greatest, the problem becomes particularly acute. Consequently multidimensional NMR experiments that rely on the DFT must either sacrifice resolution in order to be completed in reasonable time or use inordinate amounts of time to achieve the potential resolution afforded by high-field magnets. Maximum entropy (MaxEnt) reconstruction is a non-Fourier method of spectrum analysis that can provide high-resolution spectral estimates from short data records. It can also be used with nonuniformly sampled data sets. Since resolution is substantially determined by the largest evolution time sampled, nonuniform sampling enables high resolution while avoiding the need to uniformly sample at large numbers of evolution times. The Nyquist sampling theorem does not apply to nonuniformly sampled data, and artifacts that occur with the use of nonuniform sampling can be viewed as frequency-aliased signals. Strategies for suppressing nonuniform sampling artifacts include the careful design of the sampling scheme and special methods for computing the spectrum. Researchers now routinely report that they can complete an N-dimensional NMR experiment 3(N-1) times faster (a 3D experiment in one ninth of the time). As a result, high-resolution three- and four-dimensional experiments that were prohibitively time consuming are now practical

  16. NMR characterization of thin films

    Science.gov (United States)

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

    2008-11-25

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

  17. Fast 2D NMR Spectroscopy for In vivo Monitoring of Bacterial Metabolism in Complex Mixtures

    Directory of Open Access Journals (Sweden)

    Rupashree Dass

    2017-07-01

    Full Text Available The biological toolbox is full of techniques developed originally for analytical chemistry. Among them, spectroscopic experiments are very important source of atomic-level structural information. Nuclear magnetic resonance (NMR spectroscopy, although very advanced in chemical and biophysical applications, has been used in microbiology only in a limited manner. So far, mostly one-dimensional 1H experiments have been reported in studies of bacterial metabolism monitored in situ. However, low spectral resolution and limited information on molecular topology limits the usability of these methods. These problems are particularly evident in the case of complex mixtures, where spectral peaks originating from many compounds overlap and make the interpretation of changes in a spectrum difficult or even impossible. Often a suite of two-dimensional (2D NMR experiments is used to improve resolution and extract structural information from internuclear correlations. However, for dynamically changing sample, like bacterial culture, the time-consuming sampling of so-called indirect time dimensions in 2D experiments is inefficient. Here, we propose the technique known from analytical chemistry and structural biology of proteins, i.e., time-resolved non-uniform sampling. The method allows application of 2D (and multi-D experiments in the case of quickly varying samples. The indirect dimension here is sparsely sampled resulting in significant reduction of experimental time. Compared to conventional approach based on a series of 1D measurements, this method provides extraordinary resolution and is a real-time approach to process monitoring. In this study, we demonstrate the usability of the method on a sample of Escherichia coli culture affected by ampicillin and on a sample of Propionibacterium acnes, an acne causing bacterium, mixed with a dose of face tonic, which is a complicated, multi-component mixture providing complex NMR spectrum. Through our experiments

  18. “Waiting for the Bass to Drop”: Correlations between Intense Emotional Experiences and Production Techniques in Build-up and Drop Sections of Electronic Dance Music

    Directory of Open Access Journals (Sweden)

    Ragnhild Torvanger Solberg

    2014-06-01

    Full Text Available This study investigates the correlations between theories of intense emotional experiences and production techniques used in the electronic dance music (EDM sections “build-up” and “drop”, which are designed to build tension and create a heightened emotional intensity among clubbers. This is done by descriptive and interpretive music analysis, where spectrograms and a schematic model visually represent the dominant production techniques. Through a theoretical framework consisting of musical expectancy and gravity, the analysis suggests that i extensive use of uplifters, ii the “drum roll effect”, iii large frequency changes, iv removal and reintroduction of bass and bass drum and v a contrasting “breakdown” cause tension and anticipation, which seems to correlate with a possible intensification of emotional experience. This is furthermore discussed and more broadly related to the club experience seen as a whole, drawing on the psychological concepts Peak experience, Strong experiences with music (SEM and Absorption.

  19. Quenched Hydrogen Exchange NMR of Amyloid Fibrils.

    Science.gov (United States)

    Alexandrescu, Andrei T

    2016-01-01

    Amyloid fibrils are associated with a number of human diseases. These aggregatively misfolded intermolecular β-sheet assemblies constitute some of the most challenging targets in structural biology because to their complexity, size, and insolubility. Here, protocols and controls are described for experiments designed to study hydrogen-bonding in amyloid fibrils indirectly, by transferring information about amide proton occupancy in the fibrils to the dimethyl sulfoxide-denatured state. Since the denatured state is amenable to solution NMR spectroscopy, the method can provide residue-level-resolution data on hydrogen exchange for the monomers that make up the fibrils.

  20. Functional Analysis of the Nitrogen Metabolite Repression Regulator Gene nmrA in Aspergillus flavus

    Directory of Open Access Journals (Sweden)

    Xiaoyun Han

    2016-11-01

    Full Text Available In Aspergillus nidulans, the nitrogen metabolite repression regulator NmrA plays a major role in regulating the activity of the GATA transcription factor AreA during nitrogen metabolism. However, the function of nmrA in Aspergillus flavus has notbeen previously studied. Here, we report the identification and functional analysis of nmrA in A. flavus. Our work showed that the amino acid sequences of NmrA are highly conserved among Aspergillus species and that A. flavus NmrA protein contains a canonical Rossmann fold motif. Deletion of nmrA slowed the growth of A. flavus but significantly increased conidiation and sclerotia production. Moreover, seed infection experiments indicated that nmrA is required for the invasive virulence of A. flavus. In addition, the ΔnmrA mutant showed increased sensitivity to rapamycin and methyl methanesulfonate, suggesting that nmrA could be responsive to target of rapamycin signaling and DNA damage. Furthermore, quantitative real-time reverse transcription polymerase chain reaction analysis suggested that nmrA might interact with other nitrogen regulatory and catabolic genes. Our study provides a better understanding of nitrogen metabolite repression and the nitrogen metabolism network in fungi.