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Sample records for nmr correlation experiments

  1. An NMR Kinetics Experiment.

    ERIC Educational Resources Information Center

    Kaufman, Don; And Others

    1982-01-01

    Outlines advantages of and provides background information, procedures, and typical student data for an experiment determining rate of hydration of p-methyoxyphenylacetylene (III), followed by nuclear magnetic resonance spectroscopy. Reaction rate can be adjusted to meet time framework of a particular laboratory by altering concentration of…

  2. Understanding Structure-Property Correlation in Monocationic and Dicationic Ionic Liquids through Combined Fluorescence and Pulsed-Field Gradient (PFG) and Relaxation NMR Experiments.

    PubMed

    Kumar Sahu, Prabhat; Ghosh, Arindam; Sarkar, Moloy

    2015-11-05

    Steady state, time-resolved fluorescence and NMR experiments are carried out to gain deeper insights into the structure-property correlation in structurally similar monocationic and dicationic room-temperature ionic liquids (RTILs). The excitation wavelength dependent fluorescence response of fluorophore in 1-methy-3-propyllimidazolium bis(trifluoromethylsulfonyl)amide [C3MIm][NTf2] is found to be different from that of 1,6-bis(3-methylimidazolium-1-yl)hexane bis(trifluoromethylsulfonyl)amide [C6(MIm)2][NTf2]2 and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide [C6MIm][NTf2]. The outcomes of the present solvent dynamics study in [C3MIm][NTf2] when compared with those in [C6(MIm)2][NTf2]2 and in [C6MIm][NTf2] from our previous studies (Phys. Chem. Chem. Phys. 2014, 16, 12918-12928) indicate the involvement of dipolar rotation of imidazolium cation during solvation. To correlate the findings of solvation dynamics study with the dipolar rotation of the imidazolium ring, pulsed-field gradient (PFG)-NMR technique for translational diffusion coefficient measurement and (1)H as well as (19)F spin-lattice relaxation measurements are employed. NMR investigation reveals that an ultrafast component of solvation can be related to the dipolar rotation of imidazolium cation; hence, the role of dipolar rotation of cations in governing the dynamics of solvation in ILs cannot be ignored. Analysis of the rotational relaxation dynamics data by the Stokes-Einstein-Debye hydrodynamic theory unveils distinctive features of solute-solvent interaction in [C3MIm][NTf2] and [C6(MIm)2][NTf2]2.

  3. An Inversion Recovery NMR Kinetics Experiment

    ERIC Educational Resources Information Center

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

    2011-01-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

  5. An Inversion Recovery NMR Kinetics Experiment.

    PubMed

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

    2011-05-01

    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 article will enable instructors to use inversion recovery as a laboratory activity in applied NMR classes and provide research students with a convenient template with which to acquire inversion recovery data on research samples.

  6. An Inversion Recovery NMR Kinetics Experiment

    PubMed Central

    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 article will enable instructors to use inversion recovery as a laboratory activity in applied NMR classes and provide research students with a convenient template with which to acquire inversion recovery data on research samples. PMID:21552343

  7. In vivo two-dimensional NMR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Kraft, Robert A.

    1999-10-01

    The poor resolution of in-vivo one- dimensional nuclear magnetic resonance spectroscopy (NMR) has limited its clinical potential. Currently, only the large singlet methyl resonances arising from N-acetyl aspartate (NAA), choline, and creatine are quantitated in a clinical setting. Other metabolites such as myo- inositol, glutamine, glutamate, lactate, and γ- amino butyric acid (GABA) are of clinical interest but quantitation is difficult due to the overlapping resonances and limited spectral resolution. To improve the spectral resolution and distinguish between overlapping resonances, a series of two- dimensional chemical shift correlation spectroscopy experiments were developed for a 1.5 Tesla clinical imaging magnet. Two-dimensional methods are attractive for in vivo spectroscopy due to their ability to unravel overlapping resonances with the second dimension, simplifying the interpretation and quantitation of low field NMR spectra. Two-dimensional experiments acquired with mix-mode line shape negate the advantages of the second dimension. For this reason, a new experiment, REVOLT, was developed to achieve absorptive mode line shape in both dimensions. Absorptive mode experiments were compared to mixed mode experiments with respect to sensitivity, resolution, and water suppression. Detailed theoretical and experimental calculations of the optimum spin lock and radio frequency power deposition were performed. Two-dimensional spectra were acquired from human bone marrow and human brain tissue. The human brain tissue spectra clearly reveal correlations among the coupled spins of NAA, glutamine, glutamate, lactate, GABA, aspartate and myo-inositol obtained from a single experiment of 23 minutes from a volume of 59 mL. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253-1690.)

  8. BetaNMR Experiments on Liquid Samples

    NASA Astrophysics Data System (ADS)

    Gottberg, A.; Stachura, M.; Hemmingsen, L.; Macfarlane, W. A.; Bio-Beta-Nmr Collaboration; Collaps Collaboration

    2016-09-01

    In 2012 betaNMR spectroscopy was successfully applied on liquid samples; an achievement which opens new opportunities in the fields of chemistry and biochemistry. This project was motivated by the need for finding a new experimental approach to directly study biologically highly relevant metal ions, such as Mg(II), Cu(I), Ca(II), and Zn(II), which are silent in most spectroscopic techniques. The resonance spectrum recorded for Mg-31 implanted into an ionic liquid sample showed two resonances which originate from Mg ions occupying two different coordination geometries, illustrating that this technique can discriminate between different structures. This proof-of-principle result lays the foundation for studies of these metal ions at low concentrations and in environments of biological relevance where other methods are silent. The prototype chamber for bio-betaNMR allows for experiments not only on different samples such as: liquids, gels and solids, but also operates at different vacuum environments. In order to exploit the potential of betaNMR on liquid samples, tests with polarized beams of Mg-29 and Mg-31 have recently been performed at the ISAC facility at TRIUMF.

  9. Jointly deriving NMR surface relaxivity and pore size distributions by NMR relaxation experiments on partially desaturated rocks

    NASA Astrophysics Data System (ADS)

    Mohnke, O.; Hughes, B.

    2014-06-01

    Nuclear magnetic resonance (NMR) relaxometry is a geophysical method widely used in borehole and laboratory applications to nondestructively infer transport and storage properties of rocks and soils as it is directly sensitive to the water/oil content and pore sizes. However, for inferring pore sizes, NMR relaxometry data need to be calibrated with respect to a surface interaction parameter, surface relaxivity, which depends on the type and mineral constituents of the investigated rock. This study introduces an inexpensive and quick alternative to the classical calibration methods, e.g., mercury injection, pulsed field gradient (PFG) NMR, or grain size analysis, which allows for jointly estimating NMR surface relaxivity and pore size distributions using NMR relaxometry data from partially desaturated rocks. Hereby, NMR relaxation experiments are performed on the fully saturated sample and on a sample partially drained at a known differential pressure. Based on these data, the (capillary) pore radius distribution and surface relaxivity are derived by joint optimization of the Brownstein-Tarr and the Young-Laplace equation assuming parallel capillaries. Moreover, the resulting pore size distributions can be used to predict water retention curves. This inverse modeling approach—tested and validated using NMR relaxometry data measured on synthetic porous borosilicate samples with known petrophysical properties (i.e., permeability, porosity, inner surfaces, pore size distributions)—yields consistent and reproducible estimates of surface relaxivity and pore radii distributions. Also, subsequently calculated water retention curves generally correlate well with measured water retention curves.

  10. Study of correlations in molecular motion by multiple quantum NMR

    SciTech Connect

    Tang, J.H.

    1981-11-01

    Nuclear magnetic resonance is a very useful tool for characterizing molecular configurations through the measurement of transition frequencies and dipolar couplings. The measurement of spectral lineshapes, spin-lattice relaxation times, and transverse relaxation times also provide us with valuable information about correlations in molecular motion. The new technique of multiple quantum nuclear magnetic resonance has numerous advantages over the conventional single quantum NMR techniques in obtaining information about static and dynamic interactions of coupled spin systems. In the first two chapters, the theoretical background of spin Hamiltonians and the density matrix formalism of multiple quantum NMR is discussed. The creation and detection of multiple quantum coherence by multiple pulse sequence are discussed. Prototype multiple quantum spectra of oriented benzene are presented. Redfield relaxation theory and the application of multiple quantum NMR to the study of correlations in fluctuations are presented. A specific example of an oriented methyl group relaxed by paramagnetic impurities is studied in detail. The study of possible correlated motion between two coupled methyl groups by multiple quantum NMR is presented. For a six spin system it is shown that the four-quantum spectrum is sensitive to two-body correlations, and serves a ready test of correlated motion. The study of the spin-lattice dynamics of orienting or tunneling methyl groups (CH/sub 3/ and CD/sub 3/) at low temperatures is presented. The anisotropic spin-lattice relaxation of deuterated hexamethylbenzene, caused by the sixfold reorientation of the molecules, is investigated, and the NMR spectrometers and other experimental details are discussed.

  11. Generalized indirect covariance NMR formalism for establishment of multidimensional spin correlations.

    PubMed

    Snyder, David A; Brüschweiler, Rafael

    2009-11-19

    Multidimensional nuclear magnetic resonance (NMR) experiments measure spin-spin correlations, which provide important information about bond connectivities and molecular structure. However, direct observation of certain kinds of correlations can be very time-consuming due to limitations in sensitivity and resolution. Covariance NMR derives correlations between spins via the calculation of a (symmetric) covariance matrix, from which a matrix-square root produces a spectrum with enhanced resolution. Recently, the covariance concept has been adopted to the reconstruction of nonsymmetric spectra from pairs of 2D spectra that have a frequency dimension in common. Since the unsymmetric covariance NMR procedure lacks the matrix-square root step, it does not suppress relay effects and thereby may generate false positive signals due to chemical shift degeneracy. A generalized covariance formalism is presented here that embeds unsymmetric covariance processing within the context of the regular covariance transform. It permits the construction of unsymmetric covariance NMR spectra subjected to arbitrary matrix functions, such as the square root, with improved spectral properties. This formalism extends the domain of covariance NMR to include the reconstruction of nonsymmetric NMR spectra at resolutions or sensitivities that are superior to the ones achievable by direct measurements.

  12. Rocket Auroral Correlator Experiment

    NASA Technical Reports Server (NTRS)

    LaBelle, James

    2003-01-01

    Dartmouth College provided a multi-channel high- and low- frequency wave receivers, including active sensors on deployable booms, to the Rocket Auroral Correlator Experiment launched from Poker Flat, Alaska, in January 2002. College also performed preliminary analysis of the data. Details are outlined in chronological order.

  13. Sodium ion effect on silk fibroin conformation characterized by solid-state NMR and generalized 2D NMR NMR correlation

    NASA Astrophysics Data System (ADS)

    Ruan, Qing-Xia; Zhou, Ping

    2008-07-01

    In the present work, we investigated Na + ion effect on the silk fibroin (SF) conformation. Samples are Na +-involved regenerated silk fibroin films. 13C CP-MAS NMR demonstrates that as added [Na +] increases, partial silk fibroin conformation transit from helix-form to β-form at certain Na + ion concentration which is much higher than that in Bombyx mori silkworm gland. The generalized two-dimensional NMR-NMR correlation analysis reveals that silk fibroin undergoes several intermediate states during its conformation transition process as [Na +] increase. The appearance order of the intermediates is followed as: helix and/or random coil → helix-like → β-sheet-like → β-sheet, which is the same as that produced by pH decrease from 6.8 to 4.8 in the resultant regenerated silk fibroin films. The binding sites of Na + to silk fibroin might involve the carbonyl oxygen atom of certain amino acids sequence which could promote the formation of β-sheet conformation. Since the Na +sbnd O bond is weak, the ability of Na + inducing the secondary structure transition is weaker than those of Ca 2+, Cu 2+ and even K +. It is maybe a reason why the sodium content is much lower than potassium in the silkworm gland.

  14. Benchmarking NMR experiments: A relational database of protein pulse sequences

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

    Systematic benchmarking of multi-dimensional protein NMR experiments is a critical prerequisite for optimal allocation of NMR resources for structural analysis of challenging proteins, e.g. large proteins with limited solubility or proteins prone to aggregation. We propose a set of benchmarking parameters for essential protein NMR experiments organized into a lightweight (single XML file) relational database (RDB), which includes all the necessary auxiliaries (waveforms, decoupling sequences, calibration tables, setup algorithms and an RDB management system). The database is interfaced to the Spinach library ( http://spindynamics.org), which enables accurate simulation and benchmarking of NMR experiments on large spin systems. A key feature is the ability to use a single user-specified spin system to simulate the majority of deposited solution state NMR experiments, thus providing the (hitherto unavailable) unified framework for pulse sequence evaluation. This development enables predicting relative sensitivity of deposited implementations of NMR experiments, thus providing a basis for comparison, optimization and, eventually, automation of NMR analysis. The benchmarking is demonstrated with two proteins, of 170 amino acids I domain of αXβ2 Integrin and 440 amino acids NS3 helicase.

  15. Peak width issues with generalised 2D correlation NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kirwan, Gemma M.; Adams, Michael J.

    2008-12-01

    Two-dimensional spectral correlation analysis is shown to be sensitive to fluctuations in spectral peak width as a function of perturbation variable. This is particularly significant where peak width fluctuations are of similar order of magnitude as the peak width values themselves and where changes in peak width are not random but are, for example, proportional to intensity. In such cases these trends appear in the asynchronous matrix as false peaks that serve to interfere with interpretation of the data. Complex, narrow band spectra such as provided by 1H NMR spectroscopy are demonstrated to be prone to such interference. 2D correlation analysis was applied to a series of NMR spectra corresponding to a commercial wine fermentation, in which the samples collected over a period of several days exhibit dramatic changes in concentration of minor and major components. The interference due to changing peak width effects is eliminated by synthesizing the recorded spectra using a constant peak width value prior to performing 2D correlation analysis.

  16. Improved Characterization of Healthy and Malignant Tissue by NMR Line-Shape Relaxation Correlations

    PubMed Central

    Peemoeller, H.; Shenoy, R.K.; Pintar, M.M.; Kydon, D.W.; Inch, W.R.

    1982-01-01

    We performed a relaxation-line-shape correlation NMR experiment on muscle, liver, kidney, and spleen tissues of healthy mice and of mouse tumor tissue. In each tissue studied, five spin groups were resolved and characterized by their relaxation parameters. We report a previously uncharacterized semi-solid spin group and discuss briefly the value of this method for the identification of malignant tissues. PMID:7104438

  17. First NMR Experiments in the Hybrid, 40T and beyond: A challenge to traditional NMR instrumentation

    NASA Astrophysics Data System (ADS)

    Reyes, Arneil P.

    2001-03-01

    The recent commissioning of the continuous 45T hybrid magnet at NHMFL has opened new horizon for science but carried with it new challenges that forced NMR spectroscopists to reevaluate the traditional approach to NMR instrumentation. Very recently, a world record frequency at 1.5GHz has been achieved, signaling the new era of NMR probe designs that may someday blur the distinction between the classic NMR and millimeter-wave spectroscopies. No longer can we ignore stray capacitances and exposed leads in the terrain where every millimeter of cable counts. The challenge brought about by ever increasing fields and consequently, frequency, requirements has stimulated ingenuity among scientists. This is eased by accelerated growth in RF communications and computing technologies that made available advanced devices with more speed, power, bandwidth, noise immunity, flexibility, and complexity in small space at very low costs. Utilization of these devices have been paramount consideration in cutting-edge designs at NHMFL for Condensed Matter NMR and will be described in this talk. I will also discuss a number of first >33T NMR experiments to date utilizing the strength of the field to expose, as well as to induce occurrence of, new physical phenomena in condensed matter and which resulted in better understanding of the physics of materials. This work has been a result of continuing collaboration with P. L Kuhns, W. G. Moulton, W. P. Halperin (NU), and W. G. Clark (UCLA). The NHMFL is supported through the National Science Foundation and the State of Florida.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    ERIC Educational Resources Information Center

    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)

  20. A Short Set of Carbon 13-NMR Correlation Tables.

    ERIC Educational Resources Information Center

    Brown, D. W.

    1985-01-01

    Presents a short set of carbon-13 nuclear magnetic resonance (NMR) tables. These tables not only serve pedagogic purposes but also allow students to do calculations rapidly and with acceptable accuracy for a wide variety of compounds. (JN)

  1. Three-Dimensional Maximum-Quantum Correlation HMQC NMR Spectroscopy (3D MAXY-HMQC)

    NASA Astrophysics Data System (ADS)

    Liu, Maili; Mao, Xi-An; Ye, Chaohui; Nicholson, Jeremy K.; Lindon, John C.

    1997-11-01

    The extension of two-dimensional maximum-quantum correlation spectroscopy (2D MAXY NMR), which can be used to simplify complex NMR spectra, to three dimensions (3D) is described. A new pulse sequence for 3D MAXY-HMQC is presented and exemplified using the steroid drug dexamethasone. The sensitivity and coherence transfer efficiency of the MAXY NMR approach has also been assessed in relation to other HMQC- and HSQC-based 3D methods.

  2. Field Experiment Provides Ground Truth for Surface NMR Measurement

    NASA Astrophysics Data System (ADS)

    Knight, R. J.; Abraham, J. D.; Cannia, J. C.; Dlubac, K. I.; Grau, B.; Grunewald, E. D.; Irons, T.; Song, Y.; Walsh, D.

    2010-12-01

    Effective and sustainable long-term management of fresh water resources requires accurate information about the availability of water in groundwater aquifers. Proton Nuclear Magnetic Resonance (NMR) can provide a direct link to the presence of water in the pore space of geological materials through the detection of the nuclear magnetization of the hydrogen nuclei (protons) in the pore water. Of interest for groundwater applications is the measurement of the proton-NMR relaxation time constant, referred to as T2. This parameter is sensitive to the geometry of the water-filled pore space and can be related to the hydraulic conductivity. NMR logging instruments, which have been available since the 1980’s, provide direct measurements of T2 in boreholes. Surface NMR (SNMR) is a non-invasive geophysical method that uses a loop of wire on the surface to probe the NMR properties of groundwater aquifers to a depth of ~100 m, without the need for the drilling of boreholes. SNMR provides reliable measurements of a different NMR time constant referred to as T2*, that is related to, but not necessarily equivalent to, T2. The relationship between T2* and T2 is likely to depend upon the physical environment and the composition of the sampled material. In order to advance the use of SNMR as a non-invasive means of characterizing groundwater aquifers, we must answer the fundamental question: When probing a groundwater aquifer, what information is provided by T2*, the time constant measured with SNMR? Our approach was to conduct a field experiment in Nebraska, in an area underlain by the Quaternary Alluvium and Tertiary Ogallala aquifers. We first used SNMR to obtain a 1D profile of T2* to a depth of ~60 m. We then drilled a well inside the area of the SNMR loop, to a depth of ~150 m, and used the drill cuttings to describe the composition of the geologic material at the site. The borehole was kept open for 2 days to acquire logging NMR T2 measurements over the total depth. Three

  3. Faster and cleaner real-time pure shift NMR experiments.

    PubMed

    Mauhart, Johannes; Glanzer, Simon; Sakhaii, Peyman; Bermel, Wolfgang; Zangger, Klaus

    2015-10-01

    Real-time pure shift experiments provide highly resolved proton NMR spectra which do not require any special processing. Although being more sensitive than their pseudo 2D counterparts, their signal intensities per unit time are still far below regular NMR spectra. In addition, scalar coupling evolution during the individual data chunks produces decoupling sidebands. Here we show that faster and cleaner real-time pure shift spectra can be obtained through the implementation of two parameter alterations. Variation of the FID chunk lengths between individual transients significantly suppresses decoupling sidebands for any kind of real-time pure shift spectra and thus allows for example the analysis of minor components in compound mixtures. Shifting the excitation frequency between individual scans of real-time slice-selective pure shift spectra increases their sensitivity obtainable in unit time by allowing faster repetitions of acquisitions.

  4. The determination of enantiomeric excess of valine by ODESSA solid-state NMR experiment.

    PubMed

    Tadeusiak, Elzbieta J; Ciesielski, Włodzimierz; Olejniczak, Sebastian

    2006-10-01

    The enantiomeric excess (ee) can be determined by many methods; one among them is nuclear magnetic resonance in solid-state (SS NMR). In this study we used the SS NMR ODESSA experiment for determination of the ee of valine.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Efficient Resonance Assignment of Proteins in MAS NMR by Simultaneous Intra- and Inter-residue 3D Correlation Spectroscopy

    PubMed Central

    Daviso, Eugenio; Eddy, Matthew T.; Andreas, Loren B.; Griffin, Robert G.; Herzfeld, Judith

    2013-01-01

    Resonance assignment is the first step in NMR structure determination. For magic angle spinning NMR, this is typically achieved with a set of heteronuclear correlation experiments (NCaCX, NCOCX, CONCa) that utilize SPECIFIC-CP 15N-13C transfers. However, the SPECIFIC-CP transfer efficiency is often compromised by molecular dynamics and probe performance. Here we show that one-bond ZF-TEDOR 15N-13C transfers provide simultaneous NCO and NCa transfers with at least as much sensitivity as SPECIFIC-CP for some non-crystalline samples. Furthermore, a 3D TEDOR-CC experiment provides heteronuclear sidechains correlations and robustness with respect to proton decoupling and radiofrequency power instabilities. We demonstrate transfer efficiencies and connectivities by application of 3D ZF-TEDOR-DARR to a model microcrystalline protein, GB1, and a less ideal system, GvpA in intact gas vesicles. PMID:23334347

  8. Micro-scale NMR Experiments for Monitoring the Optimization of Membrane Protein Solutions for Structural Biology.

    PubMed

    Horst, Reto; Wüthrich, Kurt

    2015-07-20

    Reconstitution of integral membrane proteins (IMP) in aqueous solutions of detergent micelles has been extensively used in structural biology, using either X-ray crystallography or NMR in solution. Further progress could be achieved by establishing a rational basis for the selection of detergent and buffer conditions, since the stringent bottleneck that slows down the structural biology of IMPs is the preparation of diffracting crystals or concentrated solutions of stable isotope labeled IMPs. Here, we describe procedures to monitor the quality of aqueous solutions of [(2)H, (15)N]-labeled IMPs reconstituted in detergent micelles. This approach has been developed for studies of β-barrel IMPs, where it was successfully applied for numerous NMR structure determinations, and it has also been adapted for use with α-helical IMPs, in particular GPCRs, in guiding crystallization trials and optimizing samples for NMR studies (Horst et al., 2013). 2D [(15)N, (1)H]-correlation maps are used as "fingerprints" to assess the foldedness of the IMP in solution. For promising samples, these "inexpensive" data are then supplemented with measurements of the translational and rotational diffusion coefficients, which give information on the shape and size of the IMP/detergent mixed micelles. Using microcoil equipment for these NMR experiments enables data collection with only micrograms of protein and detergent. This makes serial screens of variable solution conditions viable, enabling the optimization of parameters such as the detergent concentration, sample temperature, pH and the composition of the buffer.

  9. Micro-scale NMR Experiments for Monitoring the Optimization of Membrane Protein Solutions for Structural Biology

    PubMed Central

    Horst, Reto; Wüthrich, Kurt

    2016-01-01

    Reconstitution of integral membrane proteins (IMP) in aqueous solutions of detergent micelles has been extensively used in structural biology, using either X-ray crystallography or NMR in solution. Further progress could be achieved by establishing a rational basis for the selection of detergent and buffer conditions, since the stringent bottleneck that slows down the structural biology of IMPs is the preparation of diffracting crystals or concentrated solutions of stable isotope labeled IMPs. Here, we describe procedures to monitor the quality of aqueous solutions of [2H, 15N]-labeled IMPs reconstituted in detergent micelles. This approach has been developed for studies of β-barrel IMPs, where it was successfully applied for numerous NMR structure determinations, and it has also been adapted for use with α-helical IMPs, in particular GPCRs, in guiding crystallization trials and optimizing samples for NMR studies (Horst et al., 2013). 2D [15N, 1H]-correlation maps are used as “fingerprints” to assess the foldedness of the IMP in solution. For promising samples, these “inexpensive” data are then supplemented with measurements of the translational and rotational diffusion coefficients, which give information on the shape and size of the IMP/detergent mixed micelles. Using microcoil equipment for these NMR experiments enables data collection with only micrograms of protein and detergent. This makes serial screens of variable solution conditions viable, enabling the optimization of parameters such as the detergent concentration, sample temperature, pH and the composition of the buffer. PMID:27077076

  10. Collaborative development for setup, execution, sharing and analytics of complex NMR experiments

    NASA Astrophysics Data System (ADS)

    Irvine, Alistair G.; Slynko, Vadim; Nikolaev, Yaroslav; Senthamarai, Russell R. P.; Pervushin, Konstantin

    2014-02-01

    Factory settings of NMR pulse sequences are rarely ideal for every scenario in which they are utilised. The optimisation of NMR experiments has for many years been performed locally, with implementations often specific to an individual spectrometer. Furthermore, these optimised experiments are normally retained solely for the use of an individual laboratory, spectrometer or even single user. Here we introduce a web-based service that provides a database for the deposition, annotation and optimisation of NMR experiments. The application uses a Wiki environment to enable the collaborative development of pulse sequences. It also provides a flexible mechanism to automatically generate NMR experiments from deposited sequences. Multidimensional NMR experiments of proteins and other macromolecules consume significant resources, in terms of both spectrometer time and effort required to analyse the results. Systematic analysis of simulated experiments can enable optimal allocation of NMR resources for structural analysis of proteins. Our web-based application (http://nmrplus.org) provides all the necessary information, includes the auxiliaries (waveforms, decoupling sequences etc.), for analysis of experiments by accurate numerical simulation of multidimensional NMR experiments. The online database of the NMR experiments, together with a systematic evaluation of their sensitivity, provides a framework for selection of the most efficient pulse sequences. The development of such a framework provides a basis for the collaborative optimisation of pulse sequences by the NMR community, with the benefits of this collective effort being available to the whole community.

  11. Accessible NMR Experiments Studying the Hydrodynamics of [subscript 15]N-Enriched Ubiquitin at Low Fields

    ERIC Educational Resources Information Center

    Thompson, Laura E.; Rovnyak, David

    2007-01-01

    We have recently developed and implemented two experiments in biomolecular NMR for an undergraduate-level biophysical chemistry laboratory with commercially available [subscript 15]N-enriched human ubiquitin. These experiments take advantage of [subscript 15]N direct detection of the NMR signal. The first experiment develops skills in acquiring…

  12. Accessible NMR Experiments Studying the Hydrodynamics of [superscript 15]N-Enriched Ubiquitin at Low Fields

    ERIC Educational Resources Information Center

    Thompson, Laura E.; Rovnyak, David

    2007-01-01

    We have recently developed and implemented two experiments in biomolecular NMR for an undergraduate-level biophysical chemistry laboratory with commercially available [superscript 15]N-enriched human ubiquitin. These experiments take advantage of [superscript 15]N direct detection of the NMR signal. The first experiment develops skills in…

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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

  15. Proton-detected heteronuclear single quantum correlation NMR spectroscopy in rigid solids with ultra-fast MAS

    PubMed Central

    Holland, Gregory P.; Cherry, Brian R.; Jenkins, Janelle E.; Yarger, Jeffery L.

    2009-01-01

    In this article, we show the potential for utilizing proton-detected heteronuclear single quantum correlation (HSQC) NMR in rigid solids under ultra-fast magic angle spinning (MAS) conditions. The indirect detection of carbon-13 from coupled neighboring hydrogen nuclei provides a sensitivity enhancement of 3 - 4 fold in crystalline amino acids over direct-detected versions. Furthermore, the sensitivity enhancement is shown to be significantly larger for disordered solids that display inhomogeneously broadened carbon-13 spectra. Latrodectus hesperus (Black Widow) dragline silk is given as an example where the sample is mass-limited and the sensitivity enhancement for the proton-detected experiment is 8 - 13 fold. The ultra-fast MAS proton-detected HSQC solid-state NMR technique has the added advantage that no proton homonuclear decoupling is applied during the experiment. Further, well-resolved, indirectly observed carbon-13 spectra can be obtained in some cases without heteronuclear proton decoupling. PMID:19857977

  16. Proton-detected heteronuclear single quantum correlation NMR spectroscopy in rigid solids with ultra-fast MAS.

    PubMed

    Holland, Gregory P; Cherry, Brian R; Jenkins, Janelle E; Yarger, Jeffery L

    2010-01-01

    In this article, we show the potential for utilizing proton-detected heteronuclear single quantum correlation (HSQC) NMR in rigid solids under ultra-fast magic angle spinning (MAS) conditions. The indirect detection of carbon-13 from coupled neighboring hydrogen nuclei provides a sensitivity enhancement of 3- to 4-fold in crystalline amino acids over direct-detected versions. Furthermore, the sensitivity enhancement is shown to be significantly larger for disordered solids that display inhomogeneously broadened carbon-13 spectra. Latrodectus hesperus (Black Widow) dragline silk is given as an example where the sample is mass-limited and the sensitivity enhancement for the proton-detected experiment is 8- to 13-fold. The ultra-fast MAS proton-detected HSQC solid-state NMR technique has the added advantage that no proton homonuclear decoupling is applied during the experiment. Further, well-resolved, indirectly observed carbon-13 spectra can be obtained in some cases without heteronuclear proton decoupling.

  17. NMR spectroscopy study of local correlations in water

    NASA Astrophysics Data System (ADS)

    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.

  18. A Solid-State NMR Experiment: Analysis of Local Structural Environments in Phosphate Glasses

    ERIC Educational Resources Information Center

    Anderson, Stanley E.; Saiki, David; Eckert, Hellmut; Meise-Gresch, Karin

    2004-01-01

    An experiment that can be used to directly study the local chemical environments of phosphorus in solid amorphous materials is demonstrated. The experiment aims at familiarizing the students of chemistry with the principles of solid-state NMR, by having them synthesize a simple phosphate glass, and making them observe the (super 31)P NMR spectrum,…

  19. Using an NMR Spectrometer to Do Magnetic Resonance Imaging: An Undergraduate Physical Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Steinmetz, Wayne E.; Maher, M. Cyrus

    2007-01-01

    A conventional Fourier-transform NMR spectrometer with a triple-axis gradient probe can function as a MRI imager. In this experiment students gain hands-on experience with MRI while they learn about important principles underlying the practice of NMR, such as gradients, multi-dimensional spectroscopy, and relaxation. Students image a biological…

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

    SciTech Connect

    Mao, Kanmi

    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

  1. Quantitative two-dimensional HSQC experiment for high magnetic field NMR spectrometers

    NASA Astrophysics Data System (ADS)

    Koskela, Harri; Heikkilä, Outi; Kilpeläinen, Ilkka; Heikkinen, Sami

    2010-01-01

    The finite RF power available on carbon channel in proton-carbon correlation experiments leads to non-uniform cross peak intensity response across carbon chemical shift range. Several classes of broadband pulses are available that alleviate this problem. Adiabatic pulses provide an excellent magnetization inversion over a large bandwidth, and very recently, novel phase-modulated pulses have been proposed that perform 90° and 180° magnetization rotations with good offset tolerance. Here, we present a study how these broadband pulses (adiabatic and phase-modulated) can improve quantitative application of the heteronuclear single quantum coherence (HSQC) experiment on high magnetic field strength NMR spectrometers. Theoretical and experimental examinations of the quantitative, offset-compensated, CPMG-adjusted HSQC (Q-OCCAHSQC) experiment are presented. The proposed experiment offers a formidable improvement to the offset performance; 13C offset-dependent standard deviation of the peak intensity was below 6% in range of ±20 kHz. This covers the carbon chemical shift range of 150 ppm, which contains the protonated carbons excluding the aldehydes, for 22.3 T NMR magnets. A demonstration of the quantitative analysis of a fasting blood plasma sample obtained from a healthy volunteer is given.

  2. Titration of Alanine Monitored by NMR Spectroscopy: A Biochemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Waller, Francis J.; And Others

    1977-01-01

    The experiment described here involves simultaneous monitoring of pH and NMR chemical shifts during an aqueous titration of alpha- and beta-alanine. This experiment is designed for use in an undergraduate biochemistry course. (MR)

  3. Temperature-Dependent Oxygen Effect on NMR D-[Formula: see text] Relaxation-Diffusion Correlation of n-Alkanes.

    PubMed

    Shikhov, Igor; Arns, Christoph H

    2016-01-01

    Nuclear magnetic resonance (NMR) diffusion-relaxation correlation experiments (D-[Formula: see text]) are widely used for the petrophysical characterisation of rocks saturated with petroleum fluids both in situ and for laboratory analyses. The encoding for both diffusion and relaxation offers increased fluid typing contrast by discriminating fluids based on their self-diffusion coefficients, while relaxation times provide information about the interaction of solid and fluid phases and associated confinement geometry (if NMR responses of pure fluids at particular temperature and pressure are known). Petrophysical interpretation of D-[Formula: see text] correlation maps is typically assisted by the "standard alkane line"-a relaxation-diffusion correlation valid for pure normal alkanes and their mixtures in the absence of restrictions to diffusing molecules and effects of internal gradients. This correlation assumes fluids are free from paramagnetic impurities. In situations where fluid samples cannot be maintained at air-free state the diffusion-relaxation response of fluids shift towards shorter relaxation times due to oxygen paramagnetic relaxation enhancement. Interpretation of such a response using the "standard alkane line" would be erroneous and is further complicated by the temperature-dependence of oxygen solubility for each component of the alkane mixture. We propose a diffusion-relaxation correlation suitable for interpretation of low-field NMR D-[Formula: see text] responses of normal alkanes and their mixtures saturating rocks over a broad temperature range, in equilibrium with atmospheric air. We review and where necessary revise existing viscosity-relaxation correlations. Findings are applied to diffusion-relaxation dependencies taking into account the temperature dependence of oxygen solubility and solvent vapour pressure. The effect is demonstrated on a partially saturated carbonate rock.

  4. 2H-DNP-enhanced 2H–13C solid-state NMR correlation spectroscopy

    PubMed Central

    Maly, Thorsten; Andreas, Loren B.; Smith, Albert A.

    2015-01-01

    Perdeuteration of biological macromolecules for magic angle spinning solid-state NMR spectroscopy can yield high-resolution 2H–13C correlation spectra and the method is therefore of great interest for the structural biology community. Here we demonstrate that the combination of sample deuteration and dynamic nuclear polarization yields resolved 2H–13C correlation spectra with a signal enhancement of ε ≥ 700 compared to a spectrum recorded with microwaves off and otherwise identical conditions. To our knowledge, this is the first time that 2H-DNP has been employed to enhance MAS-NMR spectra of a biologically relevant system. The DNP process is studied using several polarizing agents and the technique is applied to obtain 2H–13C correlation spectra of U-[2H, 13C] proline. PMID:20458422

  5. Identifying secondary structures in proteins using NMR chemical shift 3D correlation maps

    NASA Astrophysics Data System (ADS)

    Kumari, Amrita; Dorai, Kavita

    2013-06-01

    NMR chemical shifts are accurate indicators of molecular environment and have been extensively used as aids in protein structure determination. This work focuses on creating empirical 3D correlation maps of backbone chemical shift nuclei for use as identifiers of secondary structure elements in proteins. A correlated database of backbone nuclei chemical shifts was constructed from experimental structural data gathered from entries in the Protein Data Bank (PDB) as well as isotropic chemical shift values from the RefDB database. Rigorous statistical analysis of the maps led to the conclusion that specific correlations between triplets of backbone chemical shifts are best able to differentiate between different secondary structures such as α-helices, β-strands and turns. The method is compared with similar techniques that use NMR chemical shift information as aids in biomolecular structure determination and performs well in tests done on experimental data determined for different types of proteins, including large multi-domain proteins and membrane proteins.

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

    PubMed

    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.

  7. An Analysis of a Commercial Furniture Refinisher: A Comprehensive Introductory NMR Experiment.

    ERIC Educational Resources Information Center

    Markow, Peter G.; Cramer, John A.

    1983-01-01

    Describes a comprehensive nuclear magnetic resonance (NMR) experiment designed to introduce undergraduate organic chemistry students to measurement/interpretation of NMR parameters. Students investigate chemical shift analysis, spin-spin coupling, peak integrations, effect of deuterium oxide extraction, and comparisons with literature spectra;…

  8. Sensitive and robust electrophoretic NMR: Instrumentation and experiments

    NASA Astrophysics Data System (ADS)

    Hallberg, Fredrik; Furó, István; Yushmanov, Pavel V.; Stilbs, Peter

    2008-05-01

    Although simple as a concept, electrophoretic NMR (eNMR) has so far failed to find wider application. Problems encountered are mainly due to disturbing and partly irreproducible convection-like bulk flow effects from both electro-osmosis and thermal convection. Additionally, bubble formation at the electrodes and rf noise pickup has constrained the typical sample geometry to U-tube-like arrangements with a small filling factor and a low resulting NMR sensitivity. Furthermore, the sign of the electrophoretic mobility cancels out in U-tube geometries. We present here a new electrophoretic sample cell based on a vertically placed conventional NMR sample tube with bubble-suppressing palladium metal as electrode material. A suitable radiofrequency filter design prevents noise pickup by the NMR sample coil from the high-voltage leads which extend into the sensitive sample volume. Hence, the obtained signal-to-noise ratio of this cell is one order of magnitude higher than that of our previous U-tube cells. Permitted by the retention of the sign of the displacement-related signal phase in the new cell design, an experimental approach is described where bulk flow effects by electro-osmosis and/or thermal convection are compensated through parallel monitoring of a reference signal from a non-charged species in the sample. This approach, together with a CPMG-like pulse train scheme provides a superior first-order cancellation of non-electrophoretic bulk flow effects.

  9. Correlation of Mechanical Properties in Bulk Metallic Glasses with 27Al NMR Characteristics

    DTIC Science & Technology

    2011-12-01

    properties Magdalena T SANDOR , Laszlo J KECSKES , Qiang HE , Jian XU , Yue WU University of North Carolina - Chapel Hill Office of Sponsored...doi: 10.1007/s11434-011-4834-z Correlation of mechanical properties in bulk metallic glasses with 27Al NMR characteristics SANDOR Magdalena T1...bulk metallic glass, nuclear magnetic resonance, knight shift, magnetic susceptibility, mechanical properties Citation: Sandor M T, Kecskes L J

  10. Imidazole as a pH Probe: An NMR Experiment for the General Chemistry Laboratory

    ERIC Educational Resources Information Center

    Hagan, William J., Jr.; Edie, Dennis L.; Cooley, Linda B.

    2007-01-01

    The analysis describes an NMR experiment for the general chemistry laboratory, which employs an unknown imidazole solution to measure the pH values. The described mechanism can also be used for measuring the acidity within the isolated cells.

  11. Metabolic changes in flatfish hepatic tumours revealed by NMR-based metabolomics and metabolic correlation networks.

    PubMed

    Southam, Andrew D; Easton, John M; Stentiford, Grant D; Ludwig, Christian; Arvanitis, Theodoros N; Viant, Mark R

    2008-12-01

    Histopathologically well-characterized fish liver was analyzed by 800 MHz 1H NMR metabolomics to identify metabolic changes between healthy and tumor tissue. Data were analyzed by multivariate statistics and metabolic correlation networks, and results revealed elevated anaerobic metabolism and reduced choline metabolism in tumor tissue. Significant negative correlations were observed between alanine-acetate (p = 3.0 x 10(-5)) and between proline-acetate (p = 0.003) in tumors only, suggesting alanine and proline are utilized as alternative energy sources in flatfish liver tumors.

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

    PubMed

    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

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

    ERIC Educational Resources Information Center

    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…

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

    NASA Astrophysics Data System (ADS)

    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.

  15. 13C-direct detected NMR experiments for the sequential J-based resonance assignment of RNA oligonucleotides

    PubMed Central

    Richter, Christian; Kovacs, Helena; Buck, Janina; Wacker, Anna; Fürtig, Boris; Bermel, Wolfgang

    2010-01-01

    We present here a set of 13C-direct detected NMR experiments to facilitate the resonance assignment of RNA oligonucleotides. Three experiments have been developed: (1) the (H)CC-TOCSY-experiment utilizing a virtual decoupling scheme to assign the intraresidual ribose 13C-spins, (2) the (H)CPC-experiment that correlates each phosphorus with the C4′ nuclei of adjacent nucleotides via J(C,P) couplings and (3) the (H)CPC-CCH-TOCSY-experiment that correlates the phosphorus nuclei with the respective C1′,H1′ ribose signals. The experiments were applied to two RNA hairpin structures. The current set of 13C-direct detected experiments allows direct and unambiguous assignment of the majority of the hetero nuclei and the identification of the individual ribose moieties following their sequential assignment. Thus, 13C-direct detected NMR methods constitute useful complements to the conventional 1H-detected approach for the resonance assignment of oligonucleotides that is often hindered by the limited chemical shift dispersion. The developed methods can also be applied to large deuterated RNAs. Electronic supplementary material The online version of this article (doi:10.1007/s10858-010-9429-5) contains supplementary material, which is available to authorized users. PMID:20544375

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

    SciTech Connect

    Ross, J.B.A.; Schwartz, G.P.; Laws, W.R. ); Wyssbrod, H.R.; Porter, R.A. ); Michaels, C.A. )

    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.

  17. Quantum correlations in connected multipartite Bell experiments

    NASA Astrophysics Data System (ADS)

    Tavakoli, Armin

    2016-04-01

    Bell experiments measure correlations between outcomes of a number of observers measuring on a shared physical state emitted from a single source. Quantum correlations arising in such Bell experiments have been intensively studied over the last decades. Much less is known about the nature of quantum correlations arising in network structures beyond Bell experiments. Such networks can involve many independent sources emitting states to observers in accordance with the network configuration. Here, we will study classical and quantum correlations in a family of networks which can be regarded as compositions of several independent multipartite Bell experiments connected together through a central node. For such networks we present tight Bell-type inequalities which are satisfied by all classical correlations. We study properties of the violations of our inequalities by probability distributions arising in quantum theory.

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

    SciTech Connect

    Hu, Jian Zhi

    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.

  19. Structural Isomer Identification via NMR: A Nuclear Magnetic Resonance Experiment for Organic, Analytical, or Physical Chemistry.

    ERIC Educational Resources Information Center

    Szafran, Zvi

    1985-01-01

    Background information, procedures used, and typical results obtained are provided for an experiment that examines the ability of nuclear magnetic resonance (NMR) to distinguish between structural isomers via resonance multiplicities and chemical shifts. Reasons for incorporating the experiment into organic, analytical, or physical chemistry…

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

    ERIC Educational Resources Information Center

    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.…

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

    PubMed Central

    Ishima, Rieko

    2016-01-01

    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 1H-15N 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. PMID:27524944

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

    PubMed

    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.

  3. Shimming of a Magnet for Calibration of NMR Probes for the Muon g-2 Experiment

    NASA Astrophysics Data System (ADS)

    Bielajew, Rachel

    2013-10-01

    The Muon g-2 Experiment at Fermilab aims to measure the anomalous magnetic moment aμ ≡ (g-2)/2 of the muon to the precision of 0.14 parts per million. This experimental value of aμ can then be compared to the similarly precise theoretical predictions of the Standard Model in order to test the completeness of the model. The value of aμ is extracted from muons precessing in a magnetic field. The magnetic field will be measured with a set of 400 Nuclear Magnetic Resonance (NMR) probes, which have the ability to measure the field to a precision of tens of parts per billion. Before the Muon g-2 Experiment can take place, new NMR probes must be designed, built, and tested using a 1.45 Tesla test magnet at the University of Washington Center for Experimental Nuclear Physics and Astrophysics (CENPA). In order to achieve a significant signal from NMR probes, the magnetic field in which the probes are immersed must be extremely uniform. The existing magnet at CENPA has an approximately linear gradient in magnetic field of about 1 Gauss per centimeter in the smoothest direction. A pair of adjacent square Helmholtz coils was designed and built to create a linear gradient in order to cancel the existing gradient. The length of the NMR signals improved with the implementation of the coils. The results of the addition of the coils to the magnet on the signals from the NMR probes will be presented.

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

    ERIC Educational Resources Information Center

    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…

  5. An NMR Study of Isotope Effect on Keto-Enol Tautomerization: A Physical Organic Chemistry Experiment

    ERIC Educational Resources Information Center

    Atkinson, D.; Chechik, V.

    2004-01-01

    Isotope substitution often affects the rate of an organic reaction and can be used to reveal the underlying mechanism. A series of experiments that use (super 1)H NMR to determine primary and secondary isotope effects, activation parameters, and the regioselectivity of butanone enolization are described.

  6. 3D correlation NMR spectrum between three distinct heteronuclei for the characterization of inorganic samples: Application on sodium alumino-phosphate materials.

    PubMed

    Nagashima, Hiroki; Tricot, Grégory; Trébosc, Julien; Lafon, Olivier; Amoureux, Jean-Paul; Pourpoint, Frédérique

    2017-03-22

    We report here an original NMR sequence allowing the acquisition of 3D correlation NMR spectra between three distinct heteronuclei, among which two are half-integer spin quadrupolar nuclei. Furthermore, as two of them exhibit close Larmor frequency, this experiment was acquired using a standard triple-resonance probe equipped with a commercial frequency splitter. This NMR technique was tested and applied to sodium alumino-phosphate compounds with (31)P as the spin-1/2 nucleus and (23)Na and (27)Al as the close Larmor frequencies isotopes. To the best of our knowledge, such experiment with direct (31)P and indirect (27)Al and (23)Na detection is the first example of 3D NMR experiment in solids involving three distinct heteronuclei. This sequence has first been demonstrated on a mixture of Al(PO3)3 and NaAlP2O7 crystalline phases, for which a selective observation of NaAlP2O7 is possible through the 3D map edition. This 3D correlation experiment is then applied to characterize mixing and phase segregation in a partially devitrified glass that has been proposed as a material for the sequestration of radioactive waste. The (31)P-{(23)Na,(27)Al} 3D experiment conducted on the partially devitrified glass material conclusively demonstrates that the amorphous component of the material does not contain aluminum. The as-synthesized material thus presents a poor resistance against water, which is a severe limitation for its application in the radioactive waste encapsulation domain.

  7. Competing magnetic fluctuations in iron pnictide superconductors: Role of ferromagnetic spin correlations revealed by NMR

    SciTech Connect

    Wiecki, P.; Roy, B.; Johnston, D. C.; Bud’ko, S. L.; Canfield, P. C.; Furukawa, Y.

    2015-09-22

    In the iron pnictide superconductors, theoretical calculations have consistently shown enhancements of the static magnetic susceptibility at both the stripe-type antiferromagnetic and in-plane ferromagnetic (FM) wave vectors. However, the possible existence of FM fluctuations has not yet been examined from a microscopic point of view. Here, using 75As NMR data, we provide clear evidence for the existence of FM spin correlations in both the hole- and electron-doped BaFe2As2 families of iron-pnictide superconductors. Furthermore, these FM fluctuations appear to compete with superconductivity and are thus a crucial ingredient to understanding the variability of Tc and the shape of the superconducting dome in these and other iron-pnictide families.

  8. Competing magnetic fluctuations in iron pnictide superconductors: Role of ferromagnetic spin correlations revealed by NMR

    DOE PAGES

    Wiecki, P.; Roy, B.; Johnston, D. C.; ...

    2015-09-22

    In the iron pnictide superconductors, theoretical calculations have consistently shown enhancements of the static magnetic susceptibility at both the stripe-type antiferromagnetic and in-plane ferromagnetic (FM) wave vectors. However, the possible existence of FM fluctuations has not yet been examined from a microscopic point of view. Here, using 75As NMR data, we provide clear evidence for the existence of FM spin correlations in both the hole- and electron-doped BaFe2As2 families of iron-pnictide superconductors. Furthermore, these FM fluctuations appear to compete with superconductivity and are thus a crucial ingredient to understanding the variability of Tc and the shape of the superconducting domemore » in these and other iron-pnictide families.« less

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

    NASA Astrophysics Data System (ADS)

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

    1997-12-01

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

  10. Parameterized signal calibration for NMR cryoporometry experiment without external standard

    NASA Astrophysics Data System (ADS)

    Stoch, Grzegorz; Krzyżak, Artur T.

    2016-08-01

    In cryoporometric experiments non-linear effects associated with the sample and the probehead bring unwanted contributions to the total signal along with the change of temperature. The elimination of these influences often occurs with the help of an intermediate measurement of a separate liquid sample. In this paper we suggest an alternative approach under certain assumptions, solely based on data from the target experiment. In order to obtain calibration parameters the method uses all of these raw data points. Its reliability is therefore enhanced as compared to other methods based on lesser number of data points. Presented approach is automatically valid for desired temperature range. The need for intermediate measurement is removed and parameters for such a calibration are naturally adapted to the individual sample-probehead combination.

  11. Correlation of Electronic Effects in N-Alkylnicotinamides with NMR Chemical Shifts and Hydride Transfer Reactivity.

    PubMed

    Burke, James R.; Frey, Perry A.

    1996-01-26

    The (13)C and (15)N NMR chemical shifts for ring atoms of a series of N-alkylnicotinamides are shown to be correlated with their reduction potentials and reactivities toward NaBH(3)CN. The nicotinamide compounds include N-ethyl-N-benzyl-N-[p-(trifluoromethyl)benzyl]-, N-(p-cyanobenzyl)-, N-(carbomethoxymethyl)-, and N-(cyanomethyl)nicotinamides. The values of delta()13(C) for all the ring carbons increase with increasing electron-withdrawing power of the N-alkyl substituent. The value for C-4 increases the most, a range of 2.4 ppm in this series, whereas those for other atoms increase on the order of 1 ppm. The value of delta()15(N) for N-1 decreases with increasing electron-withdrawing power over a range of 20 ppm. The NMR data indicate that inductive electron withdrawal by N-alkyl substituents polarizes the pi-electron system to decrease electron density on ring carbons and increase electron density on the ring nitrogen. The values of log k (second order) for reduction of these compounds by NaBH(3)CN are proportional to the values of delta()13(C) for C-4 and inversely proportional to delta()15(N) for N-1. The reduction potentials are proportional to delta()13(C). The substituent effects are qualitatively similar to the substrate-induced electrostatic effects on the nicotinamide ring of NAD(+) at the active site of UDP-galactose 4-epimerase (Burke, J. R.; Frey, P. A. Biochemistry 1993, 32, 13220-13230). However, they differ quantitatively in that the upfield perturbation at N-1 is smaller in the enzyme and the signal for C-6 is also shifted upfield. The substrate-induced enzymatic perturbation of electron density at C-4 of NAD(+) quantitatively accounts for its increase in reactivity at the active site, but the perturbation at N-1 is less closely correlated with reactivity.

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

    PubMed

    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.

  13. Superstatistics model for T₂ distribution in NMR experiments on porous media.

    PubMed

    Correia, M D; Souza, A M; Sinnecker, J P; Sarthour, R S; Santos, B C C; Trevizan, W; Oliveira, I S

    2014-07-01

    We propose analytical functions for T2 distribution to describe transverse relaxation in high- and low-fields NMR experiments on porous media. The method is based on a superstatistics theory, and allows to find the mean and standard deviation of T2, directly from measurements. It is an alternative to multiexponential models for data decay inversion in NMR experiments. We exemplify the method with q-exponential functions and χ(2)-distributions to describe, respectively, data decay and T2 distribution on high-field experiments of fully water saturated glass microspheres bed packs, sedimentary rocks from outcrop and noisy low-field experiment on rocks. The method is general and can also be applied to biological systems.

  14. 1H Photo-CIDNP Enhancements in Heteronuclear Correlation NMR Spectroscopy

    PubMed Central

    Sekhar, Ashok; Cavagnero, Silvia

    2009-01-01

    Photochemically induced dynamic nuclear polarization (photo-CIDNP) is usually employed as a probe of solvent exposure, in biomolecular NMR. The potential of the photo-CIDNP effect for sensitivity enhancement, however, remains poorly explored. Here, we introduce 1H-photo-CIDNP in heteronuclear correlation spectroscopy at low laser irradiation power (1 W), and compare the sensitivity of various 1H-Photo-CIDNP-enhanced- (HPE) 1H◻15N heteronuclear correlation pulse sequences, including HSQC, HMQC, and SOFAST-HMQC, in terms of their ability to detect the Trp indole Hε1 resonance. Both Trp and the Trp-containing protein apoHmpH were analyzed using flavin mononucleotide as photosensitizer in aqueous solutions either containing or lacking urea. We find that 1H◻15N photo-CIDNP-SOFAST-HMQC, denoted here as HPE-SOFAST-HMQC, yields a two-fold higher signal-to-noise per unit time than the parent SOFAST-HMQC for the solvent-exposed Trp of urea-unfolded apoHmpH. Thus, HPE-SOFAST-HMQC is the most sensitive heteronuclear correlation pulse sequence for the detection of solvent-exposed Trp. PMID:19462951

  15. A magnetic gradient induced force in NMR restricted diffusion experiments

    SciTech Connect

    Ghadirian, Bahman; Stait-Gardner, Tim; Castillo, Reynaldo; Price, William S.

    2014-03-28

    We predict that the phase cancellation of a precessing magnetisation field carried by a diffusing species in a bounded geometry under certain nuclear magnetic resonance pulsed magnetic field gradient sequences results in a small force over typically micrometre length scales. Our calculations reveal that the total magnetisation energy in a pore under the influence of a pulsed gradient will be distance-dependent thus resulting in a force acting on the boundary. It is shown that this effect of the magnetisation of diffusing particles will appear as either an attractive or repulsive force depending on the geometry of the pore and magnetic properties of the material. A detailed analysis is performed for the case of a pulsed gradient spin-echo experiment on parallel planes. It is shown that the force decays exponentially in terms of the spin-spin relaxation. The proof is based on classical electrodynamics. An application of this effect to soft matter is suggested.

  16. 13C direct detected COCO-TOCSY: A tool for sequence specific assignment and structure determination in protonless NMR experiments

    NASA Astrophysics Data System (ADS)

    Balayssac, Stéphane; Jiménez, Beatriz; Piccioli, Mario

    2006-10-01

    A novel experiment is proposed to provide inter-residue sequential correlations among carbonyl spins in 13C detected, protonless NMR experiments. The COCO-TOCSY experiment connects, in proteins, two carbonyls separated from each other by three, four or even five bonds. The quantitative analysis provides structural information on backbone dihedral angles ϕ as well as on the side chain dihedral angles of Asx and Glx residues. This is the first dihedral angle constraint that can be obtained via a protonless approach. About 75% of backbone carbonyls in Calbindin D 9K, a 75 aminoacid dicalcium protein, could be sequentially connected via a COCO-TOCSY spectrum. 49 3J values were measured and related to backbone ϕ angles. Structural information can be extended to the side chain orientation of aminoacids containing carbonyl groups. Additionally, long range homonuclear coupling constants, 4JCC and 5JCC, could be measured. This constitutes an unprecedented case for proteins of medium and small size.

  17. Sensitivity Enhancement in Multiple-Quantum NMR Experiments with CPMG Detection

    NASA Astrophysics Data System (ADS)

    Lim, Kwang Hun; Nguyen, Tuan; Mazur, Tanya; Wemmer, David E.; Pines, Alexander

    2002-07-01

    We present a modified multiple-quantum (MQ) experiment, which implements the Carr-Purcell-Meiboom-Gill (CPMG) detection scheme in the static MQ NMR experiment proposed by W. S. Warren et al. (1980, J. Chem. Phys.73, 2084-2099) and exploited further by O. N. Antzutkin and R. Tycko (1999, J. Chem. Phys.110, 2749-2752). It is demonstrated that a significant enhancement in the sensitivity can be achieved by acquiring echo trains in the MQ experiments for static powder samples. The modified scheme employing the CPMG detection was superior to the original MQ experiment, in particular for the carbonyl carbon with a very large chemical shift anisotropy.

  18. FoodPro: A Web-Based Tool for Evaluating Covariance and Correlation NMR Spectra Associated with Food Processes.

    PubMed

    Chikayama, Eisuke; Yamashina, Ryo; Komatsu, Keiko; Tsuboi, Yuuri; Sakata, Kenji; Kikuchi, Jun; Sekiyama, Yasuyo

    2016-10-19

    Foods from agriculture and fishery products are processed using various technologies. Molecular mixture analysis during food processing has the potential to help us understand the molecular mechanisms involved, thus enabling better cooking of the analyzed foods. To date, there has been no web-based tool focusing on accumulating Nuclear Magnetic Resonance (NMR) spectra from various types of food processing. Therefore, we have developed a novel web-based tool, FoodPro, that includes a food NMR spectrum database and computes covariance and correlation spectra to tasting and hardness. As a result, FoodPro has accumulated 236 aqueous (extracted in D₂O) and 131 hydrophobic (extracted in CDCl₃) experimental bench-top 60-MHz NMR spectra, 1753 tastings scored by volunteers, and 139 hardness measurements recorded by a penetrometer, all placed into a core database. The database content was roughly classified into fish and vegetable groups from the viewpoint of different spectrum patterns. FoodPro can query a user food NMR spectrum, search similar NMR spectra with a specified similarity threshold, and then compute estimated tasting and hardness, covariance, and correlation spectra to tasting and hardness. Querying fish spectra exemplified specific covariance spectra to tasting and hardness, giving positive covariance for tasting at 1.31 ppm for lactate and 3.47 ppm for glucose and a positive covariance for hardness at 3.26 ppm for trimethylamine N-oxide.

  19. FoodPro: A Web-Based Tool for Evaluating Covariance and Correlation NMR Spectra Associated with Food Processes

    PubMed Central

    Chikayama, Eisuke; Yamashina, Ryo; Komatsu, Keiko; Tsuboi, Yuuri; Sakata, Kenji; Kikuchi, Jun; Sekiyama, Yasuyo

    2016-01-01

    Foods from agriculture and fishery products are processed using various technologies. Molecular mixture analysis during food processing has the potential to help us understand the molecular mechanisms involved, thus enabling better cooking of the analyzed foods. To date, there has been no web-based tool focusing on accumulating Nuclear Magnetic Resonance (NMR) spectra from various types of food processing. Therefore, we have developed a novel web-based tool, FoodPro, that includes a food NMR spectrum database and computes covariance and correlation spectra to tasting and hardness. As a result, FoodPro has accumulated 236 aqueous (extracted in D2O) and 131 hydrophobic (extracted in CDCl3) experimental bench-top 60-MHz NMR spectra, 1753 tastings scored by volunteers, and 139 hardness measurements recorded by a penetrometer, all placed into a core database. The database content was roughly classified into fish and vegetable groups from the viewpoint of different spectrum patterns. FoodPro can query a user food NMR spectrum, search similar NMR spectra with a specified similarity threshold, and then compute estimated tasting and hardness, covariance, and correlation spectra to tasting and hardness. Querying fish spectra exemplified specific covariance spectra to tasting and hardness, giving positive covariance for tasting at 1.31 ppm for lactate and 3.47 ppm for glucose and a positive covariance for hardness at 3.26 ppm for trimethylamine N-oxide. PMID:27775560

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

    ERIC Educational Resources Information Center

    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…

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

    PubMed

    Liu, Qing; Shi, Chaowei; Yu, Lu; Zhang, Longhua; Xiong, Ying; Tian, Changlin

    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 (15)N-labeled SH3 (Src homology 3) domain proteins in aqueous buffer were used to generate general order parameters (S(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(2)) were derived from the MD trajectory. Correlation analysis using the Gromos force field indicated that S(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(2) parameters from MD simulations with charges for all three histidines and with the SPC/E water model correlated well with S(2) calculated from the experimental NMR relaxation measurements, in a site-specific manner.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  4. Diffusion and conformation of peptide-functionalized polyphenylene dendrimers studied by fluorescence correlation and 13C NMR spectroscopy.

    PubMed

    Koynov, K; Mihov, G; Mondeshki, M; Moon, C; Spiess, H W; Müllen, K; Butt, H-J; Floudas, G

    2007-05-01

    We report on the combined use of fluorescence correlation spectroscopy (FCS) and 1H and 13C NMR spectroscopy to detect the size and type of peptide secondary structures in a series of poly-Z-L-lysine functionalized polyphenylene dendrimers bearing the fluorescent perylenediimide core in solution. In dilute solution, the size of the molecule as detected from FCS and 1H NMR diffusion measurements matches nicely. We show that FCS is a sensitive probe of the core size as well as of the change in the peptide secondary structure. However, FCS is less sensitive to functionality. A change in the peptide secondary conformation from beta-sheets to alpha-helices detected by 13C NMR spectroscopy gives rise to a steep increase in the hydrodynamic radii for number of residues n > or = 16. Nevertheless, helices are objects of low persistence.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    SciTech Connect

    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 {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

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

    PubMed Central

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-01

    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 1H/13C/1H 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 13C/1H and 13C/13C chemical shift correlations, the 3D 1H/13C/1H experiment also provides a COSY-type 1H/1H 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 (1H/1H chemical shift correlation spectrum) at different 13C chemical shift frequencies from the 3D 1H/13C/1H 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 1H/13C/1H experiment would be useful to study the structure and dynamics of a variety of chemical and biological

  9. SPAM-MQ-HETCOR: an improved method for heteronuclear correlation spectroscopy between quadrupolar and spin-1/2 nuclei in solid-state NMR.

    PubMed

    Wiench, Jerzy W; Tricot, Gregory; Delevoye, Laurent; Trebosc, Julien; Frye, James; Montagne, Lionel; Amoureux, Jean-Paul; Pruski, Marek

    2006-01-07

    The recently introduced concept of soft pulse added mixing (SPAM) is used in two-dimensional heteronuclear correlation (HETCOR) NMR experiments between half-integer quadrupolar and spin-1/2 nuclei. The experiments employ multiple quantum magic angle spinning (MQMAS) to remove the second order quadrupolar broadening and cross polarization (CP) or refocused INEPT for magnetization transfer. By using previously unexploited coherence pathways, the efficiency of SPAM-MQ-HETCOR NMR is increased by a factor of almost two without additional optimization. The sensitivity gain is demonstrated on a test sample, AlPO(4)-14, using CP and INEPT to correlate (27)Al and (31)P nuclei. SPAM-3Q-HETCOR is then applied to generate (27)Al-(31)P spectra of the devitrified 41Na(2)O-20.5Al(2)O(3)-38.5P(2)O(5) glass and the silicoaluminophosphate ECR-40. Finally, the method allowed the acquisition of the first high resolution solid-state correlation spectra between (27)Al and (29)Si.

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

    NASA Technical Reports Server (NTRS)

    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.

  11. Using magnetic coupling to implement 1H, 19F, 13C experiments in routine high resolution NMR probes

    NASA Astrophysics Data System (ADS)

    Bowyer, Paul; Finnigan, Jim; Marsden, Brian; Taber, Bob; Zens, Albert

    2015-12-01

    We report in this paper the design of 1H, 19F, 13C circuitry using magnetic coupling which can do on demand experiments where one of the three nuclei is observed and the other two are decoupled. The implementation of this circuitry in routine NMR probes is compared with capacitive coupling methods where it was found that by using magnetic coupling the performance of the routine NMR probe was not impacted by the addition of this circuitry. It is surmised that using this type of circuitry would be highly desirable for those chemists doing routine 19F NMR.

  12. Homodecoupled 1,1- and 1,n-ADEQUATE: Pivotal NMR Experiments for the Structure Revision of Cryptospirolepine.

    PubMed

    Saurí, Josep; Bermel, Wolfgang; Buevich, Alexei V; Sherer, Edward C; Joyce, Leo A; Sharaf, Maged H M; Schiff, Paul L; Parella, Teodor; Williamson, R Thomas; Martin, Gary E

    2015-08-24

    Cryptospirolepine is the most structurally complex alkaloid discovered and characterized thus far from any Cryptolepis specie. Characterization of several degradants of the original, sealed NMR sample a decade after the initial report called the validity of the originally proposed structure in question. We now report the development of improved, homodecoupled variants of the 1,1- and 1,n-ADEQUATE (HD-ADEQUATE) NMR experiments; utilization of these techniques was critical to successfully resolving long-standing structural questions associated with crytospirolepine.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. The long time tail of molecular velocity correlation in a confined fluid: observation by modulated gradient spin-echo NMR

    NASA Astrophysics Data System (ADS)

    Stepišnik, Janez; Callaghan, Paul T.

    2000-11-01

    In addition to the fast correlation for local stochastic motion the molecular velocity correlation function in a fluid enclosed within the pore boundaries features a slow long time tail decay [1,2]. This article presents a study by the NMR modulated gradient spin-echo method (MGSE) [3] on a system of water trapped in the space between the closely packed polystyrene beads. The results prove that the obtained dependence of spin-echo attenuation on time, gradient strength and modulation frequency nicely corresponds to the recently developed NMR approach, which is able to describe the effects of arbitrarily shaped gradient pulse sequence on the spin-echo attenuation [4,5]. With an MGSE pulse sequence, a repetitive train of RF pulses with interspersed gradient pulses periodically modulates the spin-phase, giving the spin-echo attenuation proportional to a value of the velocity correlation spectrum at the modulation frequency. It enables to extract the low-frequency correlation spectrum of confined water molecules. The function exhibits a negative long time tail characteristic (a low-frequency decay of the spectrum), that can be well fitted with the spectrum calculated from the solution of the Langevin equation for restricted diffusion (which exhibits an exponential decay) as well as with the spectrum obtained when simulating the hydrodynamics of molecular motion constrained by capillary walls (which gives an algebraic decay).

  15. Simultaneous acquisition of 2D and 3D solid-state NMR experiments for sequential assignment of oriented membrane protein samples.

    PubMed

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

    2015-05-01

    We present a new method called DAISY (Dual Acquisition orIented ssNMR spectroScopY) for the simultaneous acquisition of 2D and 3D oriented solid-state NMR experiments for membrane proteins reconstituted in mechanically or magnetically aligned lipid bilayers. DAISY utilizes dual acquisition of sine and cosine dipolar or chemical shift coherences and long living (15)N longitudinal polarization to obtain two multi-dimensional spectra, simultaneously. In these new experiments, the first acquisition gives the polarization inversion spin exchange at the magic angle (PISEMA) or heteronuclear correlation (HETCOR) spectra, the second acquisition gives PISEMA-mixing or HETCOR-mixing spectra, where the mixing element enables inter-residue correlations through (15)N-(15)N homonuclear polarization transfer. The analysis of the two 2D spectra (first and second acquisitions) enables one to distinguish (15)N-(15)N inter-residue correlations for sequential assignment of membrane proteins. DAISY can be implemented in 3D experiments that include the polarization inversion spin exchange at magic angle via I spin coherence (PISEMAI) sequence, as we show for the simultaneous acquisition of 3D PISEMAI-HETCOR and 3D PISEMAI-HETCOR-mixing experiments.

  16. Ultrafast acquisition of (1)H-(1)H dipolar correlation experiments in spinning elastomers.

    PubMed

    Rouger, Laetitia; Yon, Maxime; Sarou-Kanian, Vincent; Fayon, Franck; Dumez, Jean-Nicolas; Giraudeau, Patrick

    2017-02-09

    We show that two widely used 2D solid-state NMR (ssNMR) pulse sequences can be implemented in an ultrafast (UF) manner, and yield 2D spectra of elastomers in a single scan, under magic-angle spinning. UF 2D ssNMR provides an acceleration of one to several orders of magnitude for classic experiments.

  17. Probing phosphorylation by non-mammalian isoprenoid biosynthetic enzymes using (1)H-(31)P-(31)P correlation NMR spectroscopy.

    PubMed

    Majumdar, Ananya; Shah, Meha H; Bitok, J Kipchirchir; Hassis-LeBeau, Maria E; Freel Meyers, Caren L

    2009-09-01

    The biogenesis of isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP) is accomplished by the methylerythritol phosphate (MEP) pathway in plants, bacteria and parasites, making it a potential target for the development of anti-infective agents and herbicides. The biosynthetic enzymes comprising this pathway catalyze intriguing chemical transformations on diphosphate scaffolds, offering an opportunity to generate novel analogs in this synthetically challenging compound class. Such a biosynthetic approach to generating new diphosphate analogs may involve transformation through discrete diphosphate species, presenting unique challenges in structure determination and characterization of unnatural enzyme-generated diphosphate products produced in tandem. We have developed (1)H-(31)P-(31)P correlation NMR spectroscopy techniques for the direct characterization of crude MEP pathway enzyme products at low concentrations (200 microM to 5 mM) on a room temperature (non-cryogenic) NMR probe. Coupling the 100% natural abundance of the (31)P nucleus with the high intrinsic sensitivity of proton NMR, (1)H-(31)P-(31)P correlation spectroscopy is particularly useful for characterization of unnatural diphosphate enzyme products in the MEP pathway. As proof of principle, we demonstrate the rapid characterization of natural enzyme products of the enzymes IspD, E and F in tandem enzyme incubations. In addition, we have characterized several unnatural enzyme products using this technique, including new products of cytidyltransferase IspD bearing erythritol, glycerol and ribose components. The results of this study indicate that IspD may be a useful biocatalyst and highlight (1)H-(31)P-(31)P correlation spectroscopy as a valuable tool for the characterization of other unnatural products in non-mammalian isoprenoid biosynthesis.

  18. Magnetization-recovery experiments for static and MAS-NMR of I = 3/2 nuclei

    NASA Astrophysics Data System (ADS)

    Yesinowski, James P.

    2006-05-01

    Multifrequency pulsed NMR experiments on quadrupole-perturbed I = 3/2 spins in single crystals are shown to be useful for measuring spin-lattice relaxation parameters even for a mixture of quadrupolar plus magnetic relaxation mechanisms. Such measurements can then be related to other MAS-NMR experiments on powders. This strategy is demonstrated by studies of 71Ga and 69Ga (both I = 3/2) spin-lattice relaxation behavior in a single-crystal (film) sample of gallium nitride, GaN, at various orientations of the axially symmetric nuclear quadrupole coupling tensor. Observation of apparent single-exponential relaxation behavior in I = 3/2 saturation-recovery experiments can be misleading when individual contributing rate processes are neglected in the interpretation. The quadrupolar mechanism (dominant in this study) has both a single-quantum process ( T1Q1) and a double-quantum process ( T1Q2), whose time constants are not necessarily equal. Magnetic relaxation (in this study most likely arising from hyperfine couplings to unpaired delocalized electron spins in the conduction band) also contributes to a single-quantum process ( T1M). A strategy of multifrequency irradiation with observation of satellite and/or central transitions, incorporating different initial conditions for the level populations, provides a means of obtaining these three relaxation time constants from single-crystal 71Ga data alone. The 69Ga results provide a further check of internal consistency, since magnetic and quadrupolar contributions to its relaxation scale in opposite directions compared to 71Ga. For both perpendicular and parallel quadrupole coupling tensor symmetry axis orientations small but significant differences between T1Q1 and T1Q2 were measured, whereas for a tensor symmetry axis oriented at the magic-angle (54.74°) the values were essentially equal. Magic-angle spinning introduces a number of complications into the measurement and interpretation of the spin-lattice relaxation

  19. Enzymatic Resolution of 1-Phenylethanol and Formation of a Diastereomer: An Undergraduate H NMR Experiment To Introduce Chiral Chemistry.

    PubMed

    Smith, David H; Wilson, Mark; Ronhovde, Kyla; Wilson, Erin; Clevette, David; Lucas, Kerry; Holmes, Andrea

    2011-03-01

    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 ester diastereomer is analyzed by NMR. This experiment is suitable for group work in the laboratory as several diastereomers are synthesized and compared to determine which enantiomer of 1-phenylethanol reacts with the enzyme.

  20. Enzymatic Resolution of 1-Phenylethanol and Formation of a Diastereomer: An Undergraduate 1H NMR Experiment To Introduce Chiral Chemistry

    PubMed Central

    Smith, David H.; Wilson, Mark; Ronhovde, Kyla; Wilson, Erin; Clevette, David; Lucas, Kerry; Holmes, Andrea

    2010-01-01

    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 ester diastereomer is analyzed by NMR. This experiment is suitable for group work in the laboratory as several diastereomers are synthesized and compared to determine which enantiomer of 1-phenylethanol reacts with the enzyme. PMID:21359111

  1. Intertube effects on one-dimensional correlated state of metallic single-wall carbon nanotubes probed by 13C NMR

    NASA Astrophysics Data System (ADS)

    Serita, Noboru; Nakai, Yusuke; Matsuda, Kazuyuki; Yanagi, Kazuhiro; Miyata, Yasumitsu; Saito, Takeshi; Maniwa, Yutaka

    2017-01-01

    The electronic states in isolated single-wall carbon nanotubes (SWCNTs) have been considered as an ideal realization of a Tomonaga-Luttinger liquid (TLL). However, it remains unclear whether one-dimensional correlated states are realized under local environmental effects such as the formation of a bundle structure. Intertube effects originating from other adjacent SWCNTs within a bundle may drastically alter the one-dimensional correlated state. In order to test the validity of the TLL model in bundled SWCNTs, low-energy spin excitation is investigated by nuclear magnetic resonance (NMR). The NMR relaxation rate in bundled mixtures of metallic and semiconducting SWCNTs shows a power-law temperature dependence with a theoretically predicted exponent. This demonstrates that a TLL state with the same strength as that for effective Coulomb interactions is realized in a bundled sample, as in isolated SWCNTs. In bundled metallic SWCNTs, we found a power-law temperature dependence of the relaxation rate, but the magnitude of the relaxation rate is one order of magnitude smaller than that predicted by theory. Furthermore, we found an almost doubled magnitude of the Luttinger parameter. These results indicate suppressed spin excitations with reduced Coulomb interactions in bundled metallic SWCNTs, which are attributable to intertube interactions originating from adjacent metallic SWCNTs within a bundle. Our findings give direct evidence that bundling reduces the effective Coulomb interactions via intertube interactions within bundled metallic SWCNTs.

  2. Particle Correlations with the PHENIX Experiment

    SciTech Connect

    Johnson, S C

    2002-01-20

    Results of identical pion correlations from the first year of data collection with the PHENIX detector at RHIC ({radical}S{sub NN} = 130 GeV) are presented. PHENIX has good particle identification using an electromagnetic calorimeter for timing, leading to identified pions from .2 to 1 GeV/c. This extends the range of previously measured correlation radii at this energy to (k{sub T}) = 633MeV/c. The beam energy dependence of the HBT radii are studied in depth and no significant dependence of the transverse radii is present. The longitudinal correlation length has a moderate energy dependence. Furthermore, theoretical predictions of R{sub out}/R{sub side} severely underpredict the measured ratio, which is consistent with unity for all k{sub T}. The implications of these results are considered.

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

    PubMed

    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.

  4. Seeking Positive Experiences Can Produce Illusory Correlations

    ERIC Educational Resources Information Center

    Denrell, Jerker; Le Mens, Gael

    2011-01-01

    Individuals tend to select again alternatives about which they have positive impressions and to avoid alternatives about which they have negative impressions. Here we show how this sequential sampling feature of the information acquisition process leads to the emergence of an illusory correlation between estimates of the attributes of…

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

    ERIC Educational Resources Information Center

    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…

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

    ERIC Educational Resources Information Center

    Hartel, Aaron M.; Moore, Amy C.

    2014-01-01

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

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

    ERIC Educational Resources Information Center

    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…

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

    ERIC Educational Resources Information Center

    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.

  9. Broadband homonuclear correlation spectroscopy driven by combined R2(n)(v) sequences under fast magic angle spinning for NMR structural analysis of organic and biological solids.

    PubMed

    Hou, Guangjin; Yan, Si; Trébosc, Julien; Amoureux, Jean-Paul; Polenova, Tatyana

    2013-07-01

    We recently described a family of experiments for R2n(v) Driven Spin Diffusion (RDSD) spectroscopy suitable for homonuclear correlation experiments under fast MAS conditions [G. Hou, S. Yan, S.J. Sun, Y. Han, I.J. Byeon, J. Ahn, J. Concel, A. Samoson, A.M. Gronenborn, T. Polenova, Spin diffusion drive by R-symmetry sequencs: applications to homonuclear correlation spectroscopy in MAS NMR of biological and organic solids, J. Am. Chem. Soc. 133 (2011) 3943-3953]. In these RDSD experiments, since the broadened second-order rotational resonance conditions are dominated by the radio frequency field strength and the phase shifts, as well as the size of reintroduced dipolar couplings, the different R2n(v) sequences display unique polarization transfer behaviors and different recoupling frequency bandwidths. Herein, we present a series of modified R2n(v) sequences, dubbed COmbined R2n(v)-Driven (CORD), that yield broadband homonuclear dipolar recoupling and give rise to uniform distribution of cross peak intensities across the entire correlation spectrum. We report NMR experiments and numerical simulations demonstrating that these CORD spin diffusion sequences are suitable for broadband recoupling at a wide range of magnetic fields and MAS frequencies, including fast-MAS conditions (νr=40 kHz and above). Since these CORD sequences are largely insensitive to dipolar truncation, they are well suited for the determination of long-range distance constraints, which are indispensable for the structural characterization of a broad range of systems. Using U-(13)C,(15)N-alanine and U-(13)C,(15)N-histidine, we show that under fast-MAS conditions, the CORD sequences display polarization transfer efficiencies within broadband frequency regions that are generally higher than those offered by other existing spin diffusion pulse schemes. A 89-residue U-(13)C,(15)N-dynein light chain (LC8) protein has also been used to demonstrate that the CORD sequences exhibit uniformly high cross peak

  10. Al coordination and water speciation in hydrous aluminosilicate glasses: direct evidence from high-resolution heteronuclear 1H-27Al correlation NMR.

    PubMed

    Xue, Xianyu; Kanzaki, Masami

    2007-02-01

    In order to shed light on the dissolution mechanisms of water in depolymerized aluminosilicate melts/glasses, a comprehensive one- (1D) and two-dimensional (2D) NMR study has been carried out on hydrous Ca- and Mg-aluminosilicate glasses of a haplobasaltic composition. The applied techniques include 1D 1H MAS NMR and 27Al-->1H cross-polarization (CP) MAS NMR, and 2D 1H NOESY and double-quantum (DQ) MAS NMR, 27Al triple-quantum (3Q) MAS NMR and 27Al-->1H heteronuclear correlation (HETCOR) and 3QMAS/HETCOR NMR. Ab initio calculations were also performed to place additional constraints on the 1H NMR characteristics of AlOH and Si(OH)Al groups. This study has revealed, for the first time, the presence of free OH (i.e. (Ca, Mg)OH), SiOH and AlOH species, in addition to molecular H2O, in hydrous glasses of a depolymerized aluminosilicate composition. The AlOH groups are mostly associated with four-coordinate Al, but some are associated with five- and six-coordinate Al.

  11. (127)I NMR calculations in binary metal iodides by PBE-GGA, YS-PBE0 and mBJ exchange correlation potentials.

    PubMed

    Bashi, M; Aliabad, H A Rahnamaye; Mowlavi, A A; Ahmad, Iftikhar

    We have calculated Nuclear Magnetic Resonance (NMR) spectroscopy for (127)I (quadrupolar nuclei I=5/2) in binary metal iodides XI (X=Li, Na, K, Rb and Cs) by using PBE- GGA, YS- PBE0 and mBJ exchange correlation potentials. The results show that the nature of bonds between Iodine and metal atoms are ionic. The main contribution in NMR spectroscopy is related to the induced current inside the atomic sphere and the remainder of the unit cell volume contributes only a few ppm. Obtained NMR shifts are compared with the NMR shielding data and the NMR shielding for metal-p band varies across the series about 221ppm. Density of states results indicate that the largest contribution in the shielding comes from the I-core electrons (1s and 4d). The NMR shielding graphs show that there are negative linear correlation with slope -1.18, -1.16 and -1.01 by PBE- GGA, YS- PBE0 and mBJ, respectively. The computed results by mBJ are in good agreement with the experimental values.

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

    PubMed Central

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

    2016-01-01

    Transverse relaxation rate measurements in MAS solid-state NMR provide information about molecular motions occurring on nanoseconds-to-milliseconds (ns-ms) time scales. The measurement of heteronuclear (13C, 15N) relaxation rate constants in the presence of a spin-lock radio-frequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins has been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely (i) the role of CSA/dipolar cross-correlated relaxation (CCR), and (ii) 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 this cross-correlated relaxation rate constant depends on ns-ms motions, and can thus itself provide insight into dynamics. We find that proton spin-diffusion attenuates this cross-correlated relaxation, 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 the present manuscript reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation. PMID:27500976

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

    PubMed

    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.

  14. Analytical optimization of active bandwidth and quality factor for TOCSY experiments in NMR spectroscopy

    PubMed Central

    Coote, Paul; Bermel, Wolfgang; Wagner, Gerhard; Arthanari, Haribabu

    2016-01-01

    Active bandwidth and global quality factor are the two main metrics used to quantitatively compare the performance of TOCSY mixing sequences. Active bandwidth refers to the spectral region over which at least 50% of the magnetization is transferred via a coupling. Global quality factor scores mixing sequences according to the worst-case transfer over a range of possible mixing times and chemical shifts. Both metrics reward high transfer efficiency away from the main diagonal of a two-dimensional spectrum. They can therefore be used to design mixing sequences that will function favorably in experiments. Here, we develop optimization methods tailored to these two metrics, including precise control of off-diagonal cross peak buildup rates. These methods produce square shaped transfer efficiency profiles, directly matching the desirable properties that the metrics are intended to measure. The optimization methods are analytical, rather than numerical. The two resultant shaped pulses have significantly higher active bandwidth and quality factor, respectively, than all other known sequences. They are therefore highly suitable for use in NMR spectroscopy. We include experimental verification of these improved waveforms on small molecule and protein samples. PMID:27515670

  15. The covariance of the differences between experimental and theoretical chemical shifts as an aid for assigning two-dimensional heteronuclear correlation solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Czernek, Jiří; Brus, Jiří

    2014-07-01

    A robust method for the assignment of two-dimensional heteronuclear correlations in the solid-state NMR spectra is described. It statistically evaluates the differences between measured and theoretical (obtained from first-principles calculations of the NMR chemical shielding property of periodic materials) chemical shifts. The values of the covariance of these differences, and of the standard deviations of the respective linear correlations, are elucidative for the spectral assignment process. The efficacy of the method is demonstrated for three crystalline systems: L-tyrosine hydrochloride, L-tyrosine ansolvate, and the polymorphic form I of o-acetylsalicylic acid.

  16. Susceptibility corrections in solid-state NMR experiments with oriented membrane samples. Part I: applications

    NASA Astrophysics Data System (ADS)

    Glaser, Ralf W.; Ulrich, Anne S.

    2003-09-01

    Chemical shift referencing of solid-state NMR experiments on oriented membranes has to compensate for bulk magnetic susceptibility effects that are associated with the non-spherical sample shape, as described in the accompanying paper [J. Magn. Reson. 164 (2003) 115-127]. The resulting frequency deviations can be on the order of 10 ppm, which is serious for nuclei with a narrow chemical shift anisotropy such as 1H or 13C, and in some cases even 19F. Two referencing schemes are proposed here to compensate for these effects: A flat (0.4 mm) glass container with an isotropic reference molecule dissolved in a thin film of liquid is stacked on top of the oriented membrane sample. Alternatively, the intrinsic proton signal of the hydrated lipid can be used for chemical shift referencing. Further aspects related to magnetic susceptibility are discussed, such as air gaps in susceptibility-matched probeheads, the benefits of shimming, and limitations in the accuracy of orientational constraints. A biological application is illustrated by a series of experiments on the antimicrobial peptide PGLa, aimed at understanding its concentration-dependent membranolytic effect. To address a wide range of molar peptide/lipid ratios between 1:3000 and 1:8, multilayers of hydrated DMPC containing a 19F-labeled peptide were oriented between stacked glass plates. Maintaining an approximately constant amount of peptide gives rise to thick samples (18 plates) at low, and thin samples (3 plates) at high peptide/lipid ratio. Accurate referencing was critical to reveal a small but significant change over 5 ppm in the anisotropic chemical shift of the 19F label on the peptide, indicative of a change in the orientation and/or dynamics of PGLa in the membrane.

  17. Design of a Quantitative DEPT NMR Experiment for Carbon-13 Acquisitions

    DTIC Science & Technology

    2011-09-01

    NMR Spectroscopy. Prog. Nucl. Magn. Reson. Spectrosc. 1977, //, 79-83. 7. Shaka, A.J.; Keeler , J.; Freeman, R. Evaluation of a New Broadband Decoupling Sequence: WALTZ-16. J. Magn. Reson. 1983, 53, 313-340. 15

  18. Collection of NMR Scalar and Residual Dipolar Couplings Using a Single Experiment.

    PubMed

    Gil-Silva, Leandro F; Santamaría-Fernández, Raquel; Navarro-Vázquez, Armando; Gil, Roberto R

    2016-01-11

    A new DMSO-compatible aligning gel based on cross-linked poly(2-hydroxylethyl methacrylate) (poly-HEMA) has been developed. Due to a significant difference in bulk magnetic susceptibility between the DMSO inside and outside the gel, it is possible to simultaneously collect isotropic and anisotropic NMR data, such as residual dipolar couplings (RDC), in the same NMR tube. RDC-assisted structural analysis of menthol and the alkaloid retrorsine is reported as proof of concept.

  19. Rayleigh-Bénard percolation transition study of thermal convection in porous media: numerical simulation and NMR experiments.

    PubMed

    Weber, M; Klemm, A; Kimmich, R

    2001-05-07

    Thermal convection was studied as a function of the porosity in random-site percolation model objects in a Rayleigh-Bénard configuration. NMR velocity mapping experiments and numerical simulations using the finite-volume method are compared. Velocity histograms were evaluated and can be described by power laws in a wide range. The maximum velocity as a function of the porosity indicates a combined percolation/Rayleigh-Bénard transition.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  1. Residue-specific NH exchange rates studied by NMR diffusion experiments

    NASA Astrophysics Data System (ADS)

    Brand, Torsten; Cabrita, Eurico J.; Morris, Gareth A.; Günther, Robert; Hofmann, Hans-Jörg; Berger, Stefan

    2007-07-01

    We present a novel approach to the investigation of rapid (>2 s -1) NH exchange rates in proteins, based on residue-specific diffusion measurements. 1H, 15N-DOSY-HSQC spectra are recorded in order to observe resolved amide proton signals for most residues of the protein. Human ubiquitin was used to demonstrate the proposed method. Exchange rates are derived directly from the decay data of the diffusion experiment by applying a model deduced from the assumption of a two-site exchange with water and the "pure" diffusion coefficients of water and protein. The "pure" diffusion coefficient of the protein is determined in an experiment with selective excitation of the amide protons in order to suppress the influence of magnetization transfer from water to amide protons on the decay data. For rapidly exchanging residues a comparison of our results with the exchange rates obtained in a MEXICO experiment showed good agreement. Molecular dynamics (MD) and quantum mechanical calculations were performed to find molecular parameters correlating with the exchangeability of the NH protons. The RMS fluctuations of the amide protons, obtained from the MD simulations, together with the NH coupling constants provide a bilinear model which shows a good correlation with the experimental NH exchange rates.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. 13C-NMR spectra and contact time experiment for Skjervatjern fulvic and humic acids

    USGS Publications Warehouse

    Malcolm, R.L.

    1992-01-01

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

  4. Determination of the hyperfine magnetic field in magnetic carbon-based materials: DFT calculations and NMR experiments

    PubMed Central

    Freitas, Jair C. C.; Scopel, Wanderlã L.; Paz, Wendel S.; Bernardes, Leandro V.; Cunha-Filho, Francisco E.; Speglich, Carlos; Araújo-Moreira, Fernando M.; Pelc, Damjan; Cvitanić, Tonči; Požek, Miroslav

    2015-01-01

    The prospect of carbon-based magnetic materials is of immense fundamental and practical importance, and information on atomic-scale features is required for a better understanding of the mechanisms leading to carbon magnetism. Here we report the first direct detection of the microscopic magnetic field produced at 13C nuclei in a ferromagnetic carbon material by zero-field nuclear magnetic resonance (NMR). Electronic structure calculations carried out in nanosized model systems with different classes of structural defects show a similar range of magnetic field values (18–21 T) for all investigated systems, in agreement with the NMR experiments. Our results are strong evidence of the intrinsic nature of defect-induced magnetism in magnetic carbons and establish the magnitude of the hyperfine magnetic field created in the neighbourhood of the defects that lead to magnetic order in these materials. PMID:26434597

  5. On-flow pulsed field gradient heteronuclear correlation spectrometry in off-line LC-SPE-NMR analysis of chemicals related to the chemical weapons convention.

    PubMed

    Koskela, Harri; Ervasti, Mia; Björk, Heikki; Vanninen, Paula

    2009-02-01

    Hyphenation of liquid chromatography with nuclear magnetic resonance spectroscopy (LC-NMR) is a useful technique in the analysis of complex samples. However, application of on-flow 1H NMR spectrometry during the LC-NMR analysis usually suffers from high intensity of eluent resonances. The poor dynamic range can be improved either with use of deuterated eluents or with various signal suppression schemes. Deuterated eluents are expensive, and peak-selective signal suppression schemes are often unsatisfactory when detection of chemicals at low concentration is needed. If the analytes have a common heteronucleus, on-flow pulsed field gradient heteronuclear correlation spectrometry can offer several benefits. The analytes can be monitored selectively, while the intense nondeuterated eluent and impurity background can be effectively eliminated. In our study, on-flow one-dimensional (1D) 1H-31P heteronuclear single quantum coherence (HSQC) spectrometry was utilized in the analysis of characteristic organophosphorus degradation products of nerve agents sarin and soman during chromatographic separation. These chemicals were not detectable by UV, so their retention times were monitored using on-flow 1D 1H-31P HSQC. This enabled application of LC-NMR combined with solid-phase extraction (LC-SPE-NMR) in analysis of these organophosphorus chemicals in an alkaline decontamination solution. The analytes were extracted from the SPE cartridges with deuterated eluent, and the off-line NMR analysis was performed using a mass-sensitive microcoil probe head. The used on-flow 1D 1H-31P HSQC approach offered a high dynamic range and good detection limit (ca. 10 microg/55 nmol) with a high sampling frequency (1 point per 2 s) in the acquired pseudo-two-dimensional spectrum. No significant impurity background was present in the off-line NMR samples, and identification of the extracted analytes was straightforward.

  6. Selective Detection of 1H NMR Resonances of 13CH n Groups Using Two-Dimensional Maximum-Quantum Correlation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, M.; Farrant, R. D.; Nicholson, J. K.; Lindon, J. C.

    Methods for editing spectra based upon maximum-quantum filtering in two-dimensional 1H NMR are presented (MAXY NMR). Separation of 1H resonances from 13CH, 13CH 2, and 13CH 3 groups is demonstrated, using the coherence of the attached natural-abundance 13C spin. Two-dimensional correlation pulse sequences based on J connectivity (MAXY-COSY), total J connectivity (MAXY-TOCSY), and NOE and exchange processes (MAXY-NOESY) are given and exemplified using dexamethasone as a model compound. In addition, an improved form of a 13CH 2 only COSY spectrum (gem-COSY) is shown, and the application of z magnetic-field gradients is demonstrated as an alternative to phase cycling. The approach should have utility in the assignment of complex 1H NMR spectra which arise from peptides or complex mixtures such as biofluids.

  7. NMR-Profiles of Protein Solutions

    PubMed Central

    Pedrini, Bill; Serrano, Pedro; Mohanty, Biswaranjan; Geralt, Michael; Wüthrich, Kurt

    2014-01-01

    NMR-Profiles are quantitative one-dimensional presentations of two-dimensional [15N,1H]-correlation spectra used to monitor the quality of protein solutions prior to and during NMR structure determinations and functional studies. In our current use in structural genomics projects, a NMR-Profile is recorded at the outset of a structure determination, using a uniformly 15N-labeled micro-scale sample of the protein. We thus assess the extent to which polypeptide backbone resonance assignments can be achieved with given NMR techniques, for example, conventional triple resonance experiments or APSY-NMR. With the availability of sequence-specific polypeptide backbone resonance assignments in the course of the structure determination, an “Assigned NMR-Profile” is generated, which visualizes the variation of the 15N–1H correlation cross peak intensities along the sequence and thus maps the sequence locations of polypeptide segments for which the NMR line shapes are affected by conformational exchange or other processes. The Assigned NMR-Profile provides a guiding reference during later stages of the structure determination, and is of special interest for monitoring the protein during functional studies, where dynamic features may be modulated during physiological functions. PMID:23839514

  8. Solution behavior and complete sup 1 H and sup 13 C NMR assignments of the coenzyme B sub 12 derivative (5 prime -deoxyadenosyl)cobinamide using modern 2D NMR experiments, including 600-MHz sup 1 H NMR data

    SciTech Connect

    Pagano, T.G.; Yohannes, P.G.; Marzilli, L.G. ); Hay, B.P.; Scott, J.R.; Finke, R.G. )

    1989-02-15

    Two-dimensional (2D) NMR methods have been used to assign completely the {sup 1}H and {sup 13}C NMR spectra of the (5{prime}-deoxyadenosyl)cobinamide cation (AdoCbi{sup +}) in D{sub 2}O. Most of the {sup 1}H spectral assignments were made by using 2D homonuclear shift correlation spectroscopy (COSY), homonuclear Hartmann-Hahn spectroscopy (HOHAHA), absorption-mode (phase sensitive) 2D nuclear Overhauser effect (NOE) spectroscopy, and spin-locked NOE spectroscopy (also called ROESY, for rotating-frame Overhauser enhancement spectroscopy). Most of the protonated carbon resonances were assigned by using {sup 1}H-detected heteronuclear multiple-quantum coherence (HMQC) spectroscopy. The nonprotonated carbon resonances, as well as the remaining unassigned {sup 1}H and {sup 13}C NMR signals, were assigned from long-range {sup 1}H-{sup 13}C connectivities determined from {sup 1}H-detected multiple-bond heteronuclear multiple-quantum coherence spectroscopy (HMBC). Comparison of the {sup 13}C chemical shifts and {sup 1}H NOEs of AdoCbi{sup +} with those of coenzyme B{sup 12} ((5{prime}-deoxyadenosyl)cobalamin) and its benzimidazole-protonated, base-off form indicates that the electronic properties and structure of AdoCbi{sup +} are similar to that of coenzyme B{sup 12} in the protonated, base-off form. The {sup 13}C chemical shifts of most of the carbons of AdoCbi{sup +} do not vary significantly from those of base-off, benzimidazole-protonated coenzyme B{sup 12}, indicating that the electronic environment of the corrin ring is also similar in both compounds. However, significant differences in the chemical shifts of some of the corresponding carbons of the b, d, e, and f corrin side chains in AdoCbi{sup +} and in base-off, benzimidazole-protonated coenzyme B{sub 12} indicate that the positions of these side chains may be different in AdoCbi{sup +} compared to base-off coenzyme B{sup 12}.

  9. Investigations on computed 13C NMR one-dimensional non-refocused INEPT experiments for structural determinations in O-methylated glycosides

    NASA Astrophysics Data System (ADS)

    Pouységu, Laurent; Nobert, Philippe; Deffieux, Denis; De Jéso, Bernard; Lartigue, Jean-Claude; Pétraud, Michel; Ratier, Max

    1999-10-01

    A new one-dimensional 13C NMR approach for the determination of methoxyl substituents configuration in O-methylated glycosides is presented. Assignments are based on structural investigations by non-refocused INEPT experiments associated with numerical methods.

  10. Fluorescence correlation spectroscopy of repulsive systems: theory, simulation, and experiment.

    PubMed

    Feng, Ligang; Yang, Jingfa; Zhao, Jiang; Wang, Dapeng; Koynov, Kaloian; Butt, Hans-Jürgen

    2013-06-07

    The theoretical basis of fluorescence correlation spectroscopy (FCS) for repulsive systems, such as charged colloids or macromolecules, has been further expanded and developed. It is established that the collective correlation function can no longer be fitted using the theoretical model of non-interacting systems. Also, it is discovered that the collective correlation function can be divided into two parts: a self-part and a distinct-part, named as the self-correlation and cross-correlation function, respectively. The former indicates the self-diffusion of objects, while the latter describes mutual interactions. Dual-color fluorescence cross-correlation spectroscopy provides the direct measurements of the two parts. The particle concentration and mean squared displacement of single particles can be deduced from the self-correlation function, while the correlation volume between particles can be approximated from the cross-correlation function. In the case of charged colloids, the Debye length of the solution and particle surface charge number can be fitted from the cross-correlation function. These theoretical results are successfully proven using Brownian dynamics simulations and preliminary FCS experiments for model charged colloidal systems.

  11. Structure and Dynamics of the Aβ21–30 Peptide from the Interplay of NMR Experiments and Molecular Simulations

    PubMed Central

    Fawzi, Nicolas L.; Phillips, Aaron H.; Ruscio, Jory Z.; Doucleff, Michaeleen; Wemmer, David E.; Head-Gordon, Teresa

    2012-01-01

    We combine molecular dynamics simulations and new high-field NMR experiments to describe the solution structure of the Aβ21–30 peptide fragment that may be relevant for understanding structural mechanisms related to Alzheimer’s disease. By using two different empirical force-field combinations, we provide predictions of the three-bond scalar coupling constants (3JHNHα), chemical-shift values, 13C relaxation parameters, and rotating-frame nuclear Overhauser effect spectroscopy (ROESY) crosspeaks that can then be compared directly to the same observables measured in the corresponding NMR experiment of Aβ21–30. We find robust prediction of the 13C relaxation parameters and medium-range ROESY crosspeaks by using new generation TIP4P-Ew water and Amber ff99SB protein force fields, in which the NMR validates that the simulation yields both a structurally and dynamically correct ensemble over the entire Aβ21–30 peptide. Analysis of the simulated ensemble shows that all medium-range ROE restraints are not satisfied simultaneously and demonstrates the structural diversity of the Aβ21–30 conformations more completely than when determined from the experimental medium-range ROE restraints alone. We find that the structural ensemble of the Aβ21–30 peptide involves a majority population (~60%) of unstructured conformers, lacking any secondary structure or persistent hydrogen-bonding networks. However, the remaining minority population contains a substantial percentage of conformers with a β-turn centered at Val24 and Gly25, as well as evidence of the Asp23 to Lys28 salt bridge important to the fibril structure. This study sets the stage for robust theoretical work on Aβ1–40 and Aβ1–42, for which collection of detailed NMR data on the monomer will be more challenging because of aggregation and fibril formation on experimental timescales at physiological conditions. In addition, we believe that the interplay of modern molecular simulation and high

  12. Following Glycolysis Using 13C NMR: An Experiment Adaptable to Different Undergraduate Levels

    NASA Astrophysics Data System (ADS)

    Mega, T. L.; Carlson, C. B.; Cleary, D. A.

    1997-12-01

    This paper describes a laboratory exercise where the glycolysis of [1-13C] glucose under anaerobic conditions was followed using 13C NMR spectroscopy. The exercise is described in terms of its suitability for a variety of different undergraduate levels, although the emphasis in this paper is on its use in a n advanced chemistry laboratory course. The kinetics of the loss of glucose and the production of ethanol were investigated and found not to fit simple first or second order kinetics. In addition, the relative reaction rates of the two anomeric forms of glucose were analyzed, and it was determined that the a anomeric form reacted faster than the β anomeric form. Using proton-coupled 13C NMR, some of the metabolites were identified including ethanol (major) and glycerol (minor). Reaction and spectroscopic details are included.

  13. A set of 4D NMR experiments of enhanced resolution for easy resonance assignment in proteins

    NASA Astrophysics Data System (ADS)

    Zawadzka-Kazimierczuk, Anna; Kazimierczuk, Krzysztof; Koźmiński, Wiktor

    2010-01-01

    This paper presents examples of techniques based on the principle of random sampling that allows acquisition of NMR spectra featuring extraordinary resolution. This is due to increased dimensionality and maximum evolution time reached. The acquired spectra of CsPin protein and maltose binding protein were analyzed statistically with the aim to evaluate each technique. The results presented include exemplary spectral cross-sections. The spectral data provided by the proposed techniques allow easy assignment of backbone and side-chain resonances.

  14. The experience of mathematical beauty and its neural correlates

    PubMed Central

    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. PMID:24592230

  15. Acidic Properties and Structure-Activity Correlations of Solid Acid Catalysts Revealed by Solid-State NMR Spectroscopy.

    PubMed

    Zheng, Anmin; Li, Shenhui; Liu, Shang-Bin; Deng, Feng

    2016-04-19

    Solid acid materials with tunable structural and acidic properties are promising heterogeneous catalysts for manipulating and/or emulating the activity and selectivity of industrially important catalytic reactions. On the other hand, the performances of acid-catalyzed reactions are mostly dictated by the acidic features, namely, type (Brønsted vs Lewis acidity), amount, strength, and local environment of acid sites. The latter is relevant to their location (intra- vs extracrystalline), and possible confinement and Brønsted-Lewis acid synergy effects that may strongly affect the host-guest interactions, reaction mechanism, and shape selectivity of the catalytic system. This account aims to highlight some important applications of state-of-the-art solid-state NMR (SSNMR) techniques for exploring the structural and acidic properties of solid acid catalysts as well as their catalytic performances and relevant reaction pathway invoked. In addition, density functional theory (DFT) calculations may be exploited in conjunction with experimental SSNMR studies to verify the structure-activity correlations of the catalytic system at a microscopic scale. We describe in this Account the developments and applications of advanced ex situ and/or in situ SSNMR techniques, such as two-dimensional (2D) double-quantum magic-angle spinning (DQ MAS) homonuclear correlation spectroscopy for structural investigation of solid acids as well as study of their acidic properties. Moreover, the energies and electronic structures of the catalysts and detailed catalytic reaction processes, including the identification of reaction species, elucidation of reaction mechanism, and verification of structure-activity correlations, made available by DFT theoretical calculations were also discussed. Relevant discussions will focus primarily on results obtained from our laboratories in the past decade, including (i) quantitative and qualitative acidity characterization utilizing assorted probe molecules

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

    NASA Astrophysics Data System (ADS)

    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

  17. Fast Magic-Angle Spinning Three-Dimensional NMR Experiment for Simultaneously Probing H-H and N-H Proximities in Solids.

    PubMed

    Reddy, G N Manjunatha; Malon, Michal; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P

    2016-12-06

    A fast magic-angle spinning (MAS, 70 kHz) solid-state NMR experiment is presented that combines (1)H Double-Quantum (DQ) and (14)N-(1)H HMQC (Heteronuclear Multiple-Quantum Coherence) pulse-sequence elements, so as to simultaneously probe H-H and N-H proximities in molecular solids. The proposed experiment can be employed in both two-dimensional (2D) and three-dimensional (3D) versions: first, a 2D (14)N HMQC-filtered (1)H-DQ experiment provides specific DQ-SQ correlation peaks for proton pairs that are in close proximities to the nitrogen sites, thereby achieving spectral filtration. Second, a proton-detected three-dimensional (3D) (1)H(DQ)-(14)N(SQ)-(1)H(SQ) experiment correlates (1)H(DQ)-(1)H(SQ) chemical shifts with (14)N shifts such that longer range N···H-H correlations are observed between protons and nitrogen atoms with internuclear NH distances exceeding 3 Å. Both 2D and 3D versions of the proposed experiment are demonstrated for an amino acid hydrochloride salt, l-histidine·HCl·H2O, and a DNA nucleoside, guanosine·2H2O. In the latter case, the achieved spectral filtration ensures that DQ cross peaks are only observed for guanine NH and CH8 (1)H resonances and not ribose and water (1)H resonances, thus providing insight into the changes in the solid-state structure of this hydrate that occur over time; significant changes are observed in the NH and NH2(1)H chemical shifts as compared to the freshly recrystallized sample previously studied by Reddy et al., Cryst. Growth Des. 2015, 15, 5945.

  18. A Laboratory Experiment on How to Create Dimensionless Correlations

    ERIC Educational Resources Information Center

    Edwards, Robert V.

    2010-01-01

    An experiment is described that illustrates how chemical engineering correlations are created. Balls of different diameters and different specific gravities (all less than one) are dropped from several heights into a pool of water, and the maximum depth reached by the ball is measured. This data is used to estimate the coefficients for a…

  19. Backbone dynamics of the antifungal Psd1 pea defensin and its correlation with membrane interaction by NMR spectroscopy.

    PubMed

    de Medeiros, Luciano Neves; Angeli, Renata; Sarzedas, Carolina G; Barreto-Bergter, Eliana; Valente, Ana Paula; Kurtenbach, Eleonora; Almeida, Fabio C L

    2010-02-01

    Plant defensins are cysteine-rich cationic peptides, components of the innate immune system. The antifungal sensitivity of certain exemplars was correlated to the level of complex glycosphingolipids in the membrane of fungi strains. Psd1 is a 46 amino acid residue defensin isolated from pea seeds which exhibit antifungal activity. Its structure is characterized by the so-called cysteine-stabilized alpha/beta motif linked by three loops as determined by two-dimensional NMR. In the present work we explored the measurement of heteronuclear Nuclear Overhauser Effects, R1 and R2 (15)N relaxation ratios, and chemical shift to probe the backbone dynamics of Psd1 and its interaction with membrane mimetic systems with phosphatidylcholine (PC) or dodecylphosphocholine (DPC) with glucosylceramide (CMH) isolated from Fusarium solani. The calculated R2 values predicted a slow motion around the highly conserved among Gly12 residue and also in the region of the Turn3 His36-Trp38. The results showed that Psd1 interacts with vesicles of PC or PC:CMH in slightly different forms. The interaction was monitored by chemical shift perturbation and relaxation properties. Using this approach we could map the loops as the binding site of Psd1 with the membrane. The major binding epitope showed conformation exchange properties in the mus-ms timescale supporting the conformation selection as the binding mechanism. Moreover, the peptide corresponding to part of Loop1 (pepLoop1: Gly12 to Ser19) is also able to interact with DPC micelles acquiring a stable structure and in the presence of DPC:CMH the peptide changes to an extended conformation, exhibiting NOE mainly with the carbohydrate and ceramide parts of CMH.

  20. Identification of an Unknown Compound by Combined Use of IR, [to the first power]H NMR, [to the thirteenth power]C NMR, and Mass Spectrometry: A Real-Life Experience in Structure Determination

    ERIC Educational Resources Information Center

    Liotta, Louis J.; James-Pederson, Magdalena

    2008-01-01

    In this introductory organic chemistry experiment, the students get an opportunity to analyze and identify an unknown compound as it is done in a real-laboratory setting. First, students are instructed on the proper operation of three major instruments, NMR, IR, and GC-MS, and are given a sample of an unknown compound. The students are expected to…

  1. Phase Cycling Schemes for finite-pulse-RFDR MAS Solid State NMR Experiments

    PubMed Central

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

    2015-01-01

    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, XY414, for the fp-RFDR pulse sequence employed in 2D 1H/1H 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, XY412, XY413, XY414, and XY814 phase cycles under different spinning speeds ranging from 10 to 100 kHz. The theoretical calculations reveal the presence of second-order terms (T10T2,±2, T1,±1T2,±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 in homogeneity effects revealed that XY414 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-RFDR are also analyzed

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

    NASA Astrophysics Data System (ADS)

    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, XY414, for the fp-RFDR pulse sequence employed in 2D 1H/1H 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, XY412, XY413, XY414, and XY814 phase cycles under different spinning speeds ranging from 10 to 100 kHz. The theoretical calculations reveal the presence of second-order terms (T10T2,±2, T1,±1T2,±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 XY414 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-RFDR are also analyzed

  3. A Guided Inquiry Approach to NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

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

    1998-04-01

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

  4. The use of spin desalting columns in DMSO-quenched H/D-exchange NMR experiments.

    PubMed

    Chandak, Mahesh S; Nakamura, Takashi; Takenaka, Toshio; Chaudhuri, Tapan K; Yagi-Utsumi, Maho; Chen, Jin; Kato, Koichi; Kuwajima, Kunihiro

    2013-04-01

    Dimethylsulfoxide (DMSO)-quenched hydrogen/deuterium (H/D)-exchange is a powerful method to characterize the H/D-exchange behaviors of proteins and protein assemblies, and it is potentially useful for investigating non-protected fast-exchanging amide protons in the unfolded state. However, the method has not been used for studies on fully unfolded proteins in a concentrated denaturant or protein solutions at high salt concentrations. In all of the current DMSO-quenched H/D-exchange studies of proteins so far reported, lyophilization was used to remove D2 O from the protein solution, and the lyophilized protein was dissolved in the DMSO solution to quench the H/D exchange reactions and to measure the amide proton signals by two-dimensional nuclear magnetic resonance (2D NMR) spectra. The denaturants or salts remaining after lyophilization thus prevent the measurement of good NMR spectra. In this article, we report that the use of spin desalting columns is a very effective alternative to lyophilization for the medium exchange from the D2 O buffer to the DMSO solution. We show that the medium exchange by a spin desalting column takes only about 10 min in contrast to an overnight length of time required for lyophilization, and that the use of spin desalting columns has made it possible to monitor the H/D-exchange behavior of a fully unfolded protein in a concentrated denaturant. We report the results of unfolded ubiquitin in 6.0M guanidinium chloride.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Effect of phase fluctuations on INS and NMR experiments in the pseudogap regime of the high-Tc cuprates

    NASA Astrophysics Data System (ADS)

    Westfahl, Harry; Morr, Dirk K.

    2000-03-01

    In this talk we present a theoretical scenario for inelastic neutron (INS) and nuclear magnetic resonance (NMR) experiments in the pseudogap region of the underdoped high-Tc superconductors. Within the spin-fermion model we study the effect of phase fluctuations in the superconducting d-wave order parameter on the spin susceptibility, probed in INS and NMR experiments. We show that the spin susceptibility is determined by the average square Doppler shift, W(T), which results from the coupling between the quasiparticle momentum and the thermally excited supercurrents. Our scenario provides an explanation for the temperature dependence of the resonance peak and of the ^63Cu spin lattice relaxation rate, 1/T_1, in the region where the phase fluctuations are present. Moreover, we show that 1/T1 is a direct probe of W(T). Our results for W(T) are in good qualitative agreement with those obtained in scanning tunneling spectroscopy (Ch. Remer et al., Phys. Rev. Lett. 80), 149 (1998) and high frequency ac transport(J. Corson et al., Nature 398), 221 (1999)

  7. 13C-detected NMR experiments for measuring chemical shifts and coupling constants in nucleic acid bases.

    PubMed

    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.

  8. Fluorine detected 2D NMR experiments for the practical determination of size and sign of homonuclear F-F and heteronuclear C-F multiple bond J-coupling constants in multiple fluorinated compounds.

    PubMed

    Aspers, Ruud L E G; Ampt, Kirsten A M; Dvortsak, Peter; Jaeger, Martin; Wijmenga, Sybren S

    2013-06-01

    The use of fluorine in molecules obtained from chemical synthesis has become increasingly important within the pharmaceutical and agricultural industry. NMR characterization of these compounds is of great value with respect to their structure elucidation, their screening in metabolomics investigations and binding studies. The favorable NMR properties of the fluorine nucleus make NMR with fluorine detection of great value in this respect. A suite of NMR 2D F-F- and F-C-correlation experiments with fluorine detection was applied to the assignment of resonances, (n)J(CF)- and (n)J(FF)-couplings as well as the determination of their size and sign. The utilization of this experiment suite was exemplarily demonstrated for a highly fluorinated vinyl alkyl ether. Especially F-C HSQC and J-scaled F-C HMBC experiments allowed determining the size of the J-couplings of this compound. The relative sign of its homo- and heteronuclear couplings was achieved by different combinations of 2D NMR experiments, including non-selective and F2-selective F-C XLOC, F2-selective F-C HMQC, and F-F COSY. The F2-one/two-site selective F-C XLOC versions were found highly useful, as they led to simplifications of the common E.COSY patterns and resulted in a higher confidence level of the assignment by using selective excitation. The combination of F2-one/two-site selective F-C XLOC experiments with a F2-one-site selective F-C HMQC experiment provided the signs of all (n)J(CF)- and (n)J(FF)-couplings in the vinyl moiety of the test compound. Other combinations of experiments were found useful as well for special purposes when focusing for example on homonuclear couplings a combination of F-F COSY-10 with a F2-one-site selective F-C HMQC could be used. The E.COSY patterns in the spectra demonstrated were analyzed by use of the spin-selective displacement vectors, and in case of the XLOC also by use of the DQ- and ZQ-displacement vectors. The variety of experiments presented shall contribute to

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

    NASA Technical Reports Server (NTRS)

    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.

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

    PubMed

    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

  11. Complete backbone and DENQ side chain NMR assignments in proteins from a single experiment: implications to structure-function studies.

    PubMed

    Reddy, Jithender G; Hosur, Ramakrishna V

    2014-03-01

    Resonance assignment is the first and the most crucial step in all nuclear magnetic resonance (NMR) investigations on structure-function relationships in biological macromolecules. Often, the assignment exercise has to be repeated several times when specific interactions with ligands, substrates etc., have to be elucidated for understanding the functional mechanisms. While the protein backbone serves to provide a scaffold, the side chains interact directly with the ligands. Such investigations will be greatly facilitated, if there are rapid methods for obtaining exhaustive information with minimum of NMR experimentation. In this context, we present here a pulse sequence which exploits the recently introduced technique of parallel detection of multiple nuclei, e.g. (1)H and (13)C, and results in two 3D-data sets simultaneously. These yield complete backbone resonance assignment ((1)H(N), (15)N, (13)CO, (1)Hα/(13)Cα, and (1)Hβ/(13)Cβ chemical shifts) and side chain assignment of D, E, N and Q residues. Such an exhaustive assignment has the potential of yielding accurate 3D structures using one or more of several algorithms which calculate structures of the molecules very reliably on the basis of NMR chemical shifts alone. The side chain assignments of D, E, N, and Q will be extremely valuable for interaction studies with different ligands; D and E side chains are known to be involved in majority of catalytic activities. Utility of this experiment has been demonstrated with Ca(2+) bound M-crystallin, which contains largely D, E, N and Q residues at the metal binding sites.

  12. Structural study of synthetic mica montmorillonite by means of 2D MAS NMR experiments

    NASA Astrophysics Data System (ADS)

    Alba, M. D.; Castro, M. A.; Chain, P.; Naranjo, M.; Perdigón, A. C.

    2005-07-01

    Syn-1, is a synthetic mica montmorillonite interstratified mineral that forms one of the standard clay samples in the Clay Minerals Society Source Clays Project. However, there are still controversies regarding some structural aspects such as the interlayer composition or the location of the extra-aluminium determined by chemical analysis. The main objective of this paper is to shed light on those structural aspects that affect the reactivity of the interstratified minerals. For this purpose, we have used 1 H 29 Si and 1 H 27Al HETCOR MAS NMR to show that it is likely that the interlayer space of the beidellite part is composed of ammonium ions whereas ammonium and aluminium ions are responsible for the charge balance in the mica type layer.

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

    NASA Astrophysics Data System (ADS)

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

    1992-03-01

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

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

    PubMed

    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.

  15. Isolation and 2D NMR Studies of Alkaloids from Comptonella sessilifoliola1.

    PubMed

    Pusset, J; Lopez, J L; Pais, M; Neirabeyeh, M A; Veillon, J M

    1991-04-01

    Six known furanoquinoline alkaloids have been isolated from the wood and trunk bark of COMPTONELLA SESSILIFOLIOLA (Guillaumin) Hartley (Rutaceae). 2D NMR experiments gave the assignment of all the signals for both (1)H- and (13)C-NMR spectra. Pteleine and kokusaginine were used as models. The two-dimensional carbon-proton correlation experiments, performed for the first time on furanoquinoline alkaloids, led us to correct (13)C-NMR assignments previously described in the literature.

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

    PubMed

    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.

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

    ERIC Educational Resources Information Center

    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…

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

    ERIC Educational Resources Information Center

    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…

  19. Giant spin-orbit effects on (1)H and (13)C NMR shifts for uranium(vi) complexes revisited: role of the exchange-correlation response kernel, bonding analyses, and new predictions.

    PubMed

    Greif, Anja H; Hrobárik, Peter; Autschbach, Jochen; Kaupp, Martin

    2016-11-09

    Previous relativistic quantum-chemical predictions of unusually large (1)H and (13)C NMR chemical shifts for ligand atoms directly bonded to a diamagnetic uranium(vi) center (P. Hrobárik, V. Hrobáriková, A. H. Greif and M. Kaupp, Angew. Chem., Int. Ed., 2012, 51, 10884) have been revisited by two- and four-component relativistic density functional methods. In particular, the effect of the exchange-correlation response kernel, which had been missing in the previously used two-component version of the Amsterdam Density Functional program, has been examined. Kernel contributions are large for cases with large spin-orbit (SO) contributions to the NMR shifts and may amount to up to ∼30% of the total shifts, which means more than a 50 ppm difference for the metal-bonded carbon shifts in some extreme cases. Previous calculations with a PBE-40HF functional had provided overall reasonable predictions, due to cancellation of errors between the missing kernel contributions and the enhanced exact-exchange (EXX) admixture of 40%. In the presence of an exchange-correlation kernel, functionals with lower EXX admixtures give already good agreement with experiments, and the PBE0 functional provides reasonable predictive quality. Most importantly, the revised approach still predicts unprecedented giant (1)H NMR shifts between +30 ppm and more than +200 ppm for uranium(vi) hydride species. We also predict uranium-bonded (13)C NMR shifts for some synthetically known organometallic U(vi) complexes, for which no corresponding signals have been detected to date. In several cases, the experimental lack of these signals may be attributed to unexpected spectral regions in which some of the (13)C NMR shifts can appear, sometimes beyond the usual measurement area. An extremely large uranium-bonded (13)C shift above 550 ppm, near the upper end of the diamagnetic (13)C shift range, is predicted for a known pincer carbene complex. Bonding analyses allow in particular the magnitude of the SO

  20. Coexistence of antiferromagnetic and ferromagnetic spin correlations in SrCo2As2 revealed by 59Co and 75As NMR

    DOE PAGES

    Wiecki, P.; Ogloblichev, V.; Pandey, Abhishek; ...

    2015-06-15

    In nonsuperconducting, metallic paramagnetic SrCo2As2, inelastic neutron scattering measurements have revealed strong stripe-type q=(π,0) antiferromagnetic (AFM) spin correlations. Using nuclear magnetic resonance (NMR) measurements on 59Co and 75As nuclei, we demonstrate that stronger ferromagnetic (FM) spin correlations coexist in SrCo2As2. Our NMR data are consistent with density functional theory (DFT) calculations which show enhancements at both q=(π,0) and the in-plane FM q=0 wave vectors in static magnetic susceptibility χ(q). We suggest that the strong FM fluctuations prevent superconductivity in SrCo2As2, despite the presence of stripe-type AFM fluctuations. Since DFT calculations have consistently revealed similar enhancements of the χ(q) at bothmore » q=(π,0) and q=0 in the iron-based superconductors and parent compounds, our observation of FM correlations in SrCo2As2 calls for detailed studies of FM correlations in the iron-based superconductors.« less

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Interfaces in polymer nanocomposites - An NMR study

    NASA Astrophysics Data System (ADS)

    Böhme, Ute; Scheler, Ulrich

    2016-03-01

    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. 1H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T2 is most suited. In this presentation we report on two applications of T2 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. 14N overtone NMR spectra under magic angle spinning: Experiments and numerically exact simulations

    NASA Astrophysics Data System (ADS)

    O'Dell, Luke A.; Brinkmann, Andreas

    2013-02-01

    It was recently shown that high resolution 14N overtone NMR spectra can be obtained directly under magic angle spinning (MAS) conditions [L. A. O'Dell and C. I. Ratcliffe, Chem. Phys. Lett. 514, 168 (2011)], 10.1016/j.cplett.2011.08.030. Preliminary experimental results showed narrowed powder pattern widths, a frequency shift that is dependent on the MAS rate, and an apparent absence of spinning sidebands, observations which appeared to be inconsistent with previous theoretical treatments. Herein, we reproduce these effects using numerically exact simulations that take into account the full nuclear spin Hamiltonian. Under sample spinning, the 14N overtone signal is split into five (0, ±1, ±2) overtone sidebands separated by the spinning frequency. For a powder sample spinning at the magic angle, the +2ωr sideband is dominant while the others show significantly lower signal intensities. The resultant MAS powder patterns show characteristic quadrupolar lineshapes from which the 14N quadrupolar parameters and isotropic chemical shift can be determined. Spinning the sample at other angles is shown to alter both the shapes and relative intensities of the five overtone sidebands, with MAS providing the benefit of averaging dipolar couplings and shielding anisotropy. To demonstrate the advantages of this experimental approach, we present the 14N overtone MAS spectrum obtained from L-histidine, in which powder patterns from all three nitrogen sites are clearly resolved.

  4. (13)C NMR Metabolomics: INADEQUATE Network Analysis.

    PubMed

    Clendinen, Chaevien S; Pasquel, Christian; Ajredini, Ramadan; Edison, Arthur S

    2015-06-02

    The many advantages of (13)C NMR are often overshadowed by its intrinsically low sensitivity. Given that carbon makes up the backbone of most biologically relevant molecules, (13)C NMR offers a straightforward measurement of these compounds. Two-dimensional (13)C-(13)C correlation experiments like INADEQUATE (incredible natural abundance double quantum transfer experiment) are ideal for the structural elucidation of natural products and have great but untapped potential for metabolomics analysis. We demonstrate a new and semiautomated approach called INETA (INADEQUATE network analysis) for the untargeted analysis of INADEQUATE data sets using an in silico INADEQUATE database. We demonstrate this approach using isotopically labeled Caenorhabditis elegans mixtures.

  5. Application of 13C-labeling and 13C-13C COSY NMR experiments in the structure determination of a microbial natural product.

    PubMed

    Kwon, Yun; Park, Sunghyouk; Shin, Jongheon; Oh, Dong-Chan

    2014-08-01

    The elucidation of the structures of complex natural products bearing many quaternary carbons remains challenging, even in this advanced spectroscopic era. (13)C-(13)C COSY NMR spectroscopy shows direct couplings between (13)C and (13)C, which comprise the backbone of a natural product. Thus, this type of experiment is particularly useful for natural products bearing consecutive quaternary carbons. However, the low sensitivity of (13)C-based NMR experiments, due to the low natural abundance of the (13)C nucleus, is problematic when applying these techniques. Our efforts in the (13)C labeling of a microbial natural product, cyclopiazonic acid (1), by feeding (13)C-labeled glucose to the fungal culture, enabled us to acquire (13)C-(13)C COSY NMR spectra on a milligram scale that clearly show the carbon backbone of the compound. This is the first application of (13)C-(13)C COSY NMR experiments for a natural product. The results suggest that (13)C-(13)C COSY NMR spectroscopy can be routinely used for the structure determination of microbial natural products by (13)C-enrichment of a compound with (13)C-glucose.

  6. A Qualitative-Quantitative H-NMR Experiment for the Instrumental Analysis Laboratory.

    ERIC Educational Resources Information Center

    Phillips, John S.; Leary, James J.

    1986-01-01

    Describes an experiment combining qualitative and quantitative information from hydrogen nuclear magnetic resonance spectra. Reviews theory, discusses the experimental approach, and provides sample results. (JM)

  7. High intensity positron beam and angular correlation experiments at Livermore

    SciTech Connect

    Howell, R.H.; Rosenberg, I.J.; Meyer, P.; Fluss, M.J.

    1985-03-01

    A positron beam apparatus that produces a variable energy positron beam with sufficient intensity to perform new positron experiments in an ultrahigh vacuum environment has been installed at the Lawrence Livermore 100 MeV electron linac. We have installed two large area position sensitive gamma-ray detectors to measure angular correlations in two dimensions and a separate highly collimated detector to measure positronium energy distributions by time-of-flight velocity determination. Data from measurements on single crystals of Cu will be described.

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

    SciTech Connect

    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.

  9. Poisson’s Ratio Extrapolation from Digital Image Correlation Experiments

    DTIC Science & Technology

    2013-03-01

    5f. WORK UNIT NUMBER Q16H 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NO. Air Force Research Laboratory...ACRONYM(S) Air Force Research Laboratory (AFMC) AFRL/RQR 5 Pollux Drive 11. SPONSOR/MONITOR’S REPORT Edwards AFB CA 93524-7048 NUMBER(S) AFRL-RQ-ED-TP...Affairs Clearance Number XXXXX.    POISSON’S RATIO EXTRAPOLATION FROM DIGITAL IMAGE CORRELATION EXPERIMENTS Timothy C. Miller Air Force Research

  10. Rotary echo nutation NMR

    NASA Astrophysics Data System (ADS)

    Janssen, R.; Tijink, G. A. H.; Veeman, W. S.

    1988-01-01

    A two-dimensional solid state NMR experiment which combines rotary echoes and nutation NMR is investigated and used to study different sodium sites in zeolite NaA. It is shown that with this technique sodium ions with different relaxation rates in the rotating frame can be distinguished.

  11. Multiple acquisition of magic angle spinning solid-state NMR experiments using one receiver: Application to microcrystalline and membrane protein preparations

    NASA Astrophysics Data System (ADS)

    Gopinath, T.; Veglia, Gianluigi

    2015-04-01

    Solid-state NMR spectroscopy of proteins is a notoriously low-throughput technique. Relatively low-sensitivity and poor resolution of protein samples require long acquisition times for multidimensional NMR experiments. To speed up data acquisition, we developed a family of experiments called Polarization Optimized Experiments (POE), in which we utilized the orphan spin operators that are discarded in classical multidimensional NMR experiments, recovering them to allow simultaneous acquisition of multiple 2D and 3D experiments, all while using conventional probes with spectrometers equipped with one receiver. POE allow the concatenation of multiple 2D or 3D pulse sequences into a single experiment, thus potentially combining all of the aforementioned advances, boosting the capability of ssNMR spectrometers at least two-fold without the addition of any hardware. In this perspective, we describe the first generation of POE, such as dual acquisition MAS (or DUMAS) methods, and then illustrate the evolution of these experiments into MEIOSIS, a method that enables the simultaneous acquisition of multiple 2D and 3D spectra. Using these new pulse schemes for the solid-state NMR investigation of biopolymers makes it possible to obtain sequential resonance assignments, as well as distance restraints, in about half the experimental time. While designed for acquisition of heteronuclei, these new experiments can be easily implemented for proton detection and coupled with other recent advancements, such as dynamic nuclear polarization (DNP), to improve signal to noise. Finally, we illustrate the application of these methods to microcrystalline protein preparations as well as single and multi-span membrane proteins reconstituted in lipid membranes.

  12. Multiple acquisition of magic angle spinning solid-state NMR experiments using one receiver: application to microcrystalline and membrane protein preparations.

    PubMed

    Gopinath, T; Veglia, Gianluigi

    2015-04-01

    Solid-state NMR spectroscopy of proteins is a notoriously low-throughput technique. Relatively low-sensitivity and poor resolution of protein samples require long acquisition times for multidimensional NMR experiments. To speed up data acquisition, we developed a family of experiments called Polarization Optimized Experiments (POE), in which we utilized the orphan spin operators that are discarded in classical multidimensional NMR experiments, recovering them to allow simultaneous acquisition of multiple 2D and 3D experiments, all while using conventional probes with spectrometers equipped with one receiver. POE allow the concatenation of multiple 2D or 3D pulse sequences into a single experiment, thus potentially combining all of the aforementioned advances, boosting the capability of ssNMR spectrometers at least two-fold without the addition of any hardware. In this perspective, we describe the first generation of POE, such as dual acquisition MAS (or DUMAS) methods, and then illustrate the evolution of these experiments into MEIOSIS, a method that enables the simultaneous acquisition of multiple 2D and 3D spectra. Using these new pulse schemes for the solid-state NMR investigation of biopolymers makes it possible to obtain sequential resonance assignments, as well as distance restraints, in about half the experimental time. While designed for acquisition of heteronuclei, these new experiments can be easily implemented for proton detection and coupled with other recent advancements, such as dynamic nuclear polarization (DNP), to improve signal to noise. Finally, we illustrate the application of these methods to microcrystalline protein preparations as well as single and multi-span membrane proteins reconstituted in lipid membranes.

  13. The Bose-Einstein correlations in CDFII experiment

    SciTech Connect

    Lovás, Lubomír

    2008-01-01

    We present the results of a study of p$\\bar{p}$ collisions at √s = 1.96 TeV collected by the CDF-II experiment at Tevatron collider. The Bose-Einstein correlations of the π±π± two boson system have been studied in the minimum-bias high-multiplicity events. The research was carried out on the sample at the size of 173761 events. The two pion correlations have been retrieved. The final results were corrected to the coulomb interactions. Two different reference samples were compared and discussed. A significant two-pion correlation enhancement near origin is observed. This enhancement effect has been used to evaluate the radius of the two-pion emitter source. We have used the TOF detector to distinguish between π and K mesons. The C2(Q) function parameters have also been retrieved for the sample containing only tagged π mesons. A comparison between four different parametrizations based on two diff t theoretical approaches of the C2(Q) function is given.

  14. The Fourier Transform in Chemistry-NMR, Part 3. Multiple-Pulse Experiments.

    ERIC Educational Resources Information Center

    Williams, Kathryn R.; King, Roy W.

    1990-01-01

    Described are six multipulse experiments with an emphasis on their application to common problems in chemistry. Exercises in relaxation time measurement, spin echoes, and polarization transfer are proposed. (CW)

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

    ERIC Educational Resources Information Center

    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…

  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

    ERIC Educational Resources Information Center

    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.

    PubMed

    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. Soils, Pores, and NMR

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

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

  19. Bridging experiment and theory: A template for unifying NMR data and electronic structure calculations

    SciTech Connect

    Brown, David M. L.; Cho, Herman; de Jong, Wibe A.

    2016-02-09

    Here, the testing of theoretical models with experimental data is an integral part of the scientific method, and a logical place to search for new ways of stimulating scientific productivity. Often experiment/theory comparisons may be viewed as a workflow comprised of well-defined, rote operations distributed over several distinct computers, as exemplified by the way in which predictions from electronic structure theories are evaluated with results from spectroscopic experiments. For workflows such as this, which may be laborious and time consuming to perform manually, software that could orchestrate the operations and transfer results between computers in a seamless and automated fashion would offer major efficiency gains. Such tools also promise to alter how researchers interact with data outside their field of specialization by, e.g., making raw experimental results more accessible to theorists, and the outputs of theoretical calculations more readily comprehended by experimentalists.

  20. Bridging experiment and theory: A template for unifying NMR data and electronic structure calculations

    DOE PAGES

    Brown, David M. L.; Cho, Herman; de Jong, Wibe A.

    2016-02-09

    Here, the testing of theoretical models with experimental data is an integral part of the scientific method, and a logical place to search for new ways of stimulating scientific productivity. Often experiment/theory comparisons may be viewed as a workflow comprised of well-defined, rote operations distributed over several distinct computers, as exemplified by the way in which predictions from electronic structure theories are evaluated with results from spectroscopic experiments. For workflows such as this, which may be laborious and time consuming to perform manually, software that could orchestrate the operations and transfer results between computers in a seamless and automated fashionmore » would offer major efficiency gains. Such tools also promise to alter how researchers interact with data outside their field of specialization by, e.g., making raw experimental results more accessible to theorists, and the outputs of theoretical calculations more readily comprehended by experimentalists.« less

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

    ERIC Educational Resources Information Center

    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…

  2. Ultrafast multidimensional Laplace NMR for a rapid and sensitive chemical analysis

    NASA Astrophysics Data System (ADS)

    Ahola, Susanna; Zhivonitko, Vladimir V.; Mankinen, Otto; Zhang, Guannan; Kantola, Anu M.; Chen, Hsueh-Ying; Hilty, Christian; Koptyug, Igor V.; Telkki, Ville-Veikko

    2015-09-01

    Traditional nuclear magnetic resonance (NMR) spectroscopy relies on the versatile chemical information conveyed by spectra. To complement conventional NMR, Laplace NMR explores diffusion and relaxation phenomena to reveal details on molecular motions. Under a broad concept of ultrafast multidimensional Laplace NMR, here we introduce an ultrafast diffusion-relaxation correlation experiment enhancing the resolution and information content of corresponding 1D experiments as well as reducing the experiment time by one to two orders of magnitude or more as compared with its conventional 2D counterpart. We demonstrate that the method allows one to distinguish identical molecules in different physical environments and provides chemical resolution missing in NMR spectra. Although the sensitivity of the new method is reduced due to spatial encoding, the single-scan approach enables one to use hyperpolarized substances to boost the sensitivity by several orders of magnitude, significantly enhancing the overall sensitivity of multidimensional Laplace NMR.

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

    PubMed

    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.

  4. Sorption isotherm measurements by NMR.

    PubMed

    Leisen, Johannes; Beckham, Haskell W; Benham, Michael

    2002-01-01

    An experimental setup is described for the automated recording of sorption isotherms by NMR experiments at precisely defined levels of relative humidity (RH). Implementation is demonstrated for a cotton fabric; Bloch decays. T1 and T2* relaxation times were measured at predefined steps of increasing and decreasing relative humidities (RHs) so that a complete isotherm of NMR properties was obtained. Bloch decays were analyzed by fitting to relaxation functions consisting or a slow- and a fast-relaxing component. The fraction of slow-relaxing component was greater than the fraction of sorbed moisture determined from gravimetric sorption data. The excess slow-relaxing component was attributed to plasticized segments of the formerly rigid cellulose matrix. T1 and T2* sorption isotherms exhibit hysteresis similar to gravimetric sorption isotherms. However, correlating RH to moisture content (MC) reveals that both relaxation constants depend only on MC, and not on the history of moisture exposure.

  5. Quadrupolar solid-state NMR and repetitive experiments: Some aspects in the Liouville space. Application to spins I=1.

    PubMed

    Odin, Christophe

    2016-12-29

    The aim of this work is to generalize the Ernst-Anderson model developed to account of the steady-state regime of isolated spins I=1/2 subject to a train of strictly identical pulse sequences separated by free evolution periods of same duration. We generalize this model to the general case of spins I≥1 and general pulse sequence within the framework of the Liouville space. In particular, it is proved that under reasonable assumptions, a well defined steady-state regime is reached which is independent of the initial conditions. The general formal expressions obeyed by the steady-state density operator are given as a function of pulse propagators and relaxation operator for single and two-pulse sequences. In solid-state NMR where recycle time can be made, at the same time, much longer than typical coherence relaxation times and smaller than typical population relaxation times, further simplification leads to more tractable formula. As an example, the formalism is applied to I=1 spins with hard and soft single pulse sequence, or to the solid echo sequence. In particular, we were able to generalize the Ernst-Anderson formula to spins I=1. The pertinence of the theory is verified by comparing the theoretical and numerical simulations outputs to (2)H single crystal experiments performed on nonadecane/urea C19D40/urea-H4 compound.

  6. Multiple quantum filtered (23)Na NMR in the Langendorff perfused mouse heart: Ratio of triple/double quantum filtered signals correlates with [Na]i.

    PubMed

    Eykyn, Thomas R; Aksentijević, Dunja; Aughton, Karen L; Southworth, Richard; Fuller, William; Shattock, Michael J

    2015-09-01

    We investigate the potential of multiple quantum filtered (MQF) (23)Na NMR to probe intracellular [Na]i in the Langendorff perfused mouse heart. In the presence of Tm(DOTP) shift reagent the triple quantum filtered (TQF) signal originated largely from the intracellular sodium pool with a 32±6% contribution of the total TQF signal arising from extracellular sodium, whilst the rank 2 double-quantum filtered signal (DQF), acquired with a 54.7° flip-angle pulse, originated exclusively from the extracellular sodium pool. Given the different cellular origins of the (23)Na MQF signals we propose that the TQF/DQF ratio can be used as a semi-quantitative measure of [Na]i in the mouse heart. We demonstrate a good correlation of this ratio with [Na]i measured with shift reagent at baseline and under conditions of elevated [Na]i. We compare the measurements of [Na]i using both shift reagent and TQF/DQF ratio in a cohort of wild type mouse hearts and in a transgenic PLM(3SA) mouse expressing a non-phosphorylatable form of phospholemman, showing a modest but measurable elevation of baseline [Na]i. MQF filtered (23)Na NMR is a potentially useful tool for studying normal and pathophysiological changes in [Na]i, particularly in transgenic mouse models with altered Na regulation.

  7. Multiple quantum filtered 23Na NMR in the Langendorff perfused mouse heart: Ratio of triple/double quantum filtered signals correlates with [Na]i

    PubMed Central

    Eykyn, Thomas R.; Aksentijević, Dunja; Aughton, Karen L.; Southworth, Richard; Fuller, William; Shattock, Michael J.

    2015-01-01

    We investigate the potential of multiple quantum filtered (MQF) 23Na NMR to probe intracellular [Na]i in the Langendorff perfused mouse heart. In the presence of Tm(DOTP) shift reagent the triple quantum filtered (TQF) signal originated largely from the intracellular sodium pool with a 32 ± 6% contribution of the total TQF signal arising from extracellular sodium, whilst the rank 2 double-quantum filtered signal (DQF), acquired with a 54.7° flip-angle pulse, originated exclusively from the extracellular sodium pool. Given the different cellular origins of the 23Na MQF signals we propose that the TQF/DQF ratio can be used as a semi-quantitative measure of [Na]i in the mouse heart. We demonstrate a good correlation of this ratio with [Na]i measured with shift reagent at baseline and under conditions of elevated [Na]i. We compare the measurements of [Na]i using both shift reagent and TQF/DQF ratio in a cohort of wild type mouse hearts and in a transgenic PLM3SA mouse expressing a non-phosphorylatable form of phospholemman, showing a modest but measurable elevation of baseline [Na]i. MQF filtered 23Na NMR is a potentially useful tool for studying normal and pathophysiological changes in [Na]i, particularly in transgenic mouse models with altered Na regulation. PMID:26196304

  8. Determination of magnetic and structural properties in solids containing antiferromagnetically coupled metal centers using NMR methods. Magneto-structural correlations in anhydrous copper(II) n-butyrate

    SciTech Connect

    Campbell, G.C.; Haw, J.F.

    1988-10-19

    A new approach to the investigation of magneto-structural correlations in solids containing antiferromagnetically coupled transition-metal centers is described that illustrates the potential of NMR spectroscopy in such work. The results of a variable-temperature (VT) /sup 13/C cross-polarization magic-angle-spinning (CP/MAS) NMR investigation of anhydrous copper(II) n-butyrate, (Cu(C/sub 3/H/sub 7/COO)/sub 2/)/sub 2/ are reported. Isotropic shifts are found to be primarily contact in origin, and a statistical analysis of their temperature dependence allows the calculation of singlet-triplet energy level separations (-2J), diamagnetic shifts (delta/sub dia/), and electron-nucleus hyperfine coupling constants (A), which are shown to give insight into the mechanisms of electron delocalization along the superexchange pathway. Signal multiplicity can be related to compound structure, which was determined by using x-ray crystallography. The title compound is triclinic and has a space group of P/anti 1/ with a = 9.035 (2) /angstrom/, b = 5.192 (2) /angstrom/, c = 11.695 (3) /angstrom/, ..cap alpha.. = 85.88 (2)/degrees/, ..gamma.. = 109.32 (2)/degrees/, Z = 1, and V = 515.2 (3) /angstrom//sup 3/; the final weighted R value for 2169 reflections was 0.048. 21 references, 4 figures, 4 tables.

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

    PubMed

    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.

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

    SciTech Connect

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

    2014-06-20

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

  11. Correlation of lactate and pH in human skeletal muscle after exercise by 1H NMR.

    PubMed

    Pan, J W; Hamm, J R; Hetherington, H P; Rothman, D L; Shulman, R G

    1991-07-01

    We have made in vivo 1H NMR measurements of the time course of pH and lactate in human skeletal muscle after exercise. Spectra were obtained in a 4.7-T 30-cm bore Bruker Biospec spectrometer with a 2.5-cm diameter single surface coil. pH was determined from the shift of the endogenous carnosine H-C2 peak while lactate concentrations were determined by comparison with endogenous total creatine, taken to be 28.5 mM/kg wet wt. Fitting the data shows that the exponential decay of lactate (-0.094 +/- 0.014 min-1. t1/2 = 10.6 min) is slower than that of pH (-0.147 +/- 0.015 min-1, t1/2 = 4.7 min), n = 7 with two different volunteers. These values are significantly different with P less than 0.0005. Relaxation times of lactate and creatine were also measured for lactate quantitation; creatine T1, 1.23 +/- 12 s, T2, 136.2 +/- 26.4 ms (both in resting human muscle); lactate T1 (in postmortem rabbit muscle), 1.0 +/- 11 s and T2, 80 ms (in postexercise human muscle). At the end of intense exercise, the lactate level reached was 25.3 +/- 4.0 mM and the average pH drop was 1.0 pH unit. We discuss the implications of these measurements in conjunction with existing data on other sources of H+ flux, phosphocreatine resynthesis, H+ transport, and contribution of inorganic phosphate to buffering.

  12. Hepatocarcinogenesis tumor grading correlated with in vivo image-guided {sup 1}H-NMR spectroscopy in a rat model

    SciTech Connect

    Towner, Rheal A. . E-mail: Rheal-Towner@omrf.ouhsc.edu; Foley, Lesley M.; Painter, Dorothy M.

    2005-09-01

    Hepatocellular carcinoma (HCC) is a common malignancy worldwide, the occurrence of which is unevenly distributed. Most hepatocellular carcinoma cases present late and have a poor prognosis; therefore, early diagnosis is essential to prolong survival. Differential diagnosis with magnetic resonance imaging (MRI) is difficult. We studied the feasibility of using magnetic resonance spectroscopy (MRS) at 7.0 T for the diagnosis and grading of liver tumors. An animal model of hepatocarcinogenesis was used, which allowed tumor progression from precancerous lesions to hepatocellular carcinomas. This study was focused primarily on the grading of the tumors and its correlation with the ratio between the MRS peaks arising from MRS-detected lipid hydrogens (0.9, 1.3 and 5.3 ppm) and compared to the {gamma}-methylene hydrogens of glutamate (Glu) and glutamine (Gln) which was used as an internal reference (2.4 ppm). The lipid methylene hydrogen (1.3 ppm) to (Glu + Gln) ratio was found to correlate with the formation of differentiated small foci and (precancerous) hepatic nodules, whereas the unsaturated olefinic lipid hydrogen (5.3 ppm) to (Glu + Gln) ratio was able to correlate with the formation of late stage tumors such as adenomas and hepatocellular carcinomas. The results of our study suggest that MRS-detected alterations in lipid metabolism can be correlated with the grading of liver tumor tissue at different stages during the carcinogenesis process.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. High Resolution non-Markovianity in NMR

    PubMed Central

    Bernardes, Nadja K.; Peterson, John P. S.; Sarthour, Roberto S.; Souza, Alexandre M.; Monken, C. H.; Roditi, Itzhak; Oliveira, Ivan S.; Santos, Marcelo F.

    2016-01-01

    Memoryless time evolutions are ubiquitous in nature but often correspond to a resolution-induced approximation, i.e. there are correlations in time whose effects are undetectable. Recent advances in the dynamical control of small quantum systems provide the ideal scenario to probe some of these effects. Here we experimentally demonstrate the precise induction of memory effects on the evolution of a quantum coin (qubit) by correlations engineered in its environment. In particular, we design a collisional model in Nuclear Magnetic Resonance (NMR) and precisely control the strength of the effects by changing the degree of correlation in the environment and its time of interaction with the qubit. We also show how these effects can be hidden by the limited resolution of the measurements performed on the qubit. The experiment reinforces NMR as a test bed for the study of open quantum systems and the simulation of their classical counterparts. PMID:27669652

  15. High Resolution non-Markovianity in NMR

    NASA Astrophysics Data System (ADS)

    Bernardes, Nadja K.; Peterson, John P. S.; Sarthour, Roberto S.; Souza, Alexandre M.; Monken, C. H.; Roditi, Itzhak; Oliveira, Ivan S.; Santos, Marcelo F.

    2016-09-01

    Memoryless time evolutions are ubiquitous in nature but often correspond to a resolution-induced approximation, i.e. there are correlations in time whose effects are undetectable. Recent advances in the dynamical control of small quantum systems provide the ideal scenario to probe some of these effects. Here we experimentally demonstrate the precise induction of memory effects on the evolution of a quantum coin (qubit) by correlations engineered in its environment. In particular, we design a collisional model in Nuclear Magnetic Resonance (NMR) and precisely control the strength of the effects by changing the degree of correlation in the environment and its time of interaction with the qubit. We also show how these effects can be hidden by the limited resolution of the measurements performed on the qubit. The experiment reinforces NMR as a test bed for the study of open quantum systems and the simulation of their classical counterparts.

  16. Staphylococcal nuclease active-site amino acids: pH dependence of tyrosines and arginines by sup 13 C NMR and correlation with kinetic studies

    SciTech Connect

    Grissom, C.G.; Markley, J.L. )

    1989-03-07

    The pH and temperature dependence of the kinetic parameters of staphylococcal nuclease have been examined with three p-nitrophenyl phosphate containing DNA analogues that vary as to 3'-substituent. With wild-type (Foggi variant) nuclease (nuclease wt) and the substrates thymidine 3'-phosphate 5'-(p-nitrophenyl phosphate) (PNPdTp), thymidine 3'-methylphosphonate 5'-(p-nitrophenyl phosphate) (PNPdTp Me), and thymidine 5'-(p-nitrophenyl phosphate) (PNPdT), k{sub cat} remains nearly constant at 13 min{sup {minus}1}. However, k{sub cat}/k{sub m} with nuclease wt varies considerably. The data suggests that the inflection k{sub cat}/K{sub m} with pK{sub a} at 9.67 arises from ionization of tyrosine-85, which hydrogen bonds to the divalent 3'-phosphomonester of substrates with this substituent. The enthalpy of ionization of both deprotonation steps in the k{sub cat}/K{sub m} versus pH profile is 5 kcal/mol. {sup 13}C NMR has been used to determine the pK{sub a} values of the arginine and tyrosine residues. The results do not rule out arginine as a candidate for the acidic catalyst that protonates the 5'-ribose alkoxide prior to product release. The phenolic hydroxyl carbon of tyrosine-85 has been assigned by comparing the {sup 13}C NMR spectrum of nuclease wt and nuclease Y85F. This correlation between pK{sub a} values along with the absence of other candidates indicates that the ionization of tyrosine-85 is the pK{sub a} seen in the k{sub cat}/K{sub m} vs pH profile for substrates with a divalent 3'-phosphomonester. This conclusion is consistent with the proposed role of tyrosine-85 as a hydrogen-bond donor to the 3'-phosphomonoester of substrates poised for exonucleolytic hydrolysis.

  17. Efficient identification of flavones, flavanones and their glycosides in routine analysis via off-line combination of sensitive NMR and HPLC experiments.

    PubMed

    Blunder, Martina; Orthaber, Andreas; Bauer, Rudolf; Bucar, Franz; Kunert, Olaf

    2017-03-01

    We present a standardized, straightforward and efficient approach applicable in routine analysis of flavonoids combining sensitive NMR and HPLC experiments. The determination of the relative configuration of sugar moieties usually requires the acquisition of (13)C NMR shift values. We use a combination of HPLC and sensitive NMR experiments (1D-proton, 2D-HSQC) for the unique identification of known flavones, flavanones, flavonols and their glycosides. Owing to their broad range of polarity, we developed HPLC and UHPLC methods (H2O/MeOH/MeCN/HCOOH) which we applied and validated by analyzing 46 common flavones and flavanones and exemplified for four plant extracts. A searchable data base is provided with full data comprising complete proton and carbon resonance assignments, expansions of HSQC-spectra, HPLC parameters (retention time, relative retention factor), UV/Vis and mass spectral data of all compounds, which enables a rapid identification and routine analysis of flavones and flavanones from plant extracts and other products in nutrition and food chemistry.

  18. "Invisible" conformers of an antifungal disulfide protein revealed by constrained cold and heat unfolding, CEST-NMR experiments, and molecular dynamics calculations.

    PubMed

    Fizil, Ádám; Gáspári, Zoltán; Barna, Terézia; Marx, Florentine; Batta, Gyula

    2015-03-23

    Transition between conformational states in proteins is being recognized as a possible key factor of function. In support of this, hidden dynamic NMR structures were detected in several cases up to populations of a few percent. Here, we show by two- and three-state analysis of thermal unfolding, that the population of hidden states may weight 20-40 % at 298 K in a disulfide-rich protein. In addition, sensitive (15) N-CEST NMR experiments identified a low populated (0.15 %) state that was in slow exchange with the folded PAF protein. Remarkably, other techniques failed to identify the rest of the NMR "dark matter". Comparison of the temperature dependence of chemical shifts from experiments and molecular dynamics calculations suggests that hidden conformers of PAF differ in the loop and terminal regions and are most similar in the evolutionary conserved core. Our observations point to the existence of a complex conformational landscape with multiple conformational states in dynamic equilibrium, with diverse exchange rates presumably responsible for the completely hidden nature of a considerable fraction.

  19. NMR 13C-isotopic enrichment experiments to study carbon-partitioning into organic solutes in the red alga Grateloupia doryphora.

    PubMed

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

    2004-01-01

    The red alga Grateloupia doryphora Montagne (Howe) (Cryptonemiales, Halymeniaceae) was used as a model to investigate the effects of changes in seawater salinity on the intracellular low-molecular-weight organic compounds. Carbon-partitioning into major organic solutes was followed by 13C nuclear magnetic resonance (NMR) spectroscopy on living algae incubated in NaH13CO3-enriched seawater, and by high resolution 1H and 13C NMR experiments performed on 13C-enriched algal extracts. NMR and high performance liquid chromatography (HPLC) analyses both demonstrated that floridoside level was the most affected by changes in salinity: it rose under the hypersaline treatment and decreased under hyposaline one. Moreover, at low salinity, the high labeling of floridoside (45.3% 13C-enrichment for C1) together with its low concentrations both provided evidence of great increase in the de novo biosynthesis and turnover rate. Our experiments also demonstrated a high incorporation of photosynthetic carbon into amino acids, especially glutamate, under hypoosmotic conditions. On the other hand, isethionic acid and N-methyl-methionine sulfoxide were only partly labeled, which indicates they do not directly derive from carbon photoassimilation. In algae exposed to high salinity, elevated concentrations of floridoside coupled to a low labeling (9.4%) were observed. These results suggest that hyperosmotic conditions stimulated floridoside biosynthesis from endogen storage products rather than from carbon assimilation through photosynthesis.

  20. Physics Lab Experiments and Correlated Computer Aids. Teacher Edition.

    ERIC Educational Resources Information Center

    Gottlieb, Herbert H.

    Forty-nine physics experiments are included in the teacher's edition of this laboratory manual. Suggestions are given in margins for preparing apparatus, organizing students, and anticipating difficulties likely to be encountered. Sample data, graphs, calculations, and sample answers to leading questions are also given for each experiment. It is…

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

    NASA Astrophysics Data System (ADS)

    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.

  2. NMR CHARACTERIZATIONS OF PROPERTIES OF HETEROGENEOUS MEDIA

    SciTech Connect

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

    2005-01-01

    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.

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

    PubMed

    Ward, Meaghan E; Ritz, Emily; Ahmed, Mumdooh A M; Bamm, Vladimir V; Harauz, George; Brown, Leonid S; Ladizhansky, Vladimir

    2015-12-01

    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.

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

    PubMed

    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.

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

    PubMed

    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.

  6. First Measurements of Pion Correlations by the PHENIX Experiment

    SciTech Connect

    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.

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

    PubMed Central

    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

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

    ERIC Educational Resources Information Center

    Cavaleiro, Jose A. S.

    1987-01-01

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

  9. Properties of sesame oil by detailed 1H and 13C NMR assignments before and after ozonation and their correlation with iodine value, peroxide value, and viscosity measurements.

    PubMed

    Sega, Alessandro; Zanardi, Iacopo; Chiasserini, Luisa; Gabbrielli, Alessandro; Bocci, Velio; Travagli, Valter

    2010-02-01

    Gaseous ozone chemically reacts with unsaturated triglyceride substrates leading to ozonated derivatives with a wide potential applications, ranging from the petrochemical to the pharmaceutical industry. To date, an ultimate understanding of the ozone reactivity during sesame oil ozonation process as well as detailed (1)H and (13)C NMR assignments are lacking. A practical advantage of NMR is that a single NMR sample measurement can explain many issues, while similar analysis by traditional methods may require several independent and time-consuming measurements. Moreover, significant relationships among NMR spectra and both conventional chemical analysis and viscosity measurements have been found. Eventually, NMR could play an important role for quality attributes of ozonated oil derivatives.

  10. Developing a targeting system for bacterial membranes: measuring receptor-phosphatidylglycerol interactions with (1)H NMR, ITC and fluorescence correlation spectroscopy.

    PubMed

    Alliband, Amanda; Wang, Zifan; Thacker, Christopher; English, Douglas S; Burns, Dennis H

    2015-01-14

    An ammonium picket porphyrin that targets bacterial membranes has been prepared and shown to bind to phosphatidylglycerol (PG), a bacterial lipid, when the lipid was in solution, contained within synthetic membrane vesicles, or when in Gram-negative and Gram-positive bacterial membranes. The multifunctional receptor was designed to interact with both the phosphate anion portion and neutral glycerol portion of the lipid headgroup. The receptor's affinity and selectivity for binding to surfactant vesicles or lipid vesicles that contain PG within their membranes was directly measured using fluorescence correlation spectroscopy (FCS). FCS demonstrated that the picket porphyrin's binding pocket was complementary for the lipid headgroup, since simple Coulombic interactions alone did not induce binding. (1)H NMR and isothermal titration calorimetry (ITC) were used to determine the receptor's binding stoichiometry, receptor-lipid complex structure, binding constant, and associated thermodynamic properties of complexation in solution. The lipid-receptor binding motif in solution was shown to mirror the binding motif of membrane-bound PG and receptor. Cell lysis assays with E. coli (Gram-negative) and Bacillus thuringiensis (Gram-positive) probed with UV/Visible spectrophotometry indicated that the receptor was able to penetrate either bacterial cell wall and to bind to the bacterial inner membrane.

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

    PubMed

    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.

  12. "Quasi flexible" automatic docking processing for studying stereoselective recognition mechanisms, part 2: Prediction of DeltaDeltaG of complexation and 1H-NMR NOE correlation.

    PubMed

    Alcaro, S; Gasparrini, F; Incani, O; Caglioti, L; Pierini, M; Villani, C

    2007-04-30

    The purpose of this work is to apply the global molecular interaction evaluation ("Glob-MolInE") computational protocol to the study of two molecular complexes characterized by a chiral selector and a couple of enantiomeric selectands experimentally known to give large difference in the free energy of complexation much higher than the experimental error normally associated to the molecular mechanic calculations. We have considered the well known diastereomeric complexes between the selector (S)-N-(3,5-dinitrobenzoyl)-leucine-n-propylamide (S)-1 and the selectands (R) or (S)-N-(2-naphthyl)-alanine methyl ester 2, widely studied by enantioselective HPLC, NMR and X-ray. The experimental difference of free energy of complexation between [(S)-1*(R)-2] and [(S)-1*(S)-2] (-1.34 kcal/mol) was reproduced by the new computational protocol with an excellent confidence error. Detailed results about the conformational search, the "quasi-flexible" docking and the thermodynamic estimation are presented in this work. A remarkable correlation between the theoretical results and experimental data (NOE measurements, X-ray crystallographic structure of the [(S)-1*(S)-2] complex and the free energy of complexation) supports the validity of the computational approach and underline the importance of the conformational multiplicity in the definition of the macroscopic properties of the complex in solution.

  13. Correlation of theory and experiment for high-pressure hydrogen

    NASA Technical Reports Server (NTRS)

    Hoover, W. G.; Ross, M.; Bender, C. F.; Rogers, F. J.; Olness, R. J.

    1972-01-01

    Recent quantum calculations and high-pressure experiments both agree on the magnitude of the forces with which hydrogen molecules interact. The calculated forces have to be determined in two steps: the repulsion is determined by Hartree-Fock calculations while the attraction is deduced semiempirically. The experimental forces are inferred from recent data on hydrogen shockcompressed to 214 kbar. The agreement indicates the usefulness of a pair-potential description of dense hydrogen and suggests, using potentials consistent with both theory and experiment, that pressures of at least 1.7 Mbar will be required to make metallic hydrogen. The expected lifetime of the metal at atmospheric pressure is very short.

  14. Correlates in Children's Experiences of Parents' Racial Socialization Behaviors.

    ERIC Educational Resources Information Center

    Hughes, Diane; Johnson, Deborah

    2001-01-01

    Examined racial socialization processes among 94 African American parents of 3rd-, 4th-, and 5th-grade children as they were predicted by children's ethnic identity exploration and unfair treatment, as well as by parents' ethnic identity and discrimination experiences. Findings suggest that parental factors are most central in the racial…

  15. Correlating Sampling and Intensity Statistics in Nanoparticle Diffraction Experiments

    SciTech Connect

    Ozturk, Hande; Yan, Hanfei; Hill, John P.; Noyan, I. Cevdet

    2015-08-01

    In this article, [Öztürk, Yan, Hill & Noyan (2014). J. Appl. Cryst. 47, 1016-1025] it was shown that the sampling statistics of diffracting particle populations within a polycrystalline ensemble depended on the size of the constituent crystallites: broad X-ray peak breadths enabled some nano-sized particles to contribute more than one diffraction spot to Debye-Scherrer rings. Here it is shown that the equations proposed by Alexander, Klug & Kummer [J. Appl. Phys. (1948), 19, 742-753] (AKK) to link diffracting particle and diffracted intensity statistics are not applicable if the constituent crystallites of the powder are below 10 nm. In this size range, (i) the one-to-one correspondence between diffracting particles and Laue spots assumed in the AKK analysis is not satisfied, and (ii) the crystallographic correlation between Laue spots originating from the same grain invalidates the assumption that all diffracting plane normals are randomly oriented and uncorrelated. Such correlation produces unexpected results in the selection of diffracting grains. Three or more Laue spots from a given grain for a particular reflection can only be observed at certain wavelengths. In addition, correcting the diffracted intensity values by the traditional Lorentz term, 1/cos [theta], to compensate for the variation of particles sampled within a reflection band does not maintain fidelity to the number of poles contributing to the diffracted signal. A new term, cos [theta]B/cos [theta], corrects this problem.

  16. Correlating sampling and intensity statistics in nanoparticle diffraction experiments

    DOE PAGES

    Öztürk, Hande; Yan, Hanfei; Hill, John P.; ...

    2015-07-28

    It is shown in a previous article [Öztürk, Yan, Hill & Noyan (2014).J. Appl. Cryst.47, 1016–1025] that the sampling statistics of diffracting particle populations within a polycrystalline ensemble depended on the size of the constituent crystallites: broad X-ray peak breadths enabled some nano-sized particles to contribute more than one diffraction spot to Debye–Scherrer rings. Here it is shown that the equations proposed by Alexander, Klug & Kummer [J. Appl. Phys.(1948),19, 742–753] (AKK) to link diffracting particle and diffracted intensity statistics are not applicable if the constituent crystallites of the powder are below 10 nm. In this size range, (i) themore » one-to-one correspondence between diffracting particles and Laue spots assumed in the AKK analysis is not satisfied, and (ii) the crystallographic correlation between Laue spots originating from the same grain invalidates the assumption that all diffracting plane normals are randomly oriented and uncorrelated. Such correlation produces unexpected results in the selection of diffracting grains. For example, three or more Laue spots from a given grain for a particular reflection can only be observed at certain wavelengths. In addition, correcting the diffracted intensity values by the traditional Lorentz term, 1/cos θ, to compensate for the variation of particles sampled within a reflection band does not maintain fidelity to the number of poles contributing to the diffracted signal. A new term, cos θB/cos θ, corrects this problem.« less

  17. New Designs for NMR Core Scanning

    NASA Astrophysics Data System (ADS)

    Bluemich, B.; Anferova, S.; Talnishnikh, E.; Arnold, J.; Clauser, C.

    2006-12-01

    Within the last ten years, mobile magnetic resonance has moved from the oil field to many new areas of application. While the focus of mobile NMR in the past was on single-sided or inside-out NMR, the advent of tube-shaped Halbach magnets has introduced the conventional outside-in NMR concept to mobile NMR where the object is inside a magnet. Our Halbach magnet is constructed from small magnet blocks at light weight and low cost with a magnetic field sufficiently homogeneous. To automatize NMR measurements, the Halbach magnet is mounted on a sliding table to scan long core sections without human interaction. In homogeneous magnetic fields, the longitudinal relaxation time T1 and even the transverse relaxation time T2 are proportional to the pore diameters of rocks. Hence, the T1 and T2 signals map the pore-size distribution of the studied rock cores. For fully saturated samples the integral of the distribution curve is proportional to porosity. The porosity values from NMR measurements with the Halbach magnet are used to estimate permability. The Halbach magnet can be used for certain sample geometries in combination with exchangeable radio frequency (rf) coils with different diameters from 24 mm up to 80 mm. To measure standard Ocean Drilling Program (ODP)/Integrated Ocean Drilling Program (IODP) cores, which have a standard diameter of 60 mm and are split lengthwise after recovery, we use a surface figure-8 rf coil with an inner diameter of 60 mm. Besides 1D T2 measurements, we perform relaxation-relaxation correlation experiments, where T1 and T2 are measured in parallel. In this way, the influence of diffusion on the shape of the T2 distribution function is probed. A gradient coil system was designed to perform Pulsed Field Gradients (PFG) experiments. As the gradient coils restrict the axial access to the magnet, only cylindrical core plugs with 20 mm in diameter can be analysed by PFG NMR methods. The homogeneity of the magnetic field in the sensitive volume

  18. On the use of time-averaging restraints when deriving biomolecular structure from [Formula: see text]-coupling values obtained from NMR experiments.

    PubMed

    Smith, Lorna J; van Gunsteren, Wilfred F; Hansen, Niels

    2016-09-01

    Deriving molecular structure from [Formula: see text]-couplings obtained from NMR experiments is a challenge due to (1) the uncertainty in the Karplus relation [Formula: see text] connecting a [Formula: see text]-coupling value to a torsional angle [Formula: see text], (2) the need to account for the averaging inherent to the measurement of [Formula: see text]-couplings, and (3) the sampling road blocks that may emerge due to the multiple-valuedness of the inverse function [Formula: see text] of the function [Formula: see text]. Ways to properly handle these issues in structure refinement of biomolecules are discussed and illustrated using the protein hen egg white lysozyme as example.

  19. Hypothesis driven assessment of an NMR curriculum

    NASA Astrophysics Data System (ADS)

    Cossey, Kimberly

    the hands-on NMR modules), confidence for NMR tasks (not practiced), and confidence for general science tasks. Detailed discussion of the instruments, testing methods and experimental design used in this assessment are provided (Chapter 3). All data were analyzed quantitatively using methods adapted from the educational literature (Chapter 4). Data were analyzed and the descriptive statistics, independent t-tests between the experimental and control groups, and correlation statistics were calculated for each variable. In addition, for those variables included on the pretest, dependent t-tests between pretest and posttest scores were also calculated. The results of study 1 and study 2 were used to draw conclusions based on the hypothesis and research questions proposed in this work (Chapter 4). Data collected in this assessment were used to answer the following research questions: (1) Primary research question: Is depth of understanding of NMR linked to problem solving skills? (2) Are the NMR modules working as intended? Do they promote depth of understanding of NMR? (a) Will students who complete NMR modules have a greater depth of understanding of NMR than students who do not complete the modules? (b) Is depth of understanding increasing over the course of the experiment? (3) Is confidence an intermediary between depth of understanding and problem solving skills? Is it linked to both variables? (4) What levels of confidence are affected by the NMR modules? (a) Will confidence for the NMR class skills used in the modules themselves be greater for those who have completed the modules? (b) Will confidence for NMR tasks not practiced in the course be affected? (c) Will confidence for general science tasks be affected? (d) Are different levels of confidence (class skills, NMR tasks, general science tasks) linked to each other? Results from this NMR curriculum assessment could also have implications outside of the courses studied, and so there is potential to impact the

  20. T2-Filtered T2 - T2 Exchange NMR

    NASA Astrophysics Data System (ADS)

    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.

  1. Correlating sampling and intensity statistics in nanoparticle diffraction experiments

    SciTech Connect

    Öztürk, Hande; Yan, Hanfei; Hill, John P.; Noyan, I. Cevdet

    2015-07-28

    It is shown in a previous article [Öztürk, Yan, Hill & Noyan (2014).J. Appl. Cryst.47, 1016–1025] that the sampling statistics of diffracting particle populations within a polycrystalline ensemble depended on the size of the constituent crystallites: broad X-ray peak breadths enabled some nano-sized particles to contribute more than one diffraction spot to Debye–Scherrer rings. Here it is shown that the equations proposed by Alexander, Klug & Kummer [J. Appl. Phys.(1948),19, 742–753] (AKK) to link diffracting particle and diffracted intensity statistics are not applicable if the constituent crystallites of the powder are below 10 nm. In this size range, (i) the one-to-one correspondence between diffracting particles and Laue spots assumed in the AKK analysis is not satisfied, and (ii) the crystallographic correlation between Laue spots originating from the same grain invalidates the assumption that all diffracting plane normals are randomly oriented and uncorrelated. Such correlation produces unexpected results in the selection of diffracting grains. For example, three or more Laue spots from a given grain for a particular reflection can only be observed at certain wavelengths. In addition, correcting the diffracted intensity values by the traditional Lorentz term, 1/cos θ, to compensate for the variation of particles sampled within a reflection band does not maintain fidelity to the number of poles contributing to the diffracted signal. A new term, cos θB/cos θ, corrects this problem.

  2. Atomic-scale measurement of ultraslow Li motions in glassy LiAlSi2O6 by two-time L6i spin-alignment echo NMR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Wilkening, M.; Kuhn, A.; Heitjans, P.

    2008-08-01

    L6i spin-alignment echo (SAE) nuclear-magnetic-resonance (NMR) spectroscopy is used to monitor single-particle two-time correlation functions in LiAlSi2O6 glass. The method, here applied in the temperature range from 300 to 400 K, is sensitive to ultraslow Li hopping processes with rates (1/τSAE) down to 10 jumps/s. The use of a sample with natural L6i abundance allowed the measurement of pure NMR spin-alignment echoes which are damped with increasing mixing time exclusively by slow Li jumps, i.e., free of influences arising from, e.g., interfering spin-diffusion effects. The considerably stretched correlation functions reveal the presence of a broad distribution of jump rates. The results are comprehensively compared with those recently obtained from both L7i SAE and L7i spin-lattice relaxation NMR as well as from dc conductivity measurements. Interestingly, the activation energy of the latter, which are sensitive to long-range Li transport parameters, is in good agreement with that microscopically probed by L6i SAE NMR, here.

  3. Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

    DOE PAGES

    Alam, Todd M.; Liao, Zuolei; Nyman, May; ...

    2016-04-27

    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. Furthermore, these NMR correlations allowed characterization of local hydrogen-bond environments in uranyl U24 capsules andmore » of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

  4. Toward a Rational Design of Bioactive Glasses with Optimal Structural Features: Composition–Structure Correlations Unveiled by Solid-State NMR and MD Simulations

    PubMed Central

    2013-01-01

    The physiological responses of silicate-based bioactive glasses (BGs) are known to depend critically on both the P content (nP) of the glass and its silicate network connectivity (N̅BOSi). However, while the bioactivity generally displays a nonmonotonic dependence on nP itself, recent work suggest that it is merely the net orthophosphate content that directly links to the bioactivity. We exploit molecular dynamics (MD) simulations combined with 31P and 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy to explore the quantitative relationships between N̅BOSi, nP, and the silicate and phosphate speciations in a series of Na2O–CaO–SiO2–P2O5 glasses spanning 2.1 ≤ N̅BOSi ≤ 2.9 and variable P2O5 contents up to 6.0 mol %. The fractional population of the orthophosphate groups remains independent of nP at a fixed N̅BOSi-value, but is reduced slightly as N̅BOSi increases. Nevertheless, P remains predominantly as readily released orthophosphate ions, whose content may be altered essentially independently of the network connectivity, thereby offering a route to optimize the glass bioactivity. We discuss the observed composition-structure links in relation to known composition-bioactivity correlations, and define how Na2O–CaO–SiO2–P2O5 compositions exhibiting an optimal bioactivity can be designed by simultaneously altering three key parameters: the silicate network connectivity, the (ortho)phosphate content, and the nNa/nCa molar ratio. PMID:24364818

  5. A deeper insight into an intriguing acetonitrile-water binary mixture: synergistic effect, dynamic Stokes shift, fluorescence correlation spectroscopy, and NMR studies.

    PubMed

    Koley, Somnath; Ghosh, Subhadip

    2016-11-30

    An insight study reveals the strong synergistic solvation behaviours from reporter dye molecules within the acetonitrile (ACN)-water (WT) binary mixture. Synergism of a binary mixture refers to some unique changes of the physical and thermodynamic properties of the solvent mixture, originating from the interactions among its cosolvents, which are absent within the pure cosolvents. Synergistic solvation of a binary mixture is likely to be fundamental for greater stabilization of an excited state solute dipole; at least to some extent greater as compared to one stabilized by any of its cosolvents alone. A dynamic Stokes shift due to the solvation of an excited dipole in the ACN-WT binary mixture is found to be highly relevant to the ground state physical properties of the solute molecule (polarity, hydrophilicity, acidity, etc.). Largely different solvation times in the ACN-WT mixture are observed from different dye molecules with widely varying polarities. However, earlier study shows that dye molecules, irrespective of their varying polarities, exhibit very similar solvation times within a pure solvent (J. Phys. Chem. B, 2014, 118, 7577-7785). On further study with fluorescence correlation spectroscopy (FCS) we observed that, unlike the translational diffusion coefficient (Dt) of a dye molecule within a pure solvent, which remains the same irrespective of the location of the dye molecule inside the solvent, a broad distribution among the Dt values of a dye molecule is obtained from different locations within the ACN-WT binary mixture. Lastly our (1)H NMR study in the ACN-WT binary mixture shows the existence of strong hydrogen bond interactions among the cosolvents in the ACN-WT mixture.

  6. Toward a rational design of bioactive glasses with optimal structural features: composition-structure correlations unveiled by solid-state NMR and MD simulations.

    PubMed

    Mathew, Renny; Stevensson, Baltzar; Tilocca, Antonio; Edén, Mattias

    2014-01-23

    The physiological responses of silicate-based bioactive glasses (BGs) are known to depend critically on both the P content (n(P)) of the glass and its silicate network connectivity (N(BO)(Si)). However, while the bioactivity generally displays a nonmonotonic dependence on nP itself, recent work suggest that it is merely the net orthophosphate content that directly links to the bioactivity. We exploit molecular dynamics (MD) simulations combined with ³¹P and ²⁹Si solid-state nuclear magnetic resonance (NMR) spectroscopy to explore the quantitative relationships between N(BO)(Si), n(P), and the silicate and phosphate speciations in a series of Na₂O-CaO-SiO₂-P₂O₅ glasses spanning 2.1 ≤ N(BO)(Si) ≤ 2.9 and variable P₂O₅ contents up to 6.0 mol %. The fractional population of the orthophosphate groups remains independent of n(P) at a fixed N(BO)(Si)-value, but is reduced slightly as N(BO)(Si) increases. Nevertheless, P remains predominantly as readily released orthophosphate ions, whose content may be altered essentially independently of the network connectivity, thereby offering a route to optimize the glass bioactivity. We discuss the observed composition-structure links in relation to known composition-bioactivity correlations, and define how Na₂O-CaO-SiO₂-P₂O₅ compositions exhibiting an optimal bioactivity can be designed by simultaneously altering three key parameters: the silicate network connectivity, the (ortho)phosphate content, and the n(Na)/n(Ca) molar ratio.

  7. Experiment on parallel correlated recognition of 2030 human faces based on speckle modulation.

    PubMed

    Liao, Yi; Guo, Yunbo; Cao, Liangcai; Ma, Xiaosu; He, Qingsheng; Jin, Guofan

    2004-08-23

    In this paper, the experiment on parallel correlated recognition of 2030 human faces in Fe:LiNbO(3) crystal is detailedly presented, a very clear correlation spots array was achieved and the recognition accuracy is better than 95%. According to the experiment, it is proved that speckle modulation on the object beam of volume holographic correlators can well suppress the crosstalk, so that the multiplexing spacing is markedly reduced and the channel density is increased 10 times compared with the traditional holographic correlators without speckle modulation.

  8. Protein-Inhibitor Interaction Studies Using NMR

    PubMed Central

    Ishima, Rieko

    2015-01-01

    Solution-state NMR has been widely applied to determine the three-dimensional structure, dynamics, and molecular interactions of proteins. The designs of experiments used in protein NMR differ from those used for small-molecule NMR, primarily because the information available prior to an experiment, such as molecular mass and knowledge of the primary structure, is unique for proteins compared to small molecules. In this review article, protein NMR for structural biology is introduced with comparisons to small-molecule NMR, such as descriptions of labeling strategies and the effects of molecular dynamics on relaxation. Next, applications for protein NMR are reviewed, especially practical aspects for protein-observed ligand-protein interaction studies. Overall, the following topics are described: (1) characteristics of protein NMR, (2) methods to detect protein-ligand interactions by NMR, and (3) practical aspects of carrying out protein-observed inhibitor-protein interaction studies. PMID:26361636

  9. 3D NMR Experiments for Measuring 15N Relaxation Data of Large Proteins: Application to the 44 kDa Ectodomain of SIV gp41

    NASA Astrophysics Data System (ADS)

    Caffrey, Michael; Kaufman, Joshua; Stahl, Stephen J.; Wingfield, Paul T.; Gronenborn, Angela M.; Clore, G. Marius

    1998-12-01

    A suite of 3D NMR experiments for measuring15N-{1H} NOE,15NT1, and15NT1ρvalues in large proteins, uniformly labeled with15N and13C, is presented. These experiments are designed for proteins that exhibit extensive spectral overlap in the 2D1H-15N HSQC spectrum. The pulse sequences are readily applicable to perdeuterated samples, which increases the spectral resolution and signal-to-noise ratio, thereby permitting the characterization of protein dynamics to be extended to larger protein systems. Application of the pulse sequences is demonstrated on a perdeuterated13C/15N-labeled sample of the 44 kDa ectodomain of SIV gp41.

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

    SciTech Connect

    Marshall, William BJ J; Rearden, Bradley T

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Amide proton exchange rates of a bound pepsin inhibitor determined by isotope-edited proton NMR experiments

    SciTech Connect

    Fesik, S.W.; Luly, J.R.; Stein, H.H.; BaMaung, N.

    1987-09-30

    From a series of isotope-edited proton NMR spectra, amide proton exchange rates were measured at 20 C, 30 C, and 40/sup 0/C for a tightly bound /sup 15/N-labeled tripeptide inhibitor of porcine pepsin (IC50 = 1.7 X 10(-) M). Markedly different NH exchange rates were observed for the three amide protons of the bound inhibitor. The P1 NH exchanged much more slowly than the P2 NH and P3 NH. These results are discussed in terms of the relative solvent accessibility in the active site and the role of the NH protons of the inhibitor for hydrogen bonding to the enzyme. In this study a useful approach is demonstrated for obtaining NH exchange rates on ligands bound to biomacromolecules, the knowledge of which could be of potential utility in the design of therapeutically useful nonpeptide enzyme inhibitors from peptide leads.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. A Series of Diamagnetic Pyridine Monoimine Rhenium Complexes with Different Degrees of Metal-to-Ligand Charge Transfer: Correlating (13) C NMR Chemical Shifts with Bond Lengths in Redox-Active Ligands.

    PubMed

    Sieh, Daniel; Kubiak, Clifford P

    2016-07-18

    A set of pyridine monoimine (PMI) rhenium(I) tricarbonyl chlorido complexes with substituents of different steric and electronic properties was synthesized and fully characterized. Spectroscopic (NMR and IR) and single-crystal X-ray diffraction analyses of these complexes showed that the redox-active PMI ligands are neutral and that the overall electronic structure is little affected by the choices of the substituent at the ligand backbone. One- and two-electron reduction products were prepared from selected starting compounds and could also be characterized by multiple spectroscopic methods and X-ray diffraction. The final product of a one-electron reduction in THF is a diamagnetic metal-metal-bonded dimer after loss of the chlorido ligand. Bond lengths in and NMR chemical shifts of the PMI ligand backbone indicate partial electron transfer to the ligand. Two-electron reduction in THF also leads to the loss of the chlorido ligand and a pentacoordinate complex is obtained. The comparison with reported bond lengths and (13) C NMR chemical shifts of doubly reduced free pyridine monoaldimine ligands indicates that both redox equivalents in the doubly reduced rhenium complex investigated here are located in the PMI ligand. With diamagnetic complexes varying over three formal reduction stages at the PMI ligand we were, for the first time, able to establish correlations of the (13) C NMR chemical shifts with the relevant bond lengths in redox-active ligands over a full redox series.

  15. Conformational Properties of α- or β-(1→6)-Linked Oligosaccharides: Hamiltonian Replica Exchange MD Simulations and NMR Experiments

    PubMed Central

    2015-01-01

    Conformational sampling for a set of 10 α- or β-(1→6)-linked oligosaccharides has been studied using explicit solvent Hamiltonian replica exchange (HREX) simulations and NMR spectroscopy techniques. Validation of the force field and simulation methodology is done by comparing calculated transglycosidic J coupling constants and proton–proton distances with the corresponding NMR data. Initial calculations showed poor agreement, for example, with >3 Hz deviation of the calculated 3J(H5,H6R) values from the experimental data, prompting optimization of the ω torsion angle parameters associated with (1→6)-linkages. The resulting force field is in overall good agreement (i.e., within ∼0.5 Hz deviation) from experimental 3J(H5,H6R) values, although some small limitations are evident. Detailed hydrogen bonding analysis indicates that most of the compounds lack direct intramolecular H-bonds between the two monosaccharides; however, minor sampling of the O6···HO2′ hydrogen bond is present in three compounds. The results verify the role of the gauche effect between O5 and O6 atoms in gluco- and manno-configured pyranosides causing the ω torsion angle to sample an equilibrium between the gt and gg rotamers. Conversely, galacto-configured pyranosides sample a population distribution in equilibrium between gt and tg rotamers, while the gg rotamer populations are minor. Water radial distribution functions suggest decreased accessibility to the O6 atom in the (1→6)-linkage as compared to the O6′ atom in the nonreducing sugar. The role of bridging water molecules between two sugar moieties on the distributions of ω torsion angles in oligosaccharides is also explored. PMID:24552401

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

    PubMed

    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.

  17. The Mass-8 experiment -- Measuring the {beta}-{alpha} angular correlations

    SciTech Connect

    Amsbaugh, J.F.; Beck, M.; Braeckeleer, L. de; Storm, D.W.; Swanson, E.; Swartz, K.B.; Schagen, J.P.S. van; Wright, D.C.; Zhao, Z.

    1997-12-31

    The objective of the Mass-8 experiment is to perform a precision test of the conservation of the vector current hypothesis and a search for second class currents. The authors present preliminary data on the correlation coefficients of the {beta}-{alpha} angular correlations of the {beta}-delayed {alpha}-decays of {sup 8}Li and {sup 8}B.

  18. Simultaneously cycled NMR spectroscopy.

    PubMed

    Parish, David M; Szyperski, Thomas

    2008-04-09

    Simultaneously cycled (SC) NMR was introduced and exemplified by implementing a set of 2-D [1H,1H] SC exclusive COSY (E.COSY) NMR experiments, that is, rf pulse flip-angle cycled (SFC), rf pulse phase cycled (SPC), and pulsed field gradient (PFG) strength cycled (SGC) E.COSY. Spatially selective 1H rf pulses were applied as composite pulses such that all steps of the respective cycles were affected simultaneously in different slices of the sample. This increased the data acquisition speed for an n-step cycle n-fold. A high intrinsic sensitivity was achieved by defining the cycles in a manner that the receiver phase remains constant for all steps of the cycle. Then, the signal resulting from applying the cycle corresponded to the sum of the signals from all steps of the cycle. Hence, the detected free induction decay did not have to be separated into the contributions arising from different slices, and read-out PFGs, which not only greatly reduce sensitivity but also negatively impact lineshapes in the direct dimension, were avoided. The current implementation of SFC E.COSY reached approximately 65% of the intrinsic sensitivity of the conventional phase cycled congener, making this experiment highly attractive whenever conventional data acquisition is sampling limited. Highly resolved SC E.COSY yielding accurate 3J-coupling values was recorded for the 416 Da plant alkaloid tomatidine within 80 min, that is, 12 times faster than with conventional phase cycled E.COSY. SC NMR is applicable for a large variety of NMR experiments and thus promises to be a valuable addition to the arsenal of approaches for tackling the NMR sampling problem to avoid sampling limited data acquisition.

  19. Molecular simulations of multimodal ligand-protein binding: elucidation of binding sites and correlation with experiments.

    PubMed

    Freed, Alexander S; Garde, Shekhar; Cramer, Steven M

    2011-11-17

    Multimodal chromatography, which employs more than one mode of interaction between ligands and proteins, has been shown to have unique selectivity and high efficacy for protein purification. To test the ability of free solution molecular dynamics (MD) simulations in explicit water to identify binding regions on the protein surface and to shed light on the "pseudo affinity" nature of multimodal interactions, we performed MD simulations of a model protein ubiquitin in aqueous solution of free ligands. Comparisons of MD with NMR spectroscopy of ubiquitin mutants in solutions of free ligands show a good agreement between the two with regard to the preferred binding region on the surface of the protein and several binding sites. MD simulations also identify additional binding sites that were not observed in the NMR experiments. "Bound" ligands were found to be sufficiently flexible and to access a number of favorable conformations, suggesting only a moderate loss of ligand entropy in the "pseudo affinity" binding of these multimodal ligands. Analysis of locations of chemical subunits of the ligand on the protein surface indicated that electrostatic interaction units were located on the periphery of the preferred binding region on the protein. The analysis of the electrostatic potential, the hydrophobicity maps, and the binding of both acetate and benzene probes were used to further study the localization of individual ligand moieties. These results suggest that water-mediated electrostatic interactions help the localization and orientation of the MM ligand to the binding region with additional stability provided by nonspecific hydrophobic interactions.

  20. Application of Natural Isotopic Abundance ¹H-¹³C- and ¹H-¹⁵N-Correlated Two-Dimensional NMR for Evaluation of the Structure of Protein Therapeutics.

    PubMed

    Arbogast, Luke W; Brinson, Robert G; Marino, John P

    2016-01-01

    Methods for characterizing the higher-order structure of protein therapeutics are in great demand for establishing consistency in drug manufacturing, for detecting drug product variations resulting from modifications in the manufacturing process, and for comparing a biosimilar to an innovator reference product. In principle, solution NMR can provide a robust approach for characterization of the conformation(s) of protein therapeutics in formulation at atomic resolution. However, molecular weight limitations and the perceived need for stable isotope labeling have to date limited its practical applications in the biopharmaceutical industry. Advances in NMR magnet and console technologies, cryogenically cooled probes, and new rapid acquisition methodologies, particularly selective optimized flip-angle short transient pulse schemes and nonuniform sampling, have greatly ameliorated these limitations. Here, we describe experimental methods for the collection and analysis of 2D (1)H(N)-(15)N-amide- and (1)H-(13)C-methyl-correlated spectra applied to protein drug products at natural isotopic abundance, including representatives from the rapidly growing class of monoclonal antibody (mAb) therapeutics. Practical aspects of experimental setup and data acquisition for both standard and rapid acquisition NMR techniques are described. Furthermore, strategies for the statistical comparison of 2D (1)H(N)-(15)N-amide- and (1)H-(13)C-methyl-correlated spectra are detailed.

  1. Benzenium ion chemistry on solid metal halide superacids: in situ {sup 13}C NMR experiments and theoretical calculations

    SciTech Connect

    Xu, T.; Barich, D.H.; Torres, P.D.; Haw, J.F.

    1997-01-15

    The benzenium, toluenium, and ethylbenzenium ions were synthesized on aluminium bromide by coadsorption of the precursors with either HBr or alkyl bromide. Principal components of the {sup 13}C chemical shift tensors for the ring carbons of these species were measured from magic angle spinning spectra. The benzenium ion was static at 77 K but underwent both proton scrambling and anisotropic rotation at 298 K as well as oligomerization at higher loadings. The para form of the toluenium ion was the dominant isomer at 77 K, but a temperature-dependent equilibrium between the para and ortho isomers was observed at 273 K. The energy calculations at MP4(fc,sdq)/ 6-311+G{sup *}//MP2/6-311+G{sup *} with thermal corrections resulted in good agreement between calculated and measured proton affinities for benzene, toluene, and ethylbenzene. For toluenium ion, the energies of the ortho and meta isomers were 1.2 and 5.4 kcal/mol, respectively, above the para isomer, consistent with the temperature-dependent {sup 13}C NMR spectra in the solid state. {sup 13}C chemical shift tensors calculated at the GIAO-MP2/tzp/dz//MP2/ 6-311+G{sup *} and GIAO-MP2/tzp/dz//B3LYP/6-311+G{sup *} levels of theory were in very close agreement with each other and generally in satisfactory agreement with experimental principal components. 64 refs., 8 figs., 4 tabs.

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

    ERIC Educational Resources Information Center

    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…

  3. Euler and Potential Experiment/CFD Correlations for a Transport and Two Delta-Wing Configurations

    NASA Technical Reports Server (NTRS)

    Hicks, R. M.; Cliff, S. E.; Melton, J. E.; Langhi, R. G.; Goodsell, A. M.; Robertson, D. D.; Moyer, S. A.

    1990-01-01

    A selection of successes and failures of Computational Fluid Dynamics (CFD) is discussed. Experiment/CFD correlations involving full potential and Euler computations of the aerodynamic characteristics of four commercial transport wings and two low aspect ratio, delta wing configurations are shown. The examples consist of experiment/CFD comparisons for aerodynamic forces, moments, and pressures. Navier-Stokes equations are not considered.

  4. 1H-13C HSQC NMR spectroscopy for estimating procyanidin/prodelphinidin and cis/trans flavan-3-ol ratios of condensed tannin samples: correlation with thiolysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Studies with a diverse array of 22 condensed tannin (CT) fractions from 9 plant species demonstrated that procyanidin/prodelphinidin (PC/PD) and cis/trans flavan-3-ol ratios can be appraised by 1H-13C HSQC NMR. The method was developed from fractions containing 44 to ~100% CT, PC/PD ratios ranging f...

  5. Prior experience with negative spectral correlations promotes information integration during auditory category learning.

    PubMed

    Scharinger, Mathias; Henry, Molly J; Obleser, Jonas

    2013-07-01

    Complex sounds vary along a number of acoustic dimensions. These dimensions may exhibit correlations that are familiar to listeners due to their frequent occurrence in natural sounds-namely, speech. However, the precise mechanisms that enable the integration of these dimensions are not well understood. In this study, we examined the categorization of novel auditory stimuli that differed in the correlations of their acoustic dimensions, using decision bound theory. Decision bound theory assumes that stimuli are categorized on the basis of either a single dimension (rule based) or the combination of more than one dimension (information integration) and provides tools for assessing successful integration across multiple acoustic dimensions. In two experiments, we manipulated the stimulus distributions such that in Experiment 1, optimal categorization could be accomplished by either a rule-based or an information integration strategy, while in Experiment 2, optimal categorization was possible only by using an information integration strategy. In both experiments, the pattern of results demonstrated that unidimensional strategies were strongly preferred. Listeners focused on the acoustic dimension most closely related to pitch, suggesting that pitch-based categorization was given preference over timbre-based categorization. Importantly, in Experiment 2, listeners also relied on a two-dimensional information integration strategy, if there was immediate feedback. Furthermore, this strategy was used more often for distributions defined by a negative spectral correlation between stimulus dimensions, as compared with distributions with a positive correlation. These results suggest that prior experience with such correlations might shape short-term auditory category learning.

  6. Variable angle correlation spectroscopy

    SciTech Connect

    Lee, Young Kyo

    1994-05-01

    In this dissertation, a novel nuclear magnetic resonance (NMR) technique, variable angle correlation spectroscopy (VACSY) is described and demonstrated with 13C 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.

  7. Coexistence of antiferromagnetic and ferromagnetic spin correlations in SrCo2As2 revealed by 59Co and 75As NMR

    SciTech Connect

    Wiecki, P.; Ogloblichev, V.; Pandey, Abhishek; Johnston, D. C.; Furukawa, Y.

    2015-06-15

    In nonsuperconducting, metallic paramagnetic SrCo2As2, inelastic neutron scattering measurements have revealed strong stripe-type q=(π,0) antiferromagnetic (AFM) spin correlations. Using nuclear magnetic resonance (NMR) measurements on 59Co and 75As nuclei, we demonstrate that stronger ferromagnetic (FM) spin correlations coexist in SrCo2As2. Our NMR data are consistent with density functional theory (DFT) calculations which show enhancements at both q=(π,0) and the in-plane FM q=0 wave vectors in static magnetic susceptibility χ(q). We suggest that the strong FM fluctuations prevent superconductivity in SrCo2As2, despite the presence of stripe-type AFM fluctuations. Since DFT calculations have consistently revealed similar enhancements of the χ(q) at both q=(π,0) and q=0 in the iron-based superconductors and parent compounds, our observation of FM correlations in SrCo2As2 calls for detailed studies of FM correlations in the iron-based superconductors.

  8. Direct measurement of dipole-dipole/CSA cross-correlated relaxation by a constant-time experiment

    PubMed Central

    Liu, Yizhou; Prestegard, James H.

    2008-01-01

    Relaxation rates in NMR are usually measured by intensity modulation as a function of a relaxation delay during which the relaxation mechanism of interest is effective. Other mechanisms are often suppressed during the relaxation delay by pulse sequences which eliminate their effects, or cancel their effects when two data sets with appropriate combinations of relaxation rate effects are added. Cross-correlated relaxation (CCR) involving dipole-dipole and CSA interactions differ from auto-correlated relaxation (ACR) in that the signs of contributions can be changed by inverting the state of one spin involved in the dipole-dipole interaction. This property has been exploited previously using CPMG sequences to refocus CCR while ACR evolves. Here we report a new pulse scheme that instead eliminates intensity modulation by ACR and thus allows direct measurement of CCR. The sequence uses a constant time relaxation period for which the contribution of ACR does not change. An inversion pulse is applied at various points in the sequence to effect a decay that depends on CCR only. A 2-D experiment is also described in which chemical shift evolution in the indirect dimension can share the same constant period. This improves sensitivity by avoiding the addition of a separate indirect dimension acquisition time. We illustrate the measurement of residue specific CCR rates on the non-myristoylated yeast ARF1 protein and compare the results to those obtained following the conventional method of measuring the decay rates of the slow and fast-relaxing 15N doublets. The performances of the two methods are also quantitatively evaluated by simulation. The analysis shows that the shared constant-time CCR (SCT-CCR) method significantly improves sensitivity. PMID:18406649

  9. β-NMR

    NASA Astrophysics Data System (ADS)

    Morris, Gerald D.

    2014-01-01

    The β-NMR facility at ISAC is constructed specifically for experiments in condensed matter physics with radioactive ion beams. Using co-linear optical pumping, a 8Li + ion beam having a large nuclear spin polarisation and low energy (nominally 30 keV) can be generated. When implanted into materials these ions penetrate to shallow depths comparable to length scales of interest in the physics of surfaces and interfaces between materials. Such low-energy ions can be decelerated with simple electrostatic optics to enable depth-resolved studies of near-surface phenomena over the range of about 2-200 nm. Since the β-NMR signal is extracted from the asymmetry intrinsic to beta-decay and therefore monitors the polarisation of the radioactive probe nuclear magnetic moments, this technique is fundamentally a probe of local magnetism. More generally though, any phenomena which affects the polarisation of the implanted spins by, for example, a change in resonance frequency, line width or relaxation rate can be studied. The β-NMR program at ISAC currently supports a number of experiments in magnetism and superconductivity as well as novel ultra-thin heterostructures exhibiting properties that cannot occur in bulk materials. The general purpose zero/low field and high field spectrometers are configured to perform CW and pulsed RF nuclear magnetic resonance and spin relaxation experiments over a range of temperatures (3-300 K) and magnetic fields (0-9 T).

  10. An isotropic chemical shift-chemical shift anisotropic correlation experiment using discrete magic angle turning.

    PubMed

    Hu, Jian Zhi; Sears, Jesse A; Kwak, Ja Hun; Hoyt, David W; Wang, Yong; Peden, Charles H F

    2009-05-01

    An isotropic-anisotropic shift 2D correlation spectroscopy is introduced that combines the advantages of both magic angle turning (MAT) and magic angle hopping (MAH) technologies. In this new approach, denoted DMAT for "discrete magic angle turning", the sample rotates clockwise followed by an anticlockwise rotation of exactly the same amount with each rotation less or equal than 360 degrees but greater than 240 degrees , with the rotation speed being constant only for times related to the evolution dimension. This back and forth rotation is repeated and synchronized with a special radio frequency (RF) pulse sequence to produce an isotropic-anisotropic shift 2D correlation spectrum. For any spin-interaction of rank-2 such as chemical shift anisotropy, isotropic magnetic susceptibility interaction, and residual homo-nuclear dipolar interaction in biological fluid samples, the projection along the isotropic dimension is a high resolution spectrum. Since a less than 360 degrees sample rotation is involved, the design potentially allows for in situ control over physical parameters such as pressure, flow conditions, feed compositions, and temperature so that true in situ NMR investigations can be carried out.

  11. Molecular environment of stable iodine and radioiodine (129I) in natural organic matter: Evidence inferred from NMR and binding experiments at environmentally relevant concentrations

    NASA Astrophysics Data System (ADS)

    Xu, Chen; Zhong, Junyan; Hatcher, Patrick G.; Zhang, Saijin; Li, Hsiu-Ping; Ho, Yi-Fang; Schwehr, Kathleen A.; Kaplan, Daniel I.; Roberts, Kimberly A.; Brinkmeyer, Robin; Yeager, Chris M.; Santschi, Peter H.

    2012-11-01

    129I is a major by-product of nuclear fission and had become one of the major radiation risk drivers at Department of Energy (DOE) sites. 129I is present at elevated levels in the surface soils of the Savannah River Site (SRS) F-Area and was found to be bound predominantly to soil organic matter (SOM). Naturally bound 127I and 129I to sequentially extracted humic acids (HAs), fulvic acids (FAs) and a water extractable colloid (WEC) were measured in a 129I-contaminated wetland surface soil located on the SRS. WEC is a predominantly colloidal organic fraction obtained from soil re-suspension experiments to mimic the fraction that may be released during groundwater exfiltration, storm water or surface runoff events. For the first time, NMR techniques were applied to infer the molecular environment of naturally occurring stable iodine and radioiodine binding to SOM. Iodine uptake partitioning coefficients (Kd) by these SOM samples at ambient iodine concentrations were also measured and related to quantitative structural analyses by 13C DPMAS NMR and solution state 1H NMR on the eight humic acid fractions. By assessing the molecular environment of iodine, it was found that it was closely associated with the aromatic regions containing esterified products of phenolic and formic acids or other aliphatic carboxylic acids, amide functionalities, quinone-like structures activated by electron-donating groups (e.g., NH2), or a hemicellulose-lignin-like complex with phenyl-glycosidic linkages. However, FAs and WEC contained much greater concentrations of 127I or 129I than HAs. The contrasting radioiodine contents among the three different types of SOM (HAs, FAs and WEC) suggest that the iodine binding environment cannot be explained solely by the difference in the amount of their reactive binding sites. Instead, indirect evidence indicates that the macro-molecular conformation, such as the hydrophobic aliphatic periphery hindering the active aromatic cores and the hydrophilic

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

    PubMed

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

    2016-01-01

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

  13. Two dimensional NMR spectroscopic approaches for exploring plant metabolome: A review

    PubMed Central

    Mahrous, Engy A.; Farag, Mohamed A.

    2014-01-01

    Today, most investigations of the plant metabolome tend to be based on either nuclear magnetic resonance (NMR) spectroscopy or mass spectrometry (MS), with or without hyphenation with chromatography. Although less sensitive than MS, NMR provides a powerful complementary technique for the identification and quantification of metabolites in plant extracts. NMR spectroscopy, well appreciated by phytochemists as a particularly information-rich method, showed recent paradigm shift for the improving of metabolome(s) structural and functional characterization and for advancing the understanding of many biological processes. Furthermore, two dimensional NMR (2D NMR) experiments and the use of chemometric data analysis of NMR spectra have proven highly effective at identifying novel and known metabolites that correlate with changes in genotype or phenotype. In this review, we provide an overview of the development of NMR in the field of metabolomics with special focus on 2D NMR spectroscopic techniques and their applications in phytomedicines quality control analysis and drug discovery from natural sources, raising more attention at its potential to reduce the gap between the pace of natural products research and modern drug discovery demand. PMID:25685540

  14. Dynamic correlation length growth in superspin glass: Bridging experiments and simulations

    NASA Astrophysics Data System (ADS)

    Nakamae, S.; Crauste-Thibierge, C.; L'Hôte, D.; Vincent, E.; Dubois, E.; Dupuis, V.; Perzynski, R.

    2012-12-01

    Interacting magnetic nanoparticles display a wide variety of magnetic behaviors that are now being gathered in the emerging field of "supermagnetism." We have investigated how the out-of-equilibrium dynamics in the disordered superspin glass (SSG) state of a frozen ferrofluid sample is affected by texturation. Via magnetization relaxation experiments at low temperatures, we were able to estimate superspin correlation lengths for both textured and non-textured samples. The comparison with simulations and experiments on atomic spin glasses shows that the dynamic correlations in SSG's appear to develop in a way reminiscent to those in atomic spin glasses at intermediate time/length scales.

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

    ERIC Educational Resources Information Center

    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…

  16. Dynamically correlated spontaneous-emission laser: theory and comparison with experiment

    SciTech Connect

    Bergou, J.; Orszag, M.

    1988-02-01

    A higher-order correlated-emission laser (CEL) effect is found theoretically in a Doppler-broadened medium. A full quantum-mechanical account of the CEL in the nonlinear regime shows a large reduction in the beat-signal linewidth. This behavior is confirmed by a recent experiment.

  17. Theoretical Modeling of 99 Tc NMR Chemical Shifts

    SciTech Connect

    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.

  18. Optical pumping and xenon NMR

    SciTech Connect

    Raftery, M.D.

    1991-11-01

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

  19. Optical pumping and xenon NMR

    SciTech Connect

    Raftery, M.D.

    1991-11-01

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

  20. 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

    ERIC Educational Resources Information Center

    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…

  1. Cognitive factors correlating with the metacognition of the phenomenal properties of experience

    PubMed Central

    Mogi, Ken

    2013-01-01

    The awareness of the phenomenal qualities of one's experiences can be considered as an instance of metacognition. Although some people take qualia (sensory qualities such as the redness of red) as salient features of phenomenal experience, others have expressed views that doubt or deny the central importance of qualia. How do such cognitive heterogeneities occur? What parameters influence them? Here I examine the relationship between the awareness of the phenomenal qualities of subjective experience (qualia and free will) and general cognitive tendencies. The awareness of qualia was found to be more varied among subjects compared to the belief in free will. Various cognitive tendencies correlated with the metacognition of phenomenal experience. The awareness of qualia was found to increase significantly with age, suggesting a continuous learning process. These results suggest that heterogeneities in the metacognition of phenomenal properties of experience are important constraints in human cognition. PMID:24284832

  2. Analysis/forecast experiments with a flow-dependent correlation function using FGGE data

    NASA Technical Reports Server (NTRS)

    Baker, W. E.; Bloom, S. C.; Carus, H.; Nestler, M. S.

    1986-01-01

    The use of a flow-dependent correlation function to improve the accuracy of an optimum interpolation (OI) scheme is examined. The development of the correlation function for the OI analysis scheme used for numerical weather prediction is described. The scheme uses a multivariate surface analysis over the oceans to model the pressure-wind error cross-correlation and it has the ability to use an error correlation function that is flow- and geographically-dependent. A series of four-day data assimilation experiments, conducted from January 5-9, 1979, were used to investigate the effect of the different features of the OI scheme (error correlation) on forecast skill for the barotropic lows and highs. The skill of the OI was compared with that of a successive correlation method (SCM) of analysis. It is observed that the largest difference in the correlation statistics occurred in barotropic and baroclinic lows and highs. The comparison reveals that the OI forecasts were more accurate than the SCM forecasts.

  3. Understanding the NMR properties and conformational behavior of indole vs. azaindole group in protoberberines: NICS and NCS analysis

    NASA Astrophysics Data System (ADS)

    Kadam, Shivaji S.; Toušek, Jaromír; Maier, Lukáš; Pipíška, Matej; Sklenář, Vladimír; Marek, Radek

    2012-11-01

    We report here the preparation and the structural investigation into a series of 8-(indol-1-yl)-7,8-dihydroprotoberberine derivatives derived from berberine, palmatine, and coptisine. Structures of these new compounds were characterized mainly by 2D NMR spectroscopy and the conformational behavior was investigated by using methods of density-functional theory (DFT). PBE0/6-311+G** calculated NMR chemical shifts for selected derivatives correlate excellently with the experimental NMR data and support the structural conclusions drawn from the NMR experiments. An interesting role of the nitrogen atom in position N7' of the indole moiety in 8-(7-azaindol-1-yl)-7,8-dihydroprotoberberines as compared to other 8-indolyl derivatives is investigated in detail. The experimentally observed trends in NMR chemical shifts are rationalized by DFT calculations and analysis based on the nucleus-independent chemical shifts (NICS) and natural localized molecular orbitals (NLMOs).

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

    PubMed

    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.

  5. Two dimensional NMR and NMR relaxation studies of coal structure

    SciTech Connect

    Zilm, K.W.

    1989-01-01

    This report covers the progress made on the title project during the past reporting period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines the authors are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. The effects of very high MAS rates (>10 kHz) on cross polarization dynamics are also being investigated for similar reasons. The authors have been reinvestigating the prospects of using zero field NMR types of techniques for two dimensional NMR structural analysis of complex organic solids such as coals. Currently MAS spin rates are not sufficiently high to permit zero field in high field NMR for protons in typical organic solids, however they are compatible with {sup 13}C-{sup 13}C dipolar couplings. In collaboration with Dr. Robert Tycko of AT T Bell Laboratories, inventor of the zero field in high field NMR method, the authors have performed the first zero field in high field {sup 13}C NMR experiments. These results are described. 9 refs., 2 figs.

  6. Physical and Chemical Effects of Two-Phase Brine/Supercritical-CO2 Fluid Flow on Clastic Rocks: Real-Time Monitoring and NMR Imaging of Flow-Through Core Experiments

    NASA Astrophysics Data System (ADS)

    Shaw, C. A.; Vogt, S.; Maneval, J. E.; Brox, T.; Skidmore, M. L.; Codd, S. L.; Seymour, J. D.

    2010-12-01

    Sandstone core samples were challenged with a supercritical CO2-saturated brine mixture in a laboratory flow-through core reactor system over a range of temperatures and brine strengths. Cores of quartz arenite from the Berea formation were selected to represent ideal ‘clean’ sandstone These laboratory experiments potentially provide an analog for the acidification of pore fluids near the brine/CO2 interface during CO2 flooding of depleted clastic hydrocarbon reservoirs for carbon sequestration. Flow in the reactor was perpendicular to bedding. Initial experiments were run at 50°C and 100°C with brine concentrations of 1g/L and 10g/L (TDS) to test effects of different temperatures and brine compositions. Real-time monitoring of fluid pH and conductivity provided a measure of reaction rates. Introduction of supercritical CO2 into the brine-saturated cores initiated a reduction in pH accompanied by an increase in conductivity. NMR images of fresh cores were compared with images of challenged cores using a protocol for pixel-by-pixel comparison to determine the effects on bulk pore volume and geometry. Two types of imaging experiments were conducted: multi-slice spin echo and 3-D spin echo images. Multi-slice experiments had a slice thickness of 1.5 mm and an in-plane resolution of 0.27 mm x 0.27 mm, and 3-D experiments had a resolution of 0.47 mm x 0.55 mm x 0.55mm. Imaging results reflected the observed changes in the physical and chemical structure post-challenge. Two-dimensional relaxation correlation experiments were also conducted to probe the pore sizes, connectivity and fluid saturation of the rock cores before and after challenging. Chemical analyses and microscopic examination of the challenged cores will provide a better understanding of alteration in the cores and the changes in the volume, geometry and connectivity of pore space.

  7. Correlation, necessity, and sufficiency: Common errors in the scientific reasoning of undergraduate students for interpreting experiments.

    PubMed

    Coleman, Aaron B; Lam, Diane P; Soowal, Lara N

    2015-01-01

    Gaining an understanding of how science works is central to an undergraduate education in biology and biochemistry. The reasoning required to design or interpret experiments that ask specific questions does not come naturally, and is an essential part of the science process skills that must be learned for an understanding of how scientists conduct research. Gaps in these reasoning skills make it difficult for students to become proficient in reading primary scientific literature. In this study, we assessed the ability of students in an upper-division biochemistry laboratory class to use the concepts of correlation, necessity, and sufficiency in interpreting experiments presented in a format and context that is similar to what they would encounter when reading a journal article. The students were assessed before and after completion of a laboratory module where necessary vs. sufficient reasoning was used to design and interpret experiments. The assessment identified two types of errors that were commonly committed by students when interpreting experimental data. When presented with an experiment that only establishes a correlation between a potential intermediate and a known effect, students frequently interpreted the intermediate as being sufficient (causative) for the effect. Also, when presented with an experiment that tests only necessity for an intermediate, they frequently made unsupported conclusions about sufficiency, and vice versa. Completion of the laboratory module and instruction in necessary vs. sufficient reasoning showed some promise for addressing these common errors.

  8. PHYSICS OF OUR DAYS: Cosmic microwave background anisotropy data correlation in WMAP and Relikt-1 experiments

    NASA Astrophysics Data System (ADS)

    Skulachev, Dmitrii P.

    2010-07-01

    A comparison is made of cosmic microwave background anisotropy data obtained from the WMAP satellite in 2001 - 2006 and from the Relikt-1 satellite in 1983 - 1984. It is shown that low-temperature area found by Relikt-1 is the location of the 'coldest spot' of the WMAP radiomap. The mutual correlation of the two datasets is estimated and found to be positive for all sky regions surveyed. The conclusion is made that with the 98% probability, the Relikt-1 experiment had detected the same signal that was later identified by WMAP. A discussion is given of whether the Relikt-1 experiment parameters were chosen correctly.

  9. Two-dimensional NMR spectrometry

    SciTech Connect

    Farrar, T.C.

    1987-06-01

    This article is the second in a two-part series. In part one (ANALYTICAL CHEMISTRY, May 15) the authors discussed one-dimensional nuclear magnetic resonance (NMR) spectra and some relatively advanced nuclear spin gymnastics experiments that provide a capability for selective sensitivity enhancements. In this article and overview and some applications of two-dimensional NMR experiments are presented. These powerful experiments are important complements to the one-dimensional experiments. As in the more sophisticated one-dimensional experiments, the two-dimensional experiments involve three distinct time periods: a preparation period, t/sub 0/; an evolution period, t/sub 1/; and a detection period, t/sub 2/.

  10. Image Correlation Applied to Single Crystal Plasticity Experiments and Comparison to Strain Gage Data

    SciTech Connect

    LeBlanc, M M; Florando, J N; Lassila, D H; Schmidt, T; Tyson II, J

    2005-06-29

    Full-field optical techniques are becoming increasingly popular for measuring the deformation of materials, especially in materials that exhibit non-uniform behavior. While there are many full-field techniques available (e.g. moire interferometry, electronic speckle pattern interferometry (ESPI), holography, and image correlation [1]), for our study of the deformation of single crystals, the image correlation technique was chosen for its insensitivity to vibrations and ability to measure large strains. While the theory and development of the algorithms for image correlation have been presented elsewhere [2,3] a comparative study to a conventional strain measurement device, such as a strain gage rosette, is desired to test the robustness and accuracy of the technique. The 6 Degrees of Freedom (6DOF) experiment, which was specifically designed to validate dislocation dynamics (DD) simulations [4], is ideally suited to compare the two methods. This experiment is different from previous experiments on single crystals in that it allows the crystal to deform essentially unconstrained, in both the elastic and plastic regimes, by allowing the bottom of the sample to move as the sample is being compressed. This unconstrained motion prevents the internal crystal planes from rotating during the deformation as typically seen in the pioneering work of Schmid [5] and Taylor [6]. In the early development of the 6DOF apparatus, stacked strain gage rosettes were used to provide the strain data [7]. While very accurate at small strains, strain gages provide an averaged measurement over a small area and cannot be used to measure the inhomogeneous plastic strains that typically occur during the 6DOF experiment. An image correlation technique can measure the full-field in-plane and out-of-plane deformation that occurs in single crystals, and a comparison to the strain gage data at small strains can test the accuracy of the method.

  11. 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.

    PubMed

    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.

  12. Advanced NMR technology for bioscience and biotechnology

    SciTech Connect

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

    1998-11-01

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

  13. An Integrated Laboratory Project in NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Hudson, Reggie L.; Pendley, Bradford D.

    1988-01-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

  15. Accounting for misalignments and thermal fluctuations in fluorescence correlation spectroscopy experiments on membranes.

    PubMed

    Sanguigno, Luigi; Cosenza, Chiara; Causa, Filippo; Netti, Paolo Antonio

    2013-03-21

    Several authors have exploited the ability of the fluorescence correlation spectroscopy to probe motion at the molecular level. In a couple of decades, all their efforts have allowed the application of this technique even to the diffusion measurement of cellular components. Nowadays, the fluorescence correlation spectroscopy is considered a standard tool to measure diffusion in cells both in vivo and in vitro. Unfortunately, while the interpretation and the set-up have been consolidated for 3D diffusion measurements (i.e. diffusion in an aqueous solution), the experiments carried out on flat elements, such as membranes, show unusually high relative errors. Furthermore, long tail correlations are generally detected and ascribed to diffusion anomalies. The 2D fluorescence correlation measurements have been interpreted under certain hypotheses, whereby the membrane is assumed to be perfectly flat, motionless and aligned with the optical axes. Here, we investigated the robustness of these hypotheses, trying to understand, in an elementary but not trivial way, how misalignments and thermal fluctuations affect the temporal correlation of the intensity fluctuation collected during measurements on membranes.

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

    NASA Astrophysics Data System (ADS)

    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

  17. Quantitative 2D liquid-state NMR.

    PubMed

    Giraudeau, Patrick

    2014-06-01

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

  18. Compressed exponential decays in correlation experiments: The influence of temperature gradients and convection

    NASA Astrophysics Data System (ADS)

    Gabriel, Jan; Blochowicz, Thomas; Stühn, Bernd

    2015-03-01

    In a wide range of soft materials, correlation experiments using laser light or partially coherent X-rays report the so called compressed exponential correlation functions, i. e., decays c(t) ∝ exp(-(t/τ)β) with β > 1. In many cases, this is related to the relaxation of inner stresses, but in some systems, the source of such a phenomenon is still poorly understood. We performed multi speckle-dynamic light scattering experiments in a system of polystyrene spheres in supercooled propanediol. At low temperatures, compressed exponential decays are observed in a multispeckle experiment, in agreement with the literature findings in similar systems. At the same time, due to the particular geometry of our setup, the speckle pattern shows indication for convection in the sample due to a slight temperature gradient across the sample cuvette mounted in a cold finger cryostat. These effects increase with decreasing temperature and after a temperature jump. In some cases it can be corrected for by assuming convective flow at constant velocity. Such corrections reduce or remove compressed exponential behavior in our experiment.

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed Central

    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 (< 5 yr) residency graduates on procedural competency. Resident case volumes were correlated with survey responses by SCORE category. Results In all, 75 residents performed 11 715 operations, which were distributed by SCORE category as follows: essential-common (EC) 9935 (84.8%), essential-uncommon (EU) 889 (7.6%) and complex 891 (7.6%). Alimentary tract procedures were the most commonly performed EC (2386, 24%) and EU (504, 56.7%) procedures. The least common EC procedure was plastic 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

  1. CLIP-COSY: A Clean In-Phase Experiment for the Rapid Acquisition of COSY-type Correlations.

    PubMed

    Koos, Martin R M; Kummerlöwe, Grit; Kaltschnee, Lukas; Thiele, Christina M; Luy, Burkhard

    2016-06-27

    The COSY experiment is an essential homonuclear 2D NMR experiment for the assignment of resonances. Its multiplet line shape, however, is often overly complicated, potentially leads to signal intensity losses, and is responsible for long minimum overall acquisition times. Herein, we present CLIP-COSY, a COSY-type experiment yielding clean in-phase peaks. It can be recorded within a few minutes and benefits from enhanced signal intensities for most cross-peaks. In combination with non-uniform sampling, the experiment times can be further reduced, and the in-phase multiplets enable the application of modern homonuclear decoupling techniques in both dimensions. As antiphase cancelations are avoided, CLIP-COSY can also be applied to macromolecules and other samples with broadened lines.

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

    PubMed Central

    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

  3. Left medial orbitofrontal cortex volume correlates with skydive-elicited euphoric experience.

    PubMed

    Carlson, Joshua M; Cha, Jiook; Fekete, Tomer; Greenberg, Tsafrir; Mujica-Parodi, Lilianne R

    2016-11-01

    The medial orbitofrontal cortex has been linked to the experience of positive affect. Greater medial orbitofrontal cortex volume is associated with greater expression of positive affect and reduced medial orbital frontal cortex volume is associated with blunted positive affect. However, little is known about the experience of euphoria, or extreme joy, and how this state may relate to variability in medial orbitofrontal cortex structure. To test the hypothesis that variability in euphoric experience correlates with the volume of the medial orbitofrontal cortex, we measured individuals' (N = 31) level of self-reported euphoria in response to a highly anticipated first time skydive and measured orbitofrontal cortical volumes with structural magnetic resonance imaging. Skydiving elicited a large increase in self-reported euphoria. Participants' euphoric experience was predicted by the volume of their left medial orbitofrontal cortex such that, the greater the volume, the greater the euphoria. Further analyses indicated that the left medial orbitofrontal cortex and amygdalo-hippocampal complex independently explain variability in euphoric experience and that medial orbitofrontal cortex volume, in conjunction with other structures within the mOFC-centered corticolimbic circuit, can be used to predict individuals' euphoric experience.

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

    PubMed

    Schubert; Smalla; Schmieder; Oschkinat

    1999-11-01

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

  5. MUSIC in Triple-Resonance Experiments: Amino Acid Type-Selective 1H- 15N Correlations

    NASA Astrophysics Data System (ADS)

    Schubert, Mario; Smalla, Maika; Schmieder, Peter; Oschkinat, Hartmut

    1999-11-01

    Amino acid type-selective triple-resonance experiments can be of great help for the assignment of protein spectra, since they help to remove ambiguities in either manual or automated assignment procedures. Here, modified triple-resonance experiments that yield amino acid type-selective 1H-15N correlations are presented. They are based on novel coherence transfer schemes, the MUSIC pulse sequence elements, that replace the initial INEPT transfer and are selective for XH2 or XH3 (X can be 15N or 13C). The desired amino acid type is thereby selected based on the topology of the side chain. Experiments for Gly (G-HSQC); Ala (A-HSQC); Thr, Val, Ile, and Ala (TAVI-HSQC); Thr and Ala (TA-HSQC), as well as Asn and Gln (N-HSQC and QN-HSQC), are described. The new experiments are recorded as two-dimensional experiments and therefore need only small amounts of spectrometer time. The performance of the experiments is demonstrated with the application to two protein domains.

  6. Correlates of sexual experience among a nationally representative sample of alternative high school students.

    PubMed

    Shrier, Lydia A; Crosby, Richard

    2003-05-01

    Little is known about risk and protective factors associated with sexual experience among alternative school students that might prove useful in targeting and guiding early interventions to prevent onset of sexual risk behavior. Researchers analyzed data from the national Alternative High School Youth Risk Behavior Survey. Principal components analysis identified six risk and protective factors: weapon carrying; tobacco use; cocaine, inhalant, and needle use; alcohol and marijuana use; participation in sports; and fighting. Composite variables with significant bivariate relationships to sexual experience, as well as demographic variables, were entered into a logistic regression analysis to determine independent effects of these correlates on students' sexual experience (N = 6.037). Nearly 90% of students reported having sexual intercourse. In multivariate analysis, significant demographic correlates of sexual experience included female gender (58% more likely than males to report ever having sex), African American race (2.83 times more likely than non-Hispanic Whites), and age (28% more likely with each advancing year). Attending school in a rural or suburban region corresponded to a 31% decrease and 46% decrease, respectively, in the odds of ever having sex. Weapon carrying, and cocaine, inhalant, and needle use, were associated with a 35% and 46% increase, respectively, in the odds of ever having sex. Students reporting they had ever used alcohol or marijuana, and those reporting recent fighting behavior, were 2.7 and 1.6 times more likely, respectively, to report sexual experience. Most alternative school students have had sexual intercourse, with those students engaging in substance use, weapon carrying, and fighting behaviors being at greater risk for sexual experience. Prevention programs for high-risk youth attending alternative high schools need to consider how to promote continued abstinence among the small but important minority of alternative school

  7. Deuterium Exchange Kinetics by NMR.

    ERIC Educational Resources Information Center

    Roper, G. C.

    1985-01-01

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

  8. 1H–13C hetero-nuclear dipole–dipole couplings of methyl groups in stationary and magic angle spinning solid-state NMR experiments of peptides and proteins

    PubMed Central

    Wu, Chin H.; Das, Bibhuti B.; Opella, Stanley J.

    2010-01-01

    13C NMR of isotopically labeled methyl groups has the potential to combine spectroscopic simplicity with ease of labeling for protein NMR studies. However, in most high resolution separated local field experiments, such as polarization inversion spin exchange at the magic angle (PISEMA), that are used to measure 1H–13C hetero-nuclear dipolar couplings, the four-spin system of the methyl group presents complications. In this study, the properties of the 1H–13C hetero-nuclear dipolar interactions of 13C-labeled methyl groups are revealed through solid-state NMR experiments on a range of samples, including single crystals, stationary powders, and magic angle spinning of powders, of 13C3 labeled alanine alone and incorporated into a protein. The spectral simplifications resulting from proton detected local field (PDLF) experiments are shown to enhance resolution and simplify the interpretation of results on single crystals, magnetically aligned samples, and powders. The complementarity of stationary sample and magic angle spinning (MAS) measurements of dipolar couplings is demonstrated by applying polarization inversion spin exchange at the magic angle and magic angle spinning (PISEMAMAS) to unoriented samples. PMID:19896874

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

    ERIC Educational Resources Information Center

    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…

  10. MULTIPLE-QUANTUM NMR IN SOLIDS

    SciTech Connect

    Yen, Y-S.

    1982-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

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

    SciTech Connect

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

    2015-01-28

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

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

    SciTech Connect

    Smith, Sarah J.; Wei, Max; Sohn, Michael D.

    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.

  14. Comparison between theory and experiment for universal thermodynamics of a homogeneous, strongly correlated Fermi gas

    SciTech Connect

    Hu Hui; Liu Xiaji; Drummond, Peter D.

    2011-06-15

    We compare the theoretical predictions for universal thermodynamics of a homogeneous, strongly correlated Fermi gas with the latest experimental measurements reported by the ENS group [S. Nascimbene et al., Nature (London) 463, 1057 (2010)] and the Tokyo group [M. Horikoshi et al., Science 327, 442 (2010)]. The theoretical results are obtained using two diagrammatic theories, together with a virial expansion theory combined with a Pade approximation. We find good agreement between theory and experiment. In particular, the virial expansion, using a Pade approximation up to third order, describes the experimental results extremely well down to the superfluid transition temperature, T{sub c{approx}}0.16T{sub F}, where T{sub F} is the Fermi temperature. The comparison in this work complements our previous comparative study on the universal thermodynamics of a strongly correlated but trapped Fermi gas. The comparison also raises interesting issues about the unitary entropy and the applicability of the Pade approximation.

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

    PubMed Central

    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

  16. 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?

    PubMed

    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.

  17. NMR planar microcoil for microanalysis

    NASA Astrophysics Data System (ADS)

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

    2006-11-01

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

  18. Superoxygenated Water as an Experimental Sample for NMR Relaxometry

    ERIC Educational Resources Information Center

    Nestle, Nikolaus; Dakkouri, Marwan; Rauscher, Hubert

    2004-01-01

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

  19. Coaxial probe for nuclear magnetic resonance diffusion and relaxation correlation experiments

    SciTech Connect

    Tang, Yiqiao; Hürlimann, Martin; Mandal, Soumyajit; Paulsen, Jeffrey; Song, Yi-Qiao

    2014-02-21

    A coaxial nuclear magnetic resonance (NMR) probe is built to measure diffusion and relaxation properties of liquid samples. In particular, we demonstrate the acquisition of two-dimensional (2D) distribution functions (T{sub 1}-T{sub 2} and diffusion–T{sub 2}), essential for fluids characterization. The compact design holds promise for miniaturization, thus enabling the measurement of molecular diffusion that is inaccessible to conventional micro-NMR setups. Potential applications range from crude oil characterization to biomolecular screening and detections.

  20. Characterization of good teleoperators - What aptitudes, interests, and experience correlate with measures of teleoperator performance

    NASA Technical Reports Server (NTRS)

    Yorchak, J. P.; Hartley, C. S.; Hinman, E.

    1985-01-01

    The use of aptitude tests and questionnaries to evaluate an individuals aptitude for teleoperation is studied. The Raven Progressive Matrices Test and Differential Aptitude Tests, and a 16-item questionnaire for assessing the subject's interests, academic background, and previous experience are described. The Proto-Flight Manipulator Arm, cameras, console, hand controller, and task board utilized by the 17 engineers are examined. The correlation between aptitude scores and questionnaire responses, and operator performance is investigated. Multiple regression data reveal that the eight predictor variables are not individually significant for evaluating operator performance; however, the complete test battery is applicable for predicting 49 percent of subject variance on the criterion task.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. NMR analysis of biodiesel

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  3. A New Microcell Technique for NMR Analysis.

    ERIC Educational Resources Information Center

    Yu, Sophia J.

    1987-01-01

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

  4. Differential characterization using readily accessible NMR experiments of novel N- and O-alkylated quinolin-4-ol, 1,5-naphthyridin-4-ol and quinazolin-4-ol derivatives with antimycobacterial activity.

    PubMed

    Pitta, Eleni; Balabon, Olga; Rogacki, Maciej K; Gómez, Jesús; Cunningham, Fraser; Joosens, Jurgen; Augustyns, Koen; van der Veken, Pieter; Bates, Robert

    2017-01-05

    During the construction of bioactive molecules, regioselective alkylation of heterocyclic, N/O ambident nucleophiles is a frequently encountered synthetic transformation. In this framework, specific attention is required to unambiguously determine the structures of obtained reaction products. As part of our project on quinoloxyacetamide based antimycobacterial agents, a series of N- or O- alkylated quinolin-4-ol, 1,5-naphthyridin-4-ol and quinazolin-4-ol derivatives were prepared during the course of which we observed unexpected selectivity issues. After finding that no consistent procedure existed in the literature for assigning regioisomers of this type, we applied three readily accessible NMR experiment types ((13)C NMR, HSQC/HMBC and NOE) to resolve any uncertainties regarding the obtained regioisomeric structures. Furthermore, the antimycobacterial activity of all final compounds was evaluated with the best compound 23 showing potent antitubercular activity (MIC = 1.25 μM) without cytotoxic effects.

  5. Two dimensional NMR and NMR relaxation studies of coal structure

    SciTech Connect

    Zilm, K.W.

    1990-01-01

    This report covers the progress made on the title project and summarizes the accomplishments for the project period. Four major areas of inquiry have been pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines the authors are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. The effects of very high MAS rates (>10 kHz) on cross polarization dynamics are also being investigated for similar reasons. The authors have concentrated on a theoretical treatment of pairs of tightly coupled spin {1/2} nuclei under magic angle spinning conditions. The average Hamiltonian theory developed here is required for a quantitative understanding of two dimensional NMR experiments of such spin pairs in solids. These experiments in turn provide a means of determining connectivities between resonances in solid state NMR spectra. Development of these techniques will allow us to establish connectivities between functional components in coals. The complete description of these spin dynamics has turned out to be complex, and is necessary to provide a foundation upon which such experiments may be quantitatively interpreted in complex mixtures such as coals. 25 refs., 4 figs., 3 tabs.

  6. Radar analyses of mesoscale meteorological phenomena during the AVE/VAS correlation field experiment

    NASA Technical Reports Server (NTRS)

    Huebner, G. L.

    1984-01-01

    Radar data were collected during the selected critical times of the field experiment and subsequently analyzed for specific items. The analyses of the radar data for the AVE/VAS experiment provided statistically significant values for each of the 10 Km by 10 Km grids within radar range. The resulting information for correlation with satellite data included the following derived items that were averaged for each grid area: (1) rainfall rate in mm/hr; (2) dBZ (reflectivity) values; (3) accumulated rainfall values per hour; (4) accumulated rainfall values for a 6-hour period; (5) vertically integrated liquid water content per square meter; and (6) vertical height of the radar axis at the midpoint of each grid. Additional products derived from radar data are being investigated. An example of one such product is the derivation of the errors in integrated rainfall with different sampling periods. This is of significance for correlation with satellite data in that normally a step-function type of rainfall rate is used to derive the total rainfall over a period.

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

    PubMed Central

    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

  8. Music in depression: Neural correlates of emotional experience in remitted depression

    PubMed Central

    Aust, Sabine; Filip, Karin; Koelsch, Stefan; Grimm, Simone; Bajbouj, Malek

    2013-01-01

    AIM: To investigate neural and behavioral correlates of emotional experiences as potential vulnerability markers in remitted depression. METHODS: Fourteen remitted participants with a history of major depression and fourteen closely matched healthy control participants took part in the study. We used two psychiatric interviews (Hamilton Depression Rating Scale, Montgomery-Asberg Depression Rating Scale) and one self-report scale (Beck Depression Inventory) to assess remission. Healthy control participants were interviewed by an experienced psychiatrist to exclude those who showed any current or lifetime psychiatric or neurological disorders. To explore psychosocial and cognitive-interpersonal underpinnings of potential vulnerability markers of depression, early life stress, coping styles and alexithymia were also assessed. We induced pleasant and unpleasant emotional states using congruent combinations of music and human emotional faces to investigate neural and behavioral correlates of emotional experiences; neutral stimuli were used as a control condition. Brain responses were recorded using functional magnetic resonance imaging. Behavioral responses of pleasantness, arousal, joy and fear were measured via button-press inside the resonance imaging scanner. RESULTS: The mean age of the sample was 54.9 (± 11.3) years. There were no differences between remitted depressed (RD) (n = 14; 9 females and 5 males) and healthy participants (n = 14; 8 females and 6 males) regarding age, current degree of depression, early life stress, coping styles and alexithymia. On a neural level, RD participants showed reduced activations in the pregenual anterior cingulate cortex (pgACC) in response to pleasant [parameter estimates: -0.78 vs 0.32; t(26) = -3.41, P < 0.05] and unpleasant [parameter estimates: -0.88 vs 0.56; t(26)= -4.02, P < 0.05] emotional stimuli. Linear regression analysis revealed that pgACC activity was modulated by early life stress [β = -0.48; R2 = 0.23, F(1

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

    ERIC Educational Resources Information Center

    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.…

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

    ERIC Educational Resources Information Center

    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.…

  11. A microcoil NMR probe for coupling microscale HPLC with on-line NMR spectroscopy.

    PubMed

    Subramanian, R; Kelley, W P; Floyd, P D; Tan, Z J; Webb, A G; Sweedler, J V

    1999-12-01

    An HPLC NMR system is presented that integrates a commercial microbore HPLC system using a 0.5-mm column with a 500-MHz proton NMR spectrometer using a custom NMR probe with an observe volume of 1.1 microL and a coil fill factor of 68%. Careful attention to capillary connections and NMR flow cell design allows on-line NMR detection with no significant loss in separation efficiency when compared with a UV chromatogram. HPLC NMR is performed on mixtures of amino acids and small peptides with analyte injection amounts as small as 750 ng; the separations are accomplished in less than 10 min and individual NMR spectra are acquired with 12 s time resolution. Stopped-flow NMR is achieved by diversion of the chromatographic flow after observation of the beginning of the analyte band within the NMR flow cell. Isolation of the compound of interest within the NMR detection cell allows multidimensional experiments to be performed. A stopped-flow COSY spectrum of the peptide Phe-Ala is acquired in 3.5 h with an injected amount of 5 micrograms.

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

    PubMed

    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.

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

    PubMed

    Zhang, Zhiyong; Smith, Pieter E S; Frydman, Lucio

    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.

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

    SciTech Connect

    Zhang, Zhiyong; Smith, Pieter E. S.; Frydman, Lucio

    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.

  15. Single-scan 2D NMR: An Emerging Tool in Analytical Spectroscopy

    PubMed Central

    Giraudeau, Patrick; Frydman, Lucio

    2016-01-01

    Two-dimensional Nuclear Magnetic Resonance (2D NMR) spectroscopy is widely used in chemical and biochemical analyses. Multidimensional NMR is also witnessing an increased use in quantitative and metabolic screening applications. Conventional 2D NMR experiments, however, are affected by inherently long acquisition durations, arising from their need to sample the frequencies involved along their indirect domains in an incremented, scan-by-scan nature. A decade ago a so-called “ultrafast” (UF) approach was proposed, capable to deliver arbitrary 2D NMR spectra involving any kind of homo- or hetero-nuclear correlations, in a single scan. During the intervening years the performance of this sub-second 2D NMR methodology has been greatly improved, and UF 2D NMR is rapidly becoming a powerful analytical tool witnessing an expanded scope of applications. The present reviews summarizes the principles and the main developments which have contributed to the success of this approach, and focuses on applications which have been recently demonstrated in various areas of analytical chemistry –from the real time monitoring of chemical and biochemical processes, to extensions in hyphenated techniques and in quantitative applications. PMID:25014342

  16. A ferromagnetic shim insert for NMR magnets - Towards an integrated gyrotron for DNP-NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Ryan, Herbert; van Bentum, Jan; Maly, Thorsten

    2017-04-01

    In recent years high-field Dynamic Nuclear Polarization (DNP) enhanced NMR spectroscopy has gained significant interest. In high-field DNP-NMR experiments (⩾400 MHz 1H NMR, ⩾9.4 T) often a stand-alone gyrotron is used to generate high microwave/THz power to produce sufficiently high microwave induced B1e fields at the position of the NMR sample. These devices typically require a second, stand-alone superconducting magnet to operate. Here we present the design and realization of a ferroshim insert, to create two iso-centers inside a commercially available wide-bore NMR magnet. This work is part of a larger project to integrate a gyrotron into NMR magnets, effectively eliminating the need for a second, stand-alone superconducting magnet.

  17. Dynamics and Structure in Good Glass Formers LiCl-RH2O: A NMR and Quasielastic Neutron Scattering Study

    NASA Astrophysics Data System (ADS)

    Maurin, P.; Dupuy-Philon, J.; Jal, J.; Asahi, N.; Kamiyama, T.; Kawamura, J.; Nakamura, Y.

    The temperature behaviour of the self-diffusion coefficient and of the spin-lattice correlation time have been analysed from QENS and NMR experiments performed on LiCl-6H2O and LiCl-4H2O. Those results throw some light to primary and secondary relaxation time behaviour in these systems.

  18. 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

    SciTech Connect

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

    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.

  19. 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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    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 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.

  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.

    PubMed

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

    2014-10-21

    We discuss the effect of electron correlation on the unexpected differential sensitivity (UDS) in the (1)J(C-H) coupling constant of CH4 using a decomposition into contributions from localized molecular orbitals and compare with the (1)J(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 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. Temperature imaging by 1H NMR and suppression of convection in NMR probes

    PubMed

    Hedin; Furo

    1998-03-01

    A simple arrangement for suppressing convection in NMR probes is tested experimentally. Diffusion experiments are used to determine the onset of convection and 1H temperature imaging helps to rationalize the somewhat surprising results. A convenient new 1H NMR thermometer, CH2Br2 dissolved in a nematic thermotropic liquid crystal, is presented. Copyright 1998 Academic Press.

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

    ERIC Educational Resources Information Center

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

    2009-01-01

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

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Interfacial Ca(2+) environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced (43)Ca NMR spectroscopy.

    PubMed

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

    2017-01-27

    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.

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

    SciTech Connect

    Castromonte Flores, Cesar Manuel

    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

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

    SciTech Connect

    Wei, Max; Smith, Sarah J.; Sohn, Michael D.

    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.

  8. Influence of the penetration enhancer isopropyl myristate on stratum corneum lipid model membranes revealed by neutron diffraction and (2)H NMR experiments.

    PubMed

    Eichner, Adina; Stahlberg, Sören; Sonnenberger, Stefan; Lange, Stefan; Dobner, Bodo; Ostermann, Andreas; Schrader, Tobias E; Hauß, Thomas; Schroeter, Annett; Huster, Daniel; Neubert, Reinhard H H

    2017-05-01

    The stratum corneum (SC) provides the main barrier properties in native skin. The barrier function is attributed to the intercellular lipids, forming continuous multilamellar membranes. In this study, SC lipid membranes in model ratios were enriched with deuterated lipids in order to investigate structural and dynamical properties by neutron diffraction and (2)H solid-state NMR spectroscopy. Further, the effect of the penetration enhancer isopropyl myristate (IPM) on the structure of a well-known SC lipid model membrane containing synthetically derived methyl-branched ceramide [EOS], ceramide [AP], behenic acid and cholesterol (23/10/33/33wt%) was investigated. IPM supported the formation of a single short-periodicity phase (SPP), in which we determined the molecular organization of CER[AP] and CER[EOS]-br for the first time. Furthermore, the thermotropic phase behavior of the lipid system was analyzed by additional neutron diffraction studies as well as by (2)H solid-state NMR spectroscopy, covering temperatures of 32°C (physiological skin temperature), 50°C, and 70°C with a subsequent cooldown back to skin temperature. Both techniques revealed a phase transition and a hysteresis effect. During the cooldown, Bragg peaks corresponding to a long-periodicity phase (LPP) appeared. Additionally, (2)H NMR revealed that the IPM molecules are isotopic mobile at all temperatures.

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

    SciTech Connect

    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.

    2016-12-19

    Here, we describe a detection system designed to precisely measure multiple correlations in neutron β decay. Furthermore, the system is based on thick, large area, highly segmented silicon detectors developed in collaboration with Micron Semiconductor, Ltd. The prototype system meets specifications of 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. We have demonstrated the coincident detection of β particles and recoil protons from neutron β decay, using ultracold neutrons at the Los Alamos Neutron Science Center, . 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.

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

    DOE PAGES

    Broussard, L. J.; Oak Ridge National Lab.; Zeck, B. A.; ...

    2016-12-19

    Here, we describe a detection system designed to precisely measure multiple correlations in neutron β decay. Furthermore, the system is based on thick, large area, highly segmented silicon detectors developed in collaboration with Micron Semiconductor, Ltd. The prototype system meets specifications of 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. We have demonstrated the coincident detection of β particles and recoil protons from neutron β decay, using ultracold neutrons at the Los Alamos Neutron Science Center, . The fully instrumented detection system willmore » be implemented in the UCNB and Nab experiments, to determine the neutron β decay parameters B, a, and b.« less

  11. aCORN: An experiment to measure the electron-antineutrino correlation in neutron decay

    NASA Astrophysics Data System (ADS)

    Wietfeldt, F. E.; Byrne, J.; Collett, B.; Dewey, M. S.; Jones, G. L.; Komives, A.; Laptev, A.; Nico, J. S.; Noid, G.; Stephenson, E. J.; Stern, I.; Trull, C.; Yerozolimsky, B. G.

    2009-12-01

    The aCORN experiment is designed to make a precision ( <1%) measurement of the electron-antineutrino angular correlation ( a-coefficient) in neutron beta decay. It uses a new method proposed in 1996 by Yerozolimsky and Mostovoy. Electrons and recoil protons from neutron decay in a cold beam are detected in coincidence. The momenta of the particles are selected so that the protons form two kinematically distinct time-of-flight groups as a function of electron energy. The count rate asymmetry in these two groups is proportional to the a-coefficient. Precision spectroscopy of the protons is not required. The apparatus is currently under construction. It will be integrated and tested at the Indiana University Cyclotron Facility (IUCF) and then moved to the NIST Center for Neutron Research for the initial physics run.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    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

  14. Flight experiments measuring boundary-layer disturbances in laminar flow and correlation with stability analysis

    NASA Technical Reports Server (NTRS)

    Lee, Cynthia C.; Obara, Clifford J.; Vijgen, Paul M.; Wusk, Michael S.

    1991-01-01

    Flight test results are reported from an experiment designed to study the detailed growth of disturbances in the laminar boundary layer. A gloved wing section incorporating closely-spaced flush-mounted streamwise-located instrumentation for measuring instability frequencies and amplitude growths as well as pressure distributions was used. The growth of Tollmien-Schlichting (T-S) and crossflow instabilities is predicted by the linear e exp n method and compared to the measured boundary-layer disturbance frequencies. The predictions showed good agreement with the measured data. The results exhibited fair agreement with previous n(T-S) and n(CF) flight correlations for several of the conditions analyzed. It is inferred from the high n(T-S) values for these data that moderately swept wings at compressible speeds can withstand higher combinations of n(T-S) and n(CF) values and still remain laminar than previously thought.

  15. Children’s Experience of Posttraumatic Growth: Distinguishing General from Domain-Specific Correlates

    PubMed Central

    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. PMID:26714193

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Quantifying long-range correlations and 1/f patterns in a minimal experiment of social interaction.

    PubMed

    Bedia, Manuel G; Aguilera, Miguel; Gómez, Tomás; Larrode, David G; Seron, Francisco

    2014-01-01

    In recent years, researchers in social cognition have found the "perceptual crossing paradigm" to be both a theoretical and practical advance toward meeting particular challenges. This paradigm has been used to analyze the type of interactive processes that emerge in minimal interactions and it has allowed progress toward understanding of the principles of social cognition processes. In this paper, we analyze whether some critical aspects of these interactions could not have been observed by previous studies. We consider alternative indicators that could complete, or even lead us to rethink, the current interpretation of the results obtained from both experimental and simulated modeling in the fields of social interactions and minimal perceptual crossing. In particular, we discuss the possibility that previous experiments have been analytically constrained to a short-term dynamic type of player response. Additionally, we propose the possibility of considering these experiments from a more suitable framework based on the use and analysis of long-range correlations and fractal dynamics. We will also reveal evidence supporting the idea that social interactions are deployed along many scales of activity. Specifically, we propose that the fractal structure of the interactions could be a more adequate framework to understand the type of social interaction patterns generated in a social engagement.

  18. Quantifying long-range correlations and 1/f patterns in a minimal experiment of social interaction

    PubMed Central

    Bedia, Manuel G.; Aguilera, Miguel; Gómez, Tomás; Larrode, David G.; Seron, Francisco

    2014-01-01

    In recent years, researchers in social cognition have found the “perceptual crossing paradigm” to be both a theoretical and practical advance toward meeting particular challenges. This paradigm has been used to analyze the type of interactive processes that emerge in minimal interactions and it has allowed progress toward understanding of the principles of social cognition processes. In this paper, we analyze whether some critical aspects of these interactions could not have been observed by previous studies. We consider alternative indicators that could complete, or even lead us to rethink, the current interpretation of the results obtained from both experimental and simulated modeling in the fields of social interactions and minimal perceptual crossing. In particular, we discuss the possibility that previous experiments have been analytically constrained to a short-term dynamic type of player response. Additionally, we propose the possibility of considering these experiments from a more suitable framework based on the use and analysis of long-range correlations and fractal dynamics. We will also reveal evidence supporting the idea that social interactions are deployed along many scales of activity. Specifically, we propose that the fractal structure of the interactions could be a more adequate framework to understand the type of social interaction patterns generated in a social engagement. PMID:25429277

  19. Weak values, quantum trajectories, and the cavity-QED experiment on wave-particle correlation

    NASA Astrophysics Data System (ADS)

    Wiseman, H. M.

    2002-03-01

    Weak values as introduced by Aharonov, Albert, and Vaidman (AAV) are ensemble-average values for the results of weak measurements. They are interesting when the ensemble is preselected on a particular initial state and postselected on a particular final measurement result. It is shown that weak values arise naturally in quantum optics, as weak measurements occur whenever an open system is monitored (as by a photodetector). The quantum-trajectory theory is used to derive a generalization of AAV's formula to include (a) mixed initial conditions, (b) nonunitary evolution, (c) a generalized (nonprojective) final measurement, and (d) a non-back-action-evading weak measurement. This theory is applied to the recent cavity-QED experiment demonstrating wave particle duality [G. T. Foster, L. A. Orozco, H. M. Castro-Beltran, and H. J. Carmichael, Phys. Rev. Lett. 85, 3149 (2000)]. It is shown that the ``fractional-order'' correlation function measured in that experiment can be recast as a weak value in a form as simple as that introduced by AAV.

  20. Solvent suppression in DNP enhanced solid state NMR

    NASA Astrophysics Data System (ADS)

    Yarava, Jayasubba Reddy; Chaudhari, Sachin Rama; Rossini, Aaron J.; Lesage, Anne; Emsley, Lyndon

    2017-04-01

    We show how DNP enhanced solid-state NMR spectra can be dramatically simplified by suppression of solvent signals. This is achieved by (i) exploiting the paramagnetic relaxation enhancement of solvent signals relative to materials substrates, or (ii) by using short cross-polarization contact times to transfer hyperpolarization to only directly bonded carbon-13 nuclei in frozen solutions. The methods are evaluated for organic microcrystals, surfaces and frozen solutions. We show how this allows for the acquisition of high-resolution DNP enhanced proton-proton correlation experiments to measure inter-nuclear proximities in an organic solid.

  1. NMR reaction monitoring in flow synthesis

    PubMed Central

    Gomez, M Victoria

    2017-01-01

    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. PMID:28326137

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

    PubMed

    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.

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

    PubMed Central

    2016-01-01

    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 1H 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 1H spectra encode a wealth of information about bonds and molecular geometry that may be fully mined by 1H iterative full spin analysis (HiFSA). Fully characterized 1D 1H 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. PMID:26812443

  4. Spatial correlations and probability density function of the phase difference in a developed speckle-field: numerical and natural experiments

    NASA Astrophysics Data System (ADS)

    Mysina, N. Yu; Maksimova, L. A.; Gorbatenko, B. B.; Ryabukho, V. P.

    2015-10-01

    Investigated are statistical properties of the phase difference of oscillations in speckle-fields at two points in the far-field diffraction region, with different shapes of the scatterer aperture. Statistical and spatial nonuniformity of the probability density function of the field phase difference is established. Numerical experiments show that, for the speckle-fields with an oscillating alternating-sign transverse correlation function, a significant nonuniformity of the probability density function of the phase difference in the correlation region of the field complex amplitude, with the most probable values 0 and p, is observed. A natural statistical interference experiment using Young diagrams has confirmed the results of numerical experiments.

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

    PubMed

    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

  6. J-edited pure shift NMR for the facile measurement of (n)J(HH) for specific protons.

    PubMed

    Chaudhari, Sachin Rama; Suryaprakash, N

    2015-04-07

    We report a novel 1D J-edited pure shift NMR experiment (J-PSHIFT) that was constructed from a pseudo 2D experiment for the direct measurement of proton-proton scalar couplings. The experiment gives homonuclear broad-band (1)H-decoupled (1)H NMR spectra, which provide a single peak for chemically distinct protons, and only retain the homonuclear-scalar-coupled doublet pattern at the chemical-shift positions of the protons in the coupled network of a specific proton. This permits the direct and unambiguous measurement of the magnitudes of the couplings. The incorporation of a 1D selective correlation spectroscopy (COSY)/ total correlation spectroscopy (TOCSY) block in lieu of the initial selective pulse, results in the exclusive detection of the correlated spectrum of a specific proton.

  7. Correlation between biological and physical availabilities of phenanthrene in soils and soil humin in aging experiments

    SciTech Connect

    White, J.C.; Hunter, M.; Nam, K.; Pignatello, J.J.; Alexander, M.

    1999-08-01

    The bioavailability of an organic compound in a soil or sediment commonly declines with the soil-chemical contact time (aging). A series of parallel desorption and bioavailability experiments was carried out on phenanthrene previously aged up to {approximately}100 d in Mount Pleasant silt loam (Mt. Pleasant, NY, USA) or Pahokee peat soil to determine as a function of the aging period the degree of correlation between the reduction in bioavailability and the rate and extent of desorption and the influence of soil organic matter composition on availability. The mineralization of phenanthrene by two bacteria and the uptake of phenanthrene by earthworms showed expected declines with aging. Likewise, the rate of phenanthrene desorption in the absence of organisms decreased with aging. The decline in initial rate of mineralization or desorption was nearly an order of magnitude after 50 to 60 d of aging. Plots of normalized rates of mineralization or desorption practically coincided. Similarly, plots of normalized fraction mineralized or fraction desorbed during an arbitrary period gave comparable slopes. The partial removal of organic matter from the peat by extraction with dilute NaOH to leave the humin fraction reduced the biodegradation of phenanthrene aged for 38 and 63 d as compared to the nonextracted peat, but the effect disappeared at longer incubation times. The rate of desorption from samples of peat previously extracted with NaOH or Na{sub 4}P{sub 2}O{sub 7} declined with aging and, for a given aging period, was significantly slower than from nonextracted peat. This work shows that the reduction in bioavailability of phenanthrene over time in soil is directly correlated with reduction of its physical availability due to desorption limitations. In addition, this study shows that removal of extractable humic substances leads to a decline in the rate of desorption and in the bioavailability of the substrate.

  8. Binding of antifusion peptides with HIVgp41 from molecular dynamics simulations: quantitative correlation with experiment.

    PubMed

    Strockbine, Bentley; Rizzo, Robert C

    2007-05-15

    Peptides based on C-terminal regions of the human immunodeficiency virus (HIV) viral protein gp41 represent an important new class of antiviral therapeutics called peptide fusion inhibitors. In this study, computational methods were used to model the binding of six peptides that contain residues that pack into a conserved hydrophobic pocket on HIVgp41, an attractive target site for the development of small molecule inhibitors. Free energies of binding were computed using molecular mechanics Generalized Born surface area (MM-GBSA) methods from molecular dynamics (MD) simulations, which employed either explicit (TIP3P) or continuum Generalized Born (GB) water models and strong correlations between experimental and computational affinities were obtained in both cases. Energy decomposition of the TIP3P-MD results (r2 = 0.75) reveals that variation in experimental affinity is highly correlated with changes in intermolecular van der Waals energies (deltaE(vdw)) on both a local (residue-based, r2 = 0.94) and global (peptide-based, r2 = 0.84) scale. The results show that differential association of C-peptides with HIVgp41 is driven solely by changes within the conserved pocket supporting the hypothesis that this region is an important drug target site. Such strong agreement with experiment is notable given the large size of the ligands (34 amino-acids) relative to the small range of experimental affinities (2 kcal/mol) and demonstrates good sensitivity of this computational method for simulating peptide fusion inhibitors. Finally, inspection of simulation trajectories identified a highly populated pi-type hydrogen bond, which formed between Gln575 on the receptor and the aromatic ring of peptide ligand Phe631, which could have important implications for drug design.

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

    SciTech Connect

    Kobayashi, Takeshi; Gupta, Shalabh; Caporini, Marc A; Pecharsky, Vitalij K; Pruski, Marek

    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.

  10. Two dimensional NMR and NMR relaxation studies of coal structure

    SciTech Connect

    Zilm, K.W.

    1992-05-27

    This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with {sup 13}C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed a delineating the role of methyl group rotation in the proton NMR relaxation behavior of coals.

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

    PubMed

    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.

  12. Solution State Structure Determination of Silicate Oligomers by 29Si NMR Spectroscopy and Molecular Modeling

    SciTech Connect

    Cho, Herman M.; Felmy, Andrew R.; Craciun, Raluca; Keenum, Johnathan P.; Shah, Neil K.; Dixon, David A.

    2006-02-22

    Evidence for nine new solution state silicate oligomers has been discovered by 29Si NMR homonuclear correlation experiments of 29Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the 29Si–29Si 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 crosspeaks 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 stability of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations.

  13. Identification of allosteric PIF-pocket ligands for PDK1 using NMR-based fragment screening and 1H-15N TROSY experiments.

    PubMed

    Stockman, Brian J; Kothe, Michael; Kohls, Darcy; Weibley, Laura; Connolly, Brendan J; Sheils, Alissa L; Cao, Qing; Cheng, Alan C; Yang, Lily; Kamath, Ajith V; Ding, Yuan-Hua; Charlton, Maura E

    2009-02-01

    Aberrant activation of the phosphoinositide 3-kinase pathway because of genetic mutations of essential signalling proteins has been associated with human diseases including cancer and diabetes. The pivotal role of 3-phosphoinositide-dependent kinase-1 in the PI3K signalling cascade has made it an attractive target for therapeutic intervention. The N-terminal lobe of the 3-phosphoinositide-dependent kinase-1 catalytic domain contains a docking site which recognizes the non-catalytic C-terminal hydrophobic motifs of certain substrate kinases. The binding of substrate in this so-called PDK1 Interacting Fragment pocket allows interaction with 3-phosphoinositide-dependent kinase-1 and enhanced phosphorylation of downstream kinases. NMR spectroscopy was used to a screen 3-phosphoinositide-dependent kinase-1 domain construct against a library of chemically diverse fragments in order to identify small, ligand-efficient fragments that might interact at either the ATP site or the allosteric PDK1 Interacting Fragment pocket. While majority of the fragment hits were determined to be ATP-site binders, several fragments appeared to interact with the PDK1 Interacting Fragment pocket. Ligand-induced changes in 1H-15N TROSY spectra acquired using uniformly 15N-enriched PDK1 provided evidence to distinguish ATP-site from PDK1 Interacting Fragment-site binding. Caliper assay data and 19F NMR assay data on the PDK1 Interacting Fragment pocket fragments and structurally related compounds identified them as potential allosteric activators of PDK1 function.

  14. Measuring decision weights in recognition experiments with multiple response alternatives: comparing the correlation and multinomial-logistic-regression methods.

    PubMed

    Dai, Huanping; Micheyl, Christophe

    2012-11-01

    Psychophysical "reverse-correlation" methods allow researchers to gain insight into the perceptual representations and decision weighting strategies of individual subjects in perceptual tasks. Although these methods have gained momentum, until recently their development was limited to experiments involving only two response categories. Recently, two approaches for estimating decision weights in m-alternative experiments have been put forward. One approach extends the two-category correlation method to m > 2 alternatives; the second uses multinomial logistic regression (MLR). In this article, the relative merits of the two methods are discussed, and the issues of convergence and statistical efficiency of the methods are evaluated quantitatively using Monte Carlo simulations. The results indicate that, for a range of values of the number of trials, the estimated weighting patterns are closer to their asymptotic values for the correlation method than for the MLR method. Moreover, for the MLR method, weight estimates for different stimulus components can exhibit strong correlations, making the analysis and interpretation of measured weighting patterns less straightforward than for the correlation method. These and other advantages of the correlation method, which include computational simplicity and a close relationship to other well-established psychophysical reverse-correlation methods, make it an attractive tool to uncover decision strategies in m-alternative experiments.

  15. 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.

    PubMed

    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.

  16. Lectures on pulsed NMR

    SciTech Connect

    Pines, A.

    1988-08-01

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

  17. Lectures on pulsed NMR

    SciTech Connect

    Pines, A.

    1986-09-01

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

  18. Trauma experience among homeless female veterans: correlates and impact on housing, clinical, and psychosocial outcomes.

    PubMed

    Tsai, Jack; Rosenheck, Robert A; Decker, Suzanne E; Desai, Rani A; Harpaz-Rotem, Ilan

    2012-12-01

    This study examined lifetime exposure to traumatic events as reported by 581 homeless female veterans enrolled in a Homeless Women Veterans Program across 11 sites to characterize the types of trauma they experienced; their correlation with baseline characteristics; and their association with housing, clinical outcomes, and psychosocial functioning over a 1-year treatment period. Almost all participants endorsed multiple types and episodes of traumatic events. Among the most common were having someone close experience a serious or life-threatening illness (82%) and rape (67%). Exploratory factor analysis revealed 6 potential trauma categories: being robbed, experiencing accident or disasters, illness or death of others, combat, sexual assault, and physical assault. At baseline, trauma from sexual assault was associated with more days homeless (β = .18, p < .001), trauma from accidents or disasters was associated with poorer physical health (β = -.23, p < .001), and trauma from being robbed was related to greater use of drugs (β = .22, p < .001). Trauma reported at baseline, however, was not predictive of 1-year outcomes, suggesting type and frequency of trauma does not negatively affect the housing gains homeless women veterans can achieve through homeless services.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Complete NMR analysis of oxytocin in phosphate buffer.

    PubMed

    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.

  1. NMR logging apparatus

    DOEpatents

    Walsh, David O; Turner, Peter

    2014-05-27

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

  2. Measurement and Quantification of Heterogeneity, Flow, and Mass Transfer in Porous Media Using NMR Low-Field Techiques

    NASA Astrophysics Data System (ADS)

    Paciok, E.; Olaru, A. M.; Haber, A.; van Landeghem, M.; Haber-Pohlmeier, S.; Sucre, O. E.; Perlo, J.; Casanova, F.; Blümich, B.; RWTH Aachen Mobile Low-Field NMR

    2011-12-01

    Nuclear magnetic resonance (NMR) is renowned for its unique potential to both reveal and correlate spectroscopic, relaxometric, spatial and dynamic properties in a large variety of organic and inorganic systems. NMR has no restrictions regarding sample opacity and is an entirely non-invasive method, which makes it the ideal tool for the investigation of porous media. However, for years NMR research of soils was limited by the use of high-field NMR devices, which necessitated elaborate NMR experiments and were not applicable to bulky samples or on-site field measurements. The evolution of low-field NMR devices during the past 20 years has brought forth portable, small-scale NMR systems with open and closed magnet arrangements specialized to specific NMR applications. In combination with recent advances in 2D-NMR Laplace methodology [1], low-field NMR has opened up the possibility to study real-life microporous systems ranging from granular media to natural soils and oil well boreholes. Thus, information becomes available, which before has not been accessible with high-field NMR. In this work, we present our recent progress in mobile low-field NMR probe design for field measurements of natural soils: a slim-line logging tool, which can be rammed into the soil of interest on-site. The performance of the device is demonstrated in measurements of moisture profiles of model soils [2] and field measurements of relaxometric properties and moisture profiles of natural soils [3]. Moreover, an improved concept of the slim-line logging tool is shown, with a higher excitation volume and a better signal-to-noise due to an improved coil design. Furthermore, we present our recent results in 2D exchange relaxometry and simulation. These include relaxation-relaxation experiments on natural soils with varying degree of moisture saturation, where we could draw a connection between the relaxometric properties of the soil to its pore size-related diffusivity and to its clay content

  3. Quantitative measurement of regional blood flow with gadolinium diethylenetriaminepentaacetate bolus track NMR imaging in cerebral infarcts in rats: validation with the iodo[14C]antipyrine technique.

    PubMed Central

    Wittlich, F; Kohno, K; Mies, G; Norris, D G; Hoehn-Berlage, M

    1995-01-01

    NMR bolus track measurements were correlated with autoradiographically determined regional cerebral blood flow (rCBF). The NMR method is based on bolus infusion of the contrast agent gadolinium diethylenetriaminepentaacetate and high-speed T*2-sensitive NMR imaging. The first pass of the contrast agent through the image plane causes a transient decrease of the signal intensity. This time course of the signal intensity is transformed into relative concentrations of the contrast agent in each pixel. The mean transit time and relative blood flow and volume are calculated from such indicator dilution curves. We investigated whether this NMR technique correctly expresses the relative rCBF. The relative blood flow data, calculated from NMR bolus track experiments, and the absolute values of iodo[14C]antipyrine autoradiography were compared. A linear relationship was observed, indicating the proportionality of the transient NMR signal change with CBF. Excellent interindividual reproducibility of calibration constants is observed (r = 0.963). For a given NMR protocol, bolus track measurements calibrated with autoradiography after the experiment allow determination of absolute values for rCBF and regional blood volume. Images Fig. 2 Fig. 3 PMID:7892189

  4. WaterLOGSY NMR experiments in conjunction with molecular-dynamics simulations identify immobilized water molecules that bridge peptide mimic MDWNMHAA to anticarbohydrate antibody SYA/J6.

    PubMed

    Szczepina, Monica G; Bleile, Dustin W; Müllegger, Johannes; Lewis, Andrew R; Pinto, B Mario

    2011-10-04

    X-ray crystallographic data of the carbohydrate mimic MDWNMHAA when bound to an anti-Shigella flexneri Y mAb SYA/J6 indicate the immobilization of water molecules, that is, the presence of "bound" waters, in the active site. Water Ligand Observed via Gradient Spectroscopy (WaterLOGSY) was used in conjunction with saturation transfer difference (STD)-NMR spectroscopy to probe the existence of immobilized water molecules in the complex of MDWNMHAA 1 bound to mAb SYA/J6. Molecular dynamics simulations using the ZymeCAD Molecular Dynamics platform were then used to specify the likely locations of these water molecules. Of note, those waters involved in providing complementarity between the peptide and mAb SYA/J6 remained throughout the course of the simulation. Together, the experimental and computational protocols have been used to identify the bound water molecules present in the antibody-peptide complex.

  5. Determination of 15N chemical shift anisotropy from a membrane-bound protein by NMR spectroscopy.

    PubMed

    Pandey, Manoj Kumar; Vivekanandan, Subramanian; Ahuja, Shivani; Pichumani, Kumar; Im, Sang-Choul; Waskell, Lucy; Ramamoorthy, Ayyalusamy

    2012-06-21

    Chemical shift anisotropy (CSA) tensors are essential in the structural and dynamic studies of proteins using NMR spectroscopy. Results from relaxation studies in biomolecular solution and solid-state NMR experiments on aligned samples are routinely interpreted using well-characterized CSA tensors determined from model compounds. Since CSA tensors, particularly the (15)N CSA, highly depend on a number of parameters including secondary structure, electrostatic interaction, and the amino acid sequence, there is a need for accurately determined CSA tensors from proteins. In this study, we report the backbone amide-(15)N CSA tensors for a 16.7-kDa membrane-bound and paramagnetic-heme containing protein, rabbit Cytochrome b(5) (cytb(5)), determined using the (15)N CSA/(15)N-(1)H dipolar transverse cross-correlation rates. The mean values of (15)N CSA determined for residues in helical, sheet, and turn regions are -187.9, -166.0, and -161.1 ppm, respectively, with an overall average value of -171.7 ppm. While the average CSA value determined from this study is in good agreement with previous solution NMR experiments on small globular proteins, the CSA value determined for residues in helical conformation is slightly larger, which may be attributed to the paramagnetic effect from Fe(III) of the heme unit in cytb(5). However, like in previous solution NMR studies, the CSA values reported in this study are larger than the values measured from solid-state NMR experiments. We believe that the CSA parameters reported in this study will be useful in determining the structure, dynamics, and orientation of proteins, including membrane proteins, using NMR spectroscopy.

  6. NMR-Assisted Molecular Docking Methodologies.

    PubMed

    Sturlese, Mattia; Bellanda, Massimo; Moro, Stefano

    2015-08-01

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

  7. NMR Methods to Study Dynamic Allostery

    PubMed Central

    Grutsch, Sarina; Brüschweiler, Sven; Tollinger, Martin

    2016-01-01

    Nuclear magnetic resonance (NMR) spectroscopy provides a unique toolbox of experimental probes for studying dynamic processes on a wide range of timescales, ranging from picoseconds to milliseconds and beyond. Along with NMR hardware developments, recent methodological advancements have enabled the characterization of allosteric proteins at unprecedented detail, revealing intriguing aspects of allosteric mechanisms and increasing the proportion of the conformational ensemble that can be observed by experiment. Here, we present an overview of NMR spectroscopic methods for characterizing equilibrium fluctuations in free and bound states of allosteric proteins that have been most influential in the field. By combining NMR experimental approaches with molecular simulations, atomistic-level descriptions of the mechanisms by which allosteric phenomena take place are now within reach. PMID:26964042

  8. 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

    NASA Astrophysics Data System (ADS)

    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.

  9. Application of ChemDraw NMR Tool: Correlation of Program-Generated (Super 13)C Chemical Shifts and pK[subscript a] Values of Para-Substituted Benzoic Acids

    ERIC Educational Resources Information Center

    Hongyi Wang

    2005-01-01

    A study uses the ChemDraw nuclear magnetic resonance spectroscopy (NMR) tool to process 15 para-substituted benzoic acids and generate (super 13)C NMR chemical shifts of C1 through C5. The data were plotted against their pK[subscript a] value and a fairly good linear fit was found for pK[subscript a] versus delta[subscript c1].

  10. LIMS Instrument Package (LIP) balloon experiment: Nimbus 7 satellite correlative temperature, ozone, water vapor, and nitric acid measurements

    NASA Technical Reports Server (NTRS)

    Lee, R. B., III; Gandrud, B. W.; Robbins, D. E.; Rossi, L. C.; Swann, N. R. W.

    1982-01-01

    The Limb Infrared Monitor of the Stratosphere (LIMS) LIP balloon experiment was used to obtain correlative temperature, ozone, water vapor, and nitric acid data at altitudes between 10 and 36 kilometers. The performance of the LIMS sensor flown on the Nimbus 7 Satellite was assessed. The LIP consists of the modified electrochemical concentration cell ozonesonde, the ultraviolet absorption photometric of ozone, the water vapor infrared radiometer sonde, the chemical absorption filter instrument for nitric acid vapor, and the infrared radiometer for nitric acid vapor. The limb instrument package (LIP), its correlative sensors, and the resulting data obtained from an engineering and four correlative flights are described.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Proton-Detected Solid-State NMR Spectroscopy of Bone with Ultrafast Magic Angle Spinning

    NASA Astrophysics Data System (ADS)

    Mroue, Kamal H.; Nishiyama, Yusuke; Kumar Pandey, Manoj; Gong, Bo; McNerny, Erin; Kohn, David H.; Morris, Michael D.; Ramamoorthy, Ayyalusamy

    2015-07-01

    While obtaining high-resolution structural details from bone is highly important to better understand its mechanical strength and the effects of aging and disease on bone ultrastructure, it has been a major challenge to do so with existing biophysical techniques. Though solid-state NMR spectroscopy has the potential to reveal the structural details of bone, it suffers from poor spectral resolution and sensitivity. Nonetheless, recent developments in magic angle spinning (MAS) NMR technology have made it possible to spin solid samples up to 110 kHz frequency. With such remarkable capabilities, 1H-detected NMR experiments that have traditionally been challenging on rigid solids can now be implemented. Here, we report the first application of multidimensional 1H-detected NMR measurements on bone under ultrafast MAS conditions to provide atomistic-level elucidation of the complex heterogeneous structure of bone. Our investigations demonstrate that two-dimensional 1H/1H chemical shift correlation spectra for bone are obtainable using fp-RFDR (finite-pulse radio-frequency-driven dipolar recoupling) pulse sequence under ultrafast MAS. Our results infer that water exhibits distinct 1H-1H dipolar coupling networks with the backbone and side-chain regions in collagen. These results show the promising potential of proton-detected ultrafast MAS NMR for monitoring structural and dynamic changes caused by mechanical loading and disease in bone.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    PubMed

    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.

  16. Effects of various types of molecular dynamics on 1D and 2D (2)H NMR studied by random walk simulations

    PubMed

    Vogel; Rossler

    2000-11-01

    By carrying out random walk simulations we systematically study the effects of various types of complex molecular dynamics on (2)H NMR experiments in solids. More precisely, we calculate one-dimensional (1D) (2)H NMR spectra and the results of two dimensional (2D) (2)H NMR experiments in time domain, taking into account isotropic as well as highly restricted motions which involve rotational jumps about different finite angles. Although the dynamical models are chosen to mimic the primary and secondary relaxation in supercooled liquids and glasses, we do not intend to describe experimental results quantitatively but rather to show general effects appearing for complex reorientations. We carefully investigate whether 2D (2)H NMR in time domain, which was originally designed to measure correlation times of ultraslow motions (tau >/= 1 ms), can be used to obtain shorter tau, too. It is demonstrated that an extension of the time window to tau >/= 10 &mgr;s is possible when dealing with exponential relaxation, but that it will fail if there is a distribution of correlation times G(lgtau). Vice versa, we show that 1D (2)H NMR spectra, usually recorded to look at dynamics with tau in the microsecond regime, are also applicable for studying ultraslow motions provided that the loss of correlation is achieved step by step. Therefore, it is useful to carry out 1D and 2D NMR experiments simultaneously in order to reveal the mechanism of complex molecular motions. In addition, we demonstrate that highly restricted dynamics can be clearly observed in 1D spectra and in 2D NMR in time domain if long solid-echo delays and large evolution times are applied, respectively. Finally, unexpected observations are described which appear in the latter experiment when considering very broad distributions G(lgtau). Because of these effects, time scale and geometry of a considered motion cannot be extracted from a straightforward analysis of experimental results. Copyright 2000 Academic Press.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    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.

  19. Computational interpretation of 23Na MQMAS NMR spectra: A comprehensive investigation of the Na environment in silicate glasses

    NASA Astrophysics Data System (ADS)

    Gambuzzi, Elisa; Charpentier, Thibault; Menziani, Maria Cristina; Pedone, Alfonso

    2014-09-01

    Molecular dynamics, density functional theory calculations and 23Na NMR experiments have been used to inspect the chemical and structural characteristics of the Na environment in soda-lime silicate (CSN) and aluminosilicate (CASN) glasses. The use of an improved 3QMAS pulse sequence has allowed a clear identification of different Na sites. Average coordination numbers have been extracted by fitting the 23Na 3QMAS spectra with the computed NMR parameters. The results show that the 23Na δiso values correlate with the average distances only when the different coordination numbers are explicitly taken into account.

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

    NASA Astrophysics Data System (ADS)

    Mills, Nancy S.

    1998-06-01

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

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

    ERIC Educational Resources Information Center

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

    PubMed Central

    2017-01-01

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

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

    PubMed

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

    2017-02-21

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

  4. Solid state NMR methods for coal science. Progress report, January 1-March 31, 1985. [(CH/sub 2/O)n; crotonic acid

    SciTech Connect

    Zilm, K.W.

    1985-03-01

    This report covers the progress made on the title project during the last quarter. Areas that we have concentrated on in the last three months include carbon-13/proton chemical shift correlation in model systems, some crucial decoupling experiments, and setting up our high field /sup 2/D NMR capability. 6 figs.

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

    ERIC Educational Resources Information Center

    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,…

  6. SAGE ground truth plan: Correlative measurements for the Stratospheric Aerosol and Gas Experiment (SAGE) on the AEM-B satellite

    NASA Technical Reports Server (NTRS)

    Russell, P. B. (Editor); Cunnold, D. M.; Grams, G. W.; Laver, J.; Mccormick, M. P.; Mcmaster, L. R.; Murcray, D. G.; Pepin, T. J.; Perry, T. W.; Planet, W. G.

    1979-01-01

    The ground truth plan is outlined for correlative measurements to validate the Stratospheric Aerosol and Gas Experiment (SAGE) sensor data. SAGE will fly aboard the Applications Explorer Mission-B satellite scheduled for launch in early 1979 and measure stratospheric vertical profiles of aerosol, ozone, nitrogen dioxide, and molecular extinction between 79 N and 79 S. latitude. The plan gives details of the location and times for the simultaneous satellite/correlative measurements for the nominal launch time, the rationale and choice of the correlative sensors, their characteristics and expected accuracies, and the conversion of their data to extinction profiles. In addition, an overview of the SAGE expected instrument performance and data inversion results are presented. Various atmospheric models representative of stratospheric aerosols and ozone are used in the SAGE and correlative sensor analyses.

  7. Assessment of Biasi and Columbia University CHF correlations with GE 3x3 rod bundle experiment. [PWR; BWR

    SciTech Connect

    Chen, B.C.J.; Chien, T.H.; Sha, W.T.; Kim, J.H.

    1984-01-01

    The critical heat flux (CHF), at which a sudden degradation of heat transfer occurs without corresponding decrease in heat generation, is one of the limiting parameters for safe operation of nuclear reactors. Reactor operation beyond the CHF causes a rapid rise in fuel cladding temperature and thus should be avoided to maintain the fuel element integrity. Reactor power limits are therefore set so that a prescribed safety margin below the CHF is maintained. Two CHF correlations are evaluated for reactor core thermal hydraulic analysis: the Biasi correlation and the Columbia University correlation. The BODYFIT-2PE computer code is used for this assessment. The CHF predicted by the BODYFIT-2PE using the two correlations is compared with GE 3x3 rod bundle CHF experiment.

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

    ERIC Educational Resources Information Center

    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.

  9. Spatial correlations and probability density function of the phase difference in a developed speckle-field: numerical and natural experiments

    SciTech Connect

    Mysina, N Yu; Maksimova, L A; Ryabukho, V P; Gorbatenko, B B

    2015-10-31

    Investigated are statistical properties of the phase difference of oscillations in speckle-fields at two points in the far-field diffraction region, with different shapes of the scatterer aperture. Statistical and spatial nonuniformity of the probability density function of the field phase difference is established. Numerical experiments show that, for the speckle-fields with an oscillating alternating-sign transverse correlation function, a significant nonuniformity of the probability density function of the phase difference in the correlation region of the field complex amplitude, with the most probable values 0 and p, is observed. A natural statistical interference experiment using Young diagrams has confirmed the results of numerical experiments. (laser applications and other topics in quantum electronics)

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

    PubMed Central

    Zhalnina, Kateryna; de Quadros, Patricia D.; Gano, Kelsey A.; Davis-Richardson, Austin; Fagen, Jennie R.; Brown, Christopher T.; Giongo, Adriana; Drew, Jennifer C.; Sayavedra-Soto, Luis A.; Arp, Dan J.; Camargo, Flavio A. O.; Daroub, Samira H.; Clark, Ian M.; McGrath, Steve P.; Hirsch, Penny R.; Triplett, Eric W.

    2013-01-01

    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. PMID:23641242

  11. Correlation of satellite lightning observations with ground-based lightning experiments in Florida, Texas and Oklahoma

    NASA Technical Reports Server (NTRS)

    Edgar, B. C.; Turman, B. N.

    1982-01-01

    Satellite observations of lightning were correlated with ground-based measurements of lightning from data bases obtained at three separate sites. The percentage of ground-based observations of lightning that would be seen by an orbiting satellite was determined.

  12. COMPUTER ’EXPERIMENTS’ ON CLASSICAL FLUIDS. II. EQUILIBRIUM CORRELATION FUNCTIONS,

    DTIC Science & Technology

    Lennard - Jones potential. The behaviour of the correlation function at large distance, and that of its Fourier transform at large wave number are discussed in detail and shown to be related to the existence of a strong repulsion in the potential. A simple hard sphere model is shown to reproduce very well the Fourier transform of those correlations functions at high density, the only parameter of the model being the diameter a of the hard spheres.

  13. Analysis of DNA Sequences by An Optical Time-Integrating Correlator: Proof-Of-Concept Experiments.

    DTIC Science & Technology

    1992-05-01

    correlator. Included are experimental results for the two types of analysis specified by the processing strategy . Details of the design and construction of...fondements de la vie. Des techniques de correlation utilisant des ordinateurs numeriques sont presentement utilisees pour effectuer cette analyse mais cela...resultats experimentaux des deux types d’analyse specifies par la strategie de traitement sont presentes. La conception et la construction de generateurs des

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

    PubMed

    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.

  15. Complete (1) H NMR assignment of cedranolides.

    PubMed

    Perez-Hernandez, Nury; Gordillo-Roman, Barbara; Arrieta-Baez, Daniel; Cerda-Garcia-Rojas, Carlos M; Joseph-Nathan, Pedro

    2017-03-01

    Complete and unambiguous (1) H NMR chemical shift assignment of α-cedrene (2) and cedrol (9), as well as for α-pipitzol (1), isocedrol (10), and the six related compounds 3-8 has been established by iterative full spin analysis using the PERCH NMR software (PERCH Solutions Ltd., Kuopio, Finland). The total sets of coupling constants are described and correlated with the conformational equilibria of the five-membered ring of 1-10, which were calculated using the complete basis set method. Copyright © 2015 John Wiley & Sons, Ltd.

  16. What’s in a drop? Correlating observations and outcomes to guide macromolecular crystallization experiments

    PubMed Central

    Luft, Joseph R.; Wolfley, Jennifer R.; Snell, Edward H.

    2011-01-01

    Observations of crystallization experiments are classified as specific outcomes and integrated through a phase diagram to visualize solubility and thereby direct subsequent experiments. Specific examples are taken from our high-throughput crystallization laboratory which provided a broad scope of data from 20 million crystallization experiments on 12,500 different biological macromolecules. The methods and rationale are broadly and generally applicable in any crystallization laboratory. Through a combination of incomplete factorial sampling of crystallization cocktails, standard outcome classifications, visualization of outcomes as they relate chemically and application of a simple phase diagram approach we demonstrate how to logically design subsequent crystallization experiments. PMID:21643490

  17. Microscale simulations of NMR relaxation in porous media

    NASA Astrophysics Data System (ADS)

    Mohnke, Oliver; Klitzsch, Norbert

    2010-05-01

    ). In this respect substantial coupling effects in typical porous rocks can be observed at pore sizes about <1 μm, e.g. encountered in tight gas reservoir formations. Internal magnetic field gradients in rocks arise due to susceptibility contrasts in pore fluid and rock matrix and depend on the magnetic field strength (Larmor frequency). To model the increased relaxation rate observed in CPMG measurements due to diffusive motion in a magnetic (internal) gradient field the simulations are coupled with calculations of spatial distribution of field gradients within the simulated fluid-matrix system according to Ampere's law. Contrary to common assumptions of a constant ratio between T1 and T2 in petrophysical NMR the CPMG simulations in the presence of internal gradients show a significant increase of T1/T2 ratios with decreasing pore sizes. This implies a shift of derived signal contributions to smaller pore sizes, e.g. <1 μm, from T2 NMR experiments, and thus an underestimation of derived permeabilities. μm These simulations will also be compiled for multi-phase systems, e.g. water-air-oil, to study basic correlations between NMR and hydrological parameters of partially saturated rocks. This study was conducted within the framework of the Transregional Collaborative Research Centre 32, funded by the German Research Foundation (DFG).

  18. Microscale simulations of NMR relaxation in porous media

    NASA Astrophysics Data System (ADS)

    Mohnke, O.; Klitzsch, N.; Clauser, C.

    2009-12-01

    coupling effects in typical porous rocks can be observed at pore sizes about <1 μm, e.g. encountered in tight gas reservoir formations. Internal magnetic field gradients in rocks arise due to susceptibility contrasts in pore fluid and rock matrix and depend on the magnetic field strength (Larmor frequency). To model the increased relaxation rate observed in CPMG measurements due to diffusive motion in a magnetic (internal) gradient field the simulations are coupled with calculations of spatial distribution of field gradients within the simulated fluid-matrix system according to Ampere's law. Contrary to common assumptions of a constant ratio between T1 and T2 in petrophysical NMR the CPMG simulations in the presence of internal gradients show a significant increase of T1/T2 ratios with decreasing pore sizes. This implies a shift of derived signal contributions to smaller pore sizes, e.g. <1 μm, from T2 NMR experiments, and thus an underestimation of derived permeabilities. μm These simulations will also be compiled for multi-phase systems, e.g. water-air-oil, to study basic correlations between NMR and hydrological parameters of partially saturated rocks. This study was conducted within the framework of the Transregional Collaborative Research Centre 32, funded by the German Research Foundation (DFG).

  19. NMR characterization of pituitary tumors

    SciTech Connect

    Osbakken, M.; Gonzales, J.; Page, R.

    1984-01-01

    Twelve patients (5 male, 7 female, mean age 37.9 +- 20) with pituitary tumors were extensively evaluated with NMR imaging using a 1.5K gauss resistive magnet. Saturation recovery (SR), inversion recovery (IR) and spin echo (SE) pulse sequences were used for qualitative characterization of the lesions. T/sub 1/ calculations were also performed for brain and pituitary. Tumor histology and endocrine status were correlated with NMR data. All tumors were large with suprasellar extension (6 with prolactin secretion, 6 without). Pituitary T/sub 1/'s ranged from .2 to .64, the mean T/sub 1/ being longer than that of brain (Brain = .4 +- .04; Pit = .48 +- .14). 3 patients with histological evidence of homogeneous adenomas had long T/sub 1/'s (0.58 +- .05). 3 patients with evidence of recent or old hemorhage into the pituitary had much shorter T/sub 1/'s (0.29 +- .12). There was no relationship between prolactin secretion and T/sub 1/. Qualitative T/sub 1/ and T/sub 2/ information can be obtained by using a combination of SR, IR, and SE images. Using this method in the patients, homogeneous adenomas had similar T/sub 1/'s and longer T/sub 2/'s compared to the brain, while patients with bleeds had shorter T/sub 1/'s and T/sub 2/'s. Image T/sub 1/ characteristics correlated well with the calculated T/sub 1/ values. The range of T/sub 1/ (and potentially T/sub 2/) values which occur in apparently similar lesions are most likely due to anatomical and pathophysiological variations in these lesions. It may be ultimately possible to separate different types of pathological processes based on NMR image T/sub 1/ and T/sub 2/ characteristics after careful comparative studies of NMR and histological data are completed. The combination of calculated T/sub 1/ and T/sub 2/ with image T/sub 1/ and T/sub 2/ information may also be useful in further characterization of lesions.

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

    PubMed

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

    2009-03-02

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

  1. Microgram-scale protein structure determination by NMR.

    PubMed

    Aramini, James M; Rossi, Paolo; Anklin, Clemens; Xiao, Rong; Montelione, Gaetano T

    2007-06-01

    Using conventional triple-resonance nuclear magnetic resonance (NMR) experiments with a 1 mm triple-resonance microcoil NMR probe, we determined near complete resonance assignments and three-dimensional (3D) structure of the 68-residue Methanosarcina mazei TRAM protein using only 72 mug (6 microl, 1.4 mM) of protein. This first example of a complete solution NMR structure determined using microgram quantities of protein demonstrates the utility of microcoil-probe NMR technologies for protein samples that can be produced in only limited quantities.

  2. An optical NMR spectrometer for Larmor-beat detection and high-resolution POWER NMR

    NASA Astrophysics Data System (ADS)

    Kempf, J. G.; Marohn, J. A.; Carson, P. J.; Shykind, D. A.; Hwang, J. Y.; Miller, M. A.; Weitekamp, D. P.

    2008-06-01

    Optical nuclear magnetic resonance (ONMR) is a powerful probe of electronic properties in III-V semiconductors. Larmor-beat detection (LBD) is a sensitivity optimized, time-domain NMR version of optical detection based on the Hanle effect. Combining LBD ONMR with the line-narrowing method of POWER (perturbations observed with enhanced resolution) NMR further enables atomically detailed views of local electronic features in III-Vs. POWER NMR spectra display the distribution of resonance shifts or line splittings introduced by a perturbation, such as optical excitation or application of an electric field, that is synchronized with a NMR multiple-pulse time-suspension sequence. Meanwhile, ONMR provides the requisite sensitivity and spatial selectivity to isolate local signals within macroscopic samples. Optical NMR, LBD, and the POWER method each introduce unique demands on instrumentation. Here, we detail the design and implementation of our system, including cryogenic, optical, and radio-frequency components. The result is a flexible, low-cost system with important applications in semiconductor electronics and spin physics. We also demonstrate the performance of our systems with high-resolution ONMR spectra of an epitaxial AlGaAs /GaAs heterojunction. NMR linewidths down to 4.1Hz full width at half maximum were obtained, a 103-fold resolution enhancement relative any previous optically detected NMR experiment.

  3. The range of dynamic recrystallization of quartz - An updated correlation between nature and experiment

    NASA Astrophysics Data System (ADS)

    Stipp, Michael

    2014-05-01

    Several microstructural correlations between natural and experimental conditions for dynamic recrystallization of quartz have been proposed (e.g., Hirth et al. 2001; Stipp et al. 2002), but an attempt to unify the different results and data sets is missing. Based on additional experiments and a statistical analysis of microstructural data (e.g., Stipp et al. 2006, 2010) four characteristic microstructural zones with corresponding recrystallized grain size (D) ranges can be identified. (I) D < 3 µm: Experimental dislocation creep regime 1 of Hirth and Tullis (1992). Microstructures are characterized by porphyroclasts with serrations, bulges and very small recrystallized grains along the grain boundaries. Electron backscatter diffraction data indicate that both local grain boundary migration and subgrain rotation contribute to recrystallization, and that grain boundary sliding may operate at high strain (Stipp and Kunze, 2008). Comparable microstructures have not been observed in natural shear zones; their formation is not possible at greenschist facies conditions, because the required differential stresses would be larger than the confining pressure and so in conflict with the Goetze criterion (Kohlstedt et al. 1995). (II) D ˜3-35 µm: Experimental dislocation creep regimes 2 and 3 (Hirth and Tullis 1992), corresponding to the natural BLG zone of Stipp et al. (2002). Microstructures are again characterized by porphyroclasts with grain boundary bulges and small recrystallized grains. Compared to zone I, less strain is required to produce a considerable amount of recrystallized grains, forming "core-mantle microstuctures". (III) D ˜35-120 µm: Upper experimental dislocation creep regime 3, and natural SGR zone (Stipp et al. 2006, 2010). Microstructures are characterized by porphyroclastic ribbon grains and recrystallized grains which are about the same size or slightly larger than optical subgrains. Subgrain formation and dynamic recrystallization are initiated at

  4. Being Different: Correlates of the Experience of Teasing and Bullying at Age 11.

    ERIC Educational Resources Information Center

    Sweeting, Helen; West, Patrick

    2001-01-01

    Collected self-report data on the experience of being teased and bullied from 11-year-old children, also gathering ratings of the children from their parents, teachers, and nurses. Teasing/bullying experiences did not differ by race, physical maturity, or height, but were more likely among children who were less physically attractive, overweight,…

  5. Prevalence and correlates of psychotic experiences amongst children of depressed parents.

    PubMed

    Bevan Jones, Rhys; Mars, Becky; Collishaw, Stephan; Potter, Robert; Thapar, Ajay; Craddock, Nick; Thapar, Anita; Zammit, Stanley

    2016-09-30

    Psychotic experiences in young people are substantially more common than psychotic disorders, and are associated with distress and functional impairment. Family history of depression as well as of schizophrenia increases risk for psychotic experiences, but the prevalence of such experiences and their clinical relevance in offspring of depressed parents is unknown. Our objectives were to explore i) the prevalence of psychotic experiences amongst offspring of parents with recurrent unipolar depression and ii) the relationship between psychotic experiences and other psychopathology. Data were drawn from the 'Early Prediction of Adolescent Depression' longitudinal study of high-risk offspring (aged 9-17 years at baseline) of 337 parents with recurrent depression. Three assessments were conducted over four years. Psychopathology was assessed using the Child and Adolescent Psychiatric Assessment. Seventy-eight percent of families (n=262) had complete data on psychotic experiences at each of the three time points. During the study, 8.4% (n=22; 95% CI 5.0%, 11.8%) of offspring reported psychotic experiences on at least one occasion, and these were associated with psychiatric disorder, specifically mood and disruptive disorders, and suicidal thoughts/behaviour. Psychotic experiences amongst offspring of depressed parents index a range of psychopathology. Further research is needed to examine their clinical significance and long-term consequences.

  6. Dating, Sex, and Substance Use as Correlates of Adolescents' Subjective Experience of Age

    ERIC Educational Resources Information Center

    Arbeau, Kelly J.; Galambos, Nancy L.; Jansson, S. Mikael

    2007-01-01

    This study examined in a random community-based sample of 664 12-19-year-olds, the relation of subjective experience of age (SEA) with chronological age, dating experience, sexual activity, and substance use. The results revealed a positive linear relation between SEA and chronological age: individuals who were chronologically older felt…

  7. Bringing NMR and IR Spectroscopy to High Schools

    ERIC Educational Resources Information Center

    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…

  8. Heteronuclear Multidimensional Protein NMR in a Teaching Laboratory

    ERIC Educational Resources Information Center

    Wright, Nathan T.

    2016-01-01

    Heteronuclear multidimensional NMR techniques are commonly used to study protein structure, function, and dynamics, yet they are rarely taught at the undergraduate level. Here, we describe a senior undergraduate laboratory where students collect, process, and analyze heteronuclear multidimensional NMR experiments using an unstudied Ig domain (Ig2…

  9. NMR imaging microscopy

    SciTech Connect

    Not Available

    1986-10-01

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

  10. Review of NMR characterization of pyrolysis oils

    SciTech Connect

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

    2016-08-24

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

  11. Review of NMR characterization of pyrolysis oils

    DOE PAGES

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; ...

    2016-08-24

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

  12. Ground-Laboratory to In-Space Atomic Oxygen Correlation for the Polymer Erosion and Contamination Experiment (PEACE) Polymers

    NASA Technical Reports Server (NTRS)

    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.

  13. Correlates and consequences of parent-teen incongruence in reports of teens' sexual experience.

    PubMed

    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.

  14. Spectral evolution of gamma-ray bursts detected by the SIGNE experiment. 1: Correlation between intensity and spectral hardness

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Astrophysics Data System (ADS)

    Tarasek, Matthew R.

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

  16. NMR studies of oriented molecules

    SciTech Connect

    Sinton, S.W.

    1981-11-01

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

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

    PubMed Central

    Heller, Davide Martin; Giorgetti, Alejandro

    2010-01-01

    Nuclear magnetic resonance (NMR) spectroscopy together with X-ray crystallography, are the main techniques used for the determination of high-resolution 3D structures of biological molecules. The output of an NMR experiment includes a set of lower and upper limits for the distances (constraints) between pairs of atoms. If the number of constraints is high enough, there will be a finite number of possible conformations (models) of the macromolecule satisfying the data. Thus, the more constraints are measured, the better defined these structures will be. The availability of a user-friendly tool able to help in the analysis and interpretation of the number of experimental constraints per residue, is thus of valuable importance when assessing the levels of structure definition of NMR solved biological macromolecules, in particular, when high-quality structures are needed in techniques such as, computational biology approaches, site-directed mutagenesis experiments and/or drug design. Here, we present a free publicly available web-server, i.e. NMR Constraints Analyser, which is aimed at providing an automatic graphical analysis of the NMR experimental constraints atom by atom. The NMR Constraints Analyser server is available from the web-page http://molsim.sci.univr.it/constraint PMID:20513646

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

    PubMed

    Heller, Davide Martin; Giorgetti, Alejandro

    2010-07-01

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

  19. Contact replacement for NMR resonance assignment

    PubMed Central

    Xiong, Fei; Pandurangan, Gopal; Bailey-Kellogg, Chris

    2008-01-01

    Motivation: Complementing its traditional role in structural studies of proteins, nuclear magnetic resonance (NMR) spectroscopy is playing an increasingly important role in functional studies. NMR dynamics experiments characterize motions involved in target recognition, ligand binding, etc., while NMR chemical shift perturbation experiments identify and localize protein–protein and protein–ligand interactions. The key bottleneck in these studies is to determine the backbone resonance assignment, which allows spectral peaks to be mapped to specific atoms. This article develops a novel approach to address that bottleneck, exploiting an available X-ray structure or homology model to assign the entire backbone from a set of relatively fast and cheap NMR experiments. Results: We formulate contact replacement for resonance assignment as the problem of computing correspondences between a contact graph representing the structure and an NMR graph representing the data; the NMR graph is a significantly corrupted, ambiguous version of the contact graph. We first show that by combining connectivity and amino acid type information, and exploiting the random structure of the noise, one can provably determine unique correspondences in polynomial time with high probability, even in the presence of significant noise (a constant number of noisy edges per vertex). We then detail an efficient randomized algorithm and show that, over a variety of experimental and synthetic datasets, it is robust to typical levels of structural variation (1–2 AA), noise (250–600%) and missings (10–40%). Our algorithm achieves very good overall assignment accuracy, above 80% in α-helices, 70% in β-sheets and 60% in loop regions. Availability: Our contact replacement algorithm is implemented in platform-independent Python code. The software can be freely obtained for academic use by request from the authors. Contact: gopal@cs.purdue.edu; cbk@cs.dartmouth.edu PMID:18586716

  20. Optimizing Adiabaticity in NMR

    NASA Astrophysics Data System (ADS)

    Vandermause, Jonathan; Ramanathan, Chandrasekhar

    We demonstrate the utility of Berry's superadiabatic formalism for numerically finding control sequences that implement quasi-adiabatic unitary transformations. Using an iterative interaction picture, we design a shortcut to adiabaticity that reduces the time required to perform an adiabatic inversion pulse in liquid state NMR. We also show that it is possible to extend our scheme to two or more qubits to find adiabatic quantum transformations that are allowed by the control algebra, and demonstrate a two-qubit entangling operation in liquid state NMR. We examine the pulse lengths at which the fidelity of these adiabatic transitions break down and compare with the quantum speed limit.

  1. Protein Motions and Folding Investigated by NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Palmer, Arthur

    2002-03-01

    NMR spin relaxation spectroscopy is a powerful experimental approach for globally characterizing conformational dynamics of proteins in solution. Laboratory frame relaxation measurements are sensitive to overall rotational diffusion and internal motions on picosecond-nanosecond time scales, while rotating frame relaxation measurements are sensitive to chemical exchange processes on microsecond-millisecond time scales. The former approach is illustrated by ^15N laboratory-frame relaxation experiments as a function of temperature for the helical subdomain HP36 of the F-actin-binding headpiece domain of chicken villin. The data are analyzed using the model-free formalism to characterize order parameters and effective correlation times for intramolecular motions of individual ^15N sites. The latter approach is illustrated by ^13C Carr-Purcell-Meiboom-Gill relaxation measurements for the de novo designed α_2D protein and by ^15N rotating-frame relaxation measurements for the peripheral subunit-binding domain (PSBD) from the dihydrolopoamide acetyltransferase component of the pyruvate dehydrogenase multienzyme complex from Bacillus stearothermophilus. These experiments are used to determine the folding and unfolding kinetic rate constants for the two proteins. The results for HP36, α_2D, and PSBD illustrate the capability of current NMR methods for characterizing dynamic processes on multiple time scales in proteins.

  2. NMR evidence for the metallic nature of highly conducting polyaniline

    NASA Astrophysics Data System (ADS)

    Kolbert, A. C.; Caldarelli, S.; Thier, K. F.; Sariciftci, N. S.; Cao, Y.; Heeger, A. J.

    1995-01-01

    Polyaniline doped with camphor sulphonic acid (PANI-CSA) has been shown to yield a material that, after casting from solution in meta-cresol, exhibits a temperature-independent magnetic susceptibility [Y. Cao, P. Smith, and A. J. Heeger, Synth. Met. 48, 91 (1992); N. S. Sariciftici, A. J. Heeger, and Y. Cao, Phys. Rev. B 49, 5988 (1994)]. We report recent 13C NMR experiments on uniformly 13enriched PANI-CSA in which the 13C spin-lattice relaxation rates are shown to obey a modified Korringa relation for relaxation via the hyperfine coupling to conduction electrons. This observation of Korringa relaxation in polyaniline provides strong evidence for a metallic state in this material. An estimate is made of the Korringa enhancement factor that provides a measure of the degree of electron-electron correlations present. Two-dimensional spin-exchange experiments are also reported, which show that the 13C NMR signal results from a heterogeneity in the sample over at least a 30-Å distance scale. These results are discussed in terms of the spatial extent of the doping-induced defect.

  3. The phototoxicity of polycyclic aromatic hydrocarbons: a theoretical study of excited states and correlation to experiment.

    PubMed

    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.

  4. Clinico-radiological correlation of nutcracker syndrome: a single centre experience.

    PubMed

    Taktak, Aysel; Hakan Demirkan, Tulin; Acar, Banu; Gu R, Gökçe; Köksoy, Adem; Uncu, Nermin; Çaycı, Fatma Ş; Çakar, Nilgu N

    2017-04-01

    The term nutcracker syndrome (NS) refers to the compression of left renal vein between the aorta and the superior mesenteric artery (SMA) causing renal venous hypertension. The symptoms vary from asymptomatic hematuria to severe pelvic congestion. The purpose of this study is to evaluate the clinical characteristics of patients with NS and the correlation between clinical and laboratory findings with Doppler sonographic measurements. Sixty-three patients were evaluated (19 boys and 44 girls) since January 2004 to January 2014. The mean age of the patients was 12.21 ± 3.21 years (range 7-17). Hematuria and proteinuria disappeared during the follow up of 9/63 patients. These nine patients showed statistically significant difference in upright SMA angles (p= 0.035). Doppler sonographic evaluation is a non-invasive method for diagnosis NS. Upright SMA angle measurement is more efficient than supine SMA angle measurement on clinicoradiological correlation.

  5. Chromatographic Separation and NMR An Integrated Approach in Pharmaceutical Development.

    PubMed

    Gonnella, Nina C

    2012-01-01

    Over the past 10 years, major improvements in the performance of LC-NMR have been realized. The addition of postcolumn SPE, advances in probe technology including cryogenic probes and microcoil probes, improved solvent suppression pulse sequences, and shielded magnets with better homogeneity have all contributed to rapid advancements in this technology. Application of LC-NMR to problems in pharmaceutical development has had a major impact on structure elucidation studies. LC-NMR has been successfully applied to determine the structures of degradation products, impurities, mixtures of compounds, and metabolites. Use of stop flow techniques with LC-NMR experiments has been a critical means of identifying unstable compounds and studying conformational kinetics. The integration of SPE as an intermediate step between the LC unit and the NMR spectrometer has vastly improved the power of the hyphenated technique in trace analysis applications. Online postcolumn enrichment of chromatographic peaks by SPE dramatically reduces the NMR acquisition times by allowing repeated injections to be trapped onto the same cartridge or different cartridges. Because protonated solvents can be easily removed with a drying procedure, solvents and buffers may be freely chosen for maximizing chromatographic separation without compromising NMR spectral quality. The compound of interest may then be eluted from an SPE cartridge using deuterated organic solvent, which helps to reduce dynamic range issues. When combined with cryogenically cooled microcapillary probes, the sensitivity of the NMR signal increases about 10-fold over conventional room temperature probes, enabling full structure characterization at the microgram level. Heteronuclear experiments with concentrations previously only possible in a limited number of cases have now become standard experiments. The availability of HSQC and HMBC experiments and microcoil/cryogenic technology opens the possibility of using LC-(SPE) NMR for the

  6. Simulation and experiment research of face recognition with modified multi-method morphological correlation algorithm

    NASA Astrophysics Data System (ADS)

    Yang, Yu; Xuping, Zhang

    2007-03-01

    Morphological definition of similarity degree of gray-scale image and general definition of morphological correlation (GMC) are proposed. Hardware and software design for a compact joint transform correlator are presented in order to implement GMC. Two kinds of modified general morphological correlation algorithm are proposed. The gray-scale image is decomposed into a set of binary image slices in certain decomposition method. In the first algorithm, the edge of each binary joint image slice is detected, width adjustability of which is investigated, and the joint power spectrum of the edge is summed. In the second algorithm, the joint power spectrum of each pair is binarized or thinned and then summed in one situation, and the summation of the joint power spectrums of these pairs is binarized or thinned in the other situation. Computer-simulation results and real face image recognition results indicate that the modified algorithm can improve the discrimination capabilities with respect to the gray-scale face images of high similarity.

  7. Decipher correlation patterns post prostatectomy: initial experience from 2 342 prospective patients

    PubMed Central

    Den, R B; Santiago-Jimenez, M; Alter, J; Schliekelman, M; Wagner, J R; Renzulli II, J F; Lee, D I; Brito, C G; Monahan, K; Gburek, B; Kella, N; Vallabhan, G; Abdollah, F; Trabulsi, E J; Lallas, C D; Gomella, L G; Woodlief, T L; Haddad, Z; Lam, L L C; Deheshi, S; Wang, Q; Choeurng, V; du Plessis, M; Jordan, J; Parks, B; Shin, H; Buerki, C; Yousefi, K; Davicioni, E; Patel, V R; Shah, N L

    2016-01-01

    Background: Currently, there are multiple commercially available RNA-based biomarkers that are Medicare approved and suggested for use by the National Comprehensive Cancer Network guidelines. There is uncertainty as to which patients benefit from genomic testing and for whom these tests should be ordered. Here, we examined the correlation patterns of Decipher assay to understand the relationship between the Decipher and patient tumor characteristics. Methods: De-identified Decipher test results (including Decipher risk scores and clinicopathologic data) from 2 342 consecutive radical prostatectomy (RP) patients tested between January and September 2015 were analyzed. For clinical testing, tumor specimen from the highest Gleason grade was sampled using a 1.5 mm tissue punch. Decipher scores were calculated based on a previously locked model. Correlations between Decipher score and clinicopathologic variables were computed using Spearman's rank correlation. Mixed-effect linear models were used to study the association of practice type and Decipher score. The significance level was 0.05 for all tests. Results: Decipher score had a positive correlation with pathologic Gleason score (PGS; r=0.37, 95% confidence interval (CI) 0.34−0.41), pathologic T-stage (r=0.31, 95% CI 0.28−0.35), CAPRA-S (r=0.32, 95% CI 0.28−0.37) and patient age (r=0.09, 95% CI 0.05-0.13). Decipher reclassified 52%, 76% and 40% of patients in CAPRA-S low-, intermediate- and high-risk groups, respectively. We detected a 28% incidence of high-risk disease through the Decipher score in pT2 patients and 7% low risk in pT3b/pT4, PGS 8−10 patients. There was no significant difference in the Decipher score between patients from community centers and those from academic centers (P=0.82). Conclusions: Although Decipher correlated with baseline tumor characteristics for over 2 000 patients, there was significant reclassification of tumor aggressiveness as compared to clinical parameters alone

  8. Determination of Unknown Concentrations of Sodium Acetate Using the Method of Standard Addition and Proton NMR: An Experiment for the Undergraduate Analytical Chemistry Laboratory

    ERIC Educational Resources Information Center

    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…

  9. Determination of the Rotational Barrier for Kinetically Stable Conformational Isomers via NMR and 2D TLC: An Introductory Organic Chemistry Experiment

    ERIC Educational Resources Information Center

    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).…

  10. Correlated two-particle diffusion in dense colloidal suspensions at early times: Theory and comparison to experiment.

    PubMed

    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.

  11. Correlated two-particle diffusion in dense colloidal suspensions at early times: Theory and comparison to experiment

    NASA Astrophysics Data System (ADS)

    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.

  12. Women Exiting Street-Based Sex Work: Correlations between Ethno-Racial Identity, Number of Children, and Violent Experiences.

    PubMed

    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.

  13. Structure of an anti-HIV-1 hammerhead ribozyme complex with a 17-mer DNA substrate analog of HIV-1 gag RNA and a mechanism for the cleavage reaction: 750 MHz NMR and computer experiments

    NASA Technical Reports Server (NTRS)

    Ojha, R. P.; Dhingra, M. M.; Sarma, M. H.; Myer, Y. P.; Setlik, R. F.; Shibata, M.; Kazim, A. L.; Ornstein, R. L.; Rein, R.; Turner, C. J.; Sarma, R. H.

    1997-01-01

    The structure of an anti-HIV-1 ribozyme-DNA abortive substrate complex was investigated by 750 MHz NMR and computer modeling experiments. The ribozyme was a chimeric molecule with 30 residues-18 DNA nucleotides, and 12 RNA residues in the conserved core. The DNA substrate analog had 17 residues. The chimeric ribozyme and the DNA substrate formed a shortened ribozyme-abortive substrate complex of 47 nucleotides with two DNA stems (stems I and III) and a loop consisting of the conserved core residues. Circular dichroism spectra showed that the DNA stems assume A-family conformation at the NMR concentration and a temperature of 15 degrees C, contrary to the conventional wisdom that DNA duplexes in aqueous solution populate entirely in the B-form. It is proposed that the A-family RNA residues at the core expand the A-family initiated at the core into the DNA stems because of the large free energy requirement for the formation of A/B junctions. Assignments of the base H8/H6 protons and H1' of the 47 residues were made by a NOESY walk. In addition to the methyl groups of all T's, the imino resonances of stems I and III and AH2's were assigned from appropriate NOESY walks. The extracted NMR data along with available crystallographic data, were used to derive a structural model of the complex. Stems I and III of the final model displayed a remarkable similarity to the A form of DNA; in stem III, a GC base pair was found to be moving into the floor of the minor groove defined by flanking AT pairs; data suggest the formation of a buckled rhombic structure with the adjacent pair; in addition, the base pair at the interface of stem III and the loop region displayed deformed geometry. The loop with the catalytic core, and the immediate region of the stems displayed conformational multiplicity within the NMR time scale. A catalytic mechanism for ribozyme action based on the derived structure, and consistent with biochemical data in the literature, is proposed. The complex

  14. Learning Style and Other Correlates of Performance on a Scanning Experiment.

    ERIC Educational Resources Information Center

    Maxwell, Martha J.

    The relationship between learning style (impulsivity-constriction and stability-anxiety), reading scores, and scanning performance was investigated. Twenty high school students enrolled in a precollege reading and study skills program participated in an 80-trial (10-session) scanning experiment. The task involved searching for a target sentence…

  15. Correlation, Necessity, and Sufficiency: Common Errors in the Scientific Reasoning of Undergraduate Students for Interpreting Experiments

    ERIC Educational Resources Information Center

    Coleman, Aaron B.; Lam, Diane P.; Soowal, Lara N.

    2015-01-01

    Gaining an understanding of how science works is central to an undergraduate education in biology and biochemistry. The reasoning required to design or interpret experiments that ask specific questions does not come naturally, and is an essential part of the science process skills that must be learned for an understanding of how scientists conduct…

  16. Factor Structure and Correlates of the Dissociative Experiences Scale in a Large Offender Sample

    ERIC Educational Resources Information Center

    Ruiz, Mark A.; Poythress, Norman G.; Lilienfeld, Scott O.; Douglas, Kevin S.

    2008-01-01

    The authors examined the psychometric properties, factor structure, and construct validity of the Dissociative Experiences Scale (DES) in a large offender sample (N = 1,515). Although the DES is widely used with community and clinical samples, minimal work has examined offender samples. Participants were administered self-report and interview…

  17. Modern NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Jelinski, Lynn W.

    1984-01-01

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

  18. Autonomous driving in NMR.

    PubMed

    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.

  19. Radiation damping in microcoil NMR probes

    NASA Astrophysics Data System (ADS)

    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-μL). 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.

  20. Radiation damping in microcoil NMR probes.

    PubMed

    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.

  1. Magic angle spinning NMR of paramagnetic proteins.

    PubMed

    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.

  2. Correlation between Electron Transport and Shear Alfven Activity in the National Spherical Torus Experiment

    SciTech Connect

    Stutman, D.; Delgado-Aparicio, L.; Finkenthal, M.; Tritz, K.; Gorelenkov, N.; Fredrickson, E.; Kaye, S.; Mazzucato, E.

    2009-03-20

    We report the observation of a correlation between shear Alfven eigenmode activity and electron transport in plasma regimes where the electron temperature gradient is flat, and thus the drive for temperature gradient microinstabilities is absent. Plasmas having rapid central electron transport show intense, broadband global Alfven eigenmode (GAE) activity in the 0.5-1.1 MHz range, while plasmas with low transport are essentially GAE-free. The first theoretical assessment of a GAE-electron transport connection indicates that overlapping modes can resonantly couple to the bulk thermal electrons and induce their stochastic diffusion.

  3. Combined models for data from in vitro-in vivo correlation experiments.

    PubMed

    Jacobs, Tom; Rossenu, Stefaan; Dunne, Adrian; Molenberghs, Geert; Straetemans, Roel; Bijnens, Luc

    2008-01-01

    A method is presented to describe the in vitro-in vivo correlation (IVIVC) of an extended release drug formulation. This extended release drug product is overencapsulated with immediate release material. The heterogeneity of the capsule is modelled using a combined model of an extended release and an immediate release pharmacokinetic profile. Whereas an IVIVC is conventionally performed using a two-stage procedure, the model uses a one-stage convolution-based method. The method is applied to a Galantamine controlled release formulation, an acetylcholinesterase inhibitor for the treatment of Alzheimer's disease. The average percentage prediction error indicated a good fit of the new model.

  4. A methodology for high resolution digital image correlation in high temperature experiments

    NASA Astrophysics Data System (ADS)

    Blaber, Justin; Adair, Benjamin S.; Antoniou, Antonia

    2015-03-01

    We propose a methodology for performing high resolution Digital Image Correlation (DIC) analysis during high-temperature mechanical tests. Specifically, we describe a technique for producing a stable, high-quality pattern on metal surfaces along with a simple optical system that uses a visible-range camera and a long-range microscope. The results are analyzed with a high-quality open-source DIC software developed by us. Using the proposed technique, we successfully acquired high-resolution strain maps of the crack tip field in a nickel superalloy sample at 1000 °C.

  5. Anomalous echo: Exploring abnormal experience correlates of emotional motor resonance in Schizophrenia Spectrum.

    PubMed

    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.

  6. EEG gamma coherence and other correlates of subjective reports during ayahuasca experiences.

    PubMed

    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.

  7. Adverse childhood experiences (ACEs), genetic polymorphisms and neurochemical correlates in experimentation with psychotropic drugs among adolescents.

    PubMed

    Somaini, L; Donnini, C; Manfredini, M; Raggi, M A; Saracino, M A; Gerra, M L; Amore, M; Leonardi, C; Serpelloni, G; Gerra, G

    2011-08-01

    Epidemiological and clinical data show frequent associations between adverse childhood experiences (ACEs) and substance abuse susceptibility particularly in adolescents. A large body of evidences suggests that the possible dysregulation of neuroendocrine responses as well as neurotransmitters function induced by childhood traumatic experiences and emotional neglect could constitute one of the essential biological changes implementing substance abuse vulnerability. Moreover, genotype variables and its environment interactions have been associated with an increased risk for early onset substance abuse. In this paper we present several data that support the hypothesis of the involvement of hypothalamus-pituitary-adrenal (HPA) axis in mediating the combined effect of early adverse experiences and gene variants affecting neurotransmission. The presented data also confirm the relationship between basal plasma levels of cortisol and ACTH, on the one hand, and retrospective measures of neglect during childhood on the other hand: the higher the mother and father neglect (CECA-Q) scores are, the higher the plasma levels of the two HPA hormones are. Furthermore, such positive relationship has been proved to be particularly effective and important when associated with the "S" promoter polymorphism of the gene encoding the 5-HTT transporter, both in homozygote and heterozygote individuals.

  8. Correlation of Process Data and Electrochemical Noise to Assess Kraft Digester Corrosion: Spring Grove Experiment

    SciTech Connect

    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

  9. BOOK REVIEW: NMR Imaging of Materials

    NASA Astrophysics Data System (ADS)

    Blümich, Bernhard

    2003-09-01

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

  10. Proton NMR Spectra: Deceptively Simple and Deceptively Complex Examples.

    ERIC Educational Resources Information Center

    Gurst, J. E.; And Others

    1985-01-01

    Describes relatively simple nuclear magnetic resonance (NMR) experiments that demonstrate unexpected results of the deceptively simple and deceptively complex types. Background information, experimental procedures, and typical results obtained are included. (JN)

  11. Picoliter H-1 NMR Spectroscopy

    SciTech Connect

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

    2002-02-01

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

  12. Site-selective Cu deposition on Pt dendrimer-encapsulated nanoparticles: correlation of theory and experiment.

    PubMed

    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.

  13. OPENCORE NMR: open-source core modules for implementing an integrated FPGA-based NMR spectrometer.

    PubMed

    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.

  14. OPENCORE NMR: Open-source core modules for implementing an integrated FPGA-based NMR spectrometer

    NASA Astrophysics Data System (ADS)

    Takeda, Kazuyuki

    2008-06-01

    A tool kit for implementing an integrated FPGA-based NMR spectrometer [K. Takeda, A highly integrated FPGA-based nuclear magnetic resonance spectrometer, Rev. Sci. Instrum. 78 (2007) 033103], referred to as the OPENCORE NMR spectrometer, is open to public. The system is composed of an FPGA chip and several peripheral boards for USB communication, direct-digital synthesis (DDS), RF transmission, signal acquisition, etc. Inside the FPGA chip have been implemented a number of digital modules including three pulse programmers, the digital part of DDS, a digital quadrature demodulator, dual digital low-pass filters, and a PC interface. These FPGA core modules are written in VHDL, and their source codes are available on our website. This work aims at providing sufficient information with which one can, given some facility in circuit board manufacturing, reproduce the OPENCORE NMR spectrometer presented here. Also, the users are encouraged to modify the design of spectrometer according to their own specific needs. A home-built NMR spectrometer can serve complementary roles to a sophisticated commercial spectrometer, should one comes across such new ideas that require heavy modification to hardware inside the spectrometer. This work can lower the barrier of building a handmade NMR spectrometer in the laboratory, and promote novel and exciting NMR experiments.

  15. Structural investigations on betacyanin pigments by LC NMR and 2D NMR spectroscopy.

    PubMed

    Stintzing, Florian C; Conrad, Jürgen; Klaiber, Iris; Beifuss, Uwe; Carle, Reinhold

    2004-02-01

    Four betacyanin pigments were analysed by LC NMR and subjected to extensive NMR characterisation after isolation. Previously, low pH values were applied for NMR investigations of betalains resulting in rapid degradation of the purified substances thus preventing extensive NMR studies. Consequently, up to now only one single (13)C NMR spectrum of a betalain pigment, namely that of neobetanin (=14,15-dehydrobetanin), was available. Because of its sufficient stability under highly acidic conditions otherwise detrimental for betacyanins, this pigment remained an exemption. Since betalains are most stable in the pH range of 5-7, a new solvent system has been developed allowing improved data acquisition through improved pigment stability at near neutral pH. Thus, not only (1)H, but for the first time also partial (13)C data of betanin, isobetanin, phyllocactin and hylocerenin isolated from red-purple pitaya [Hylocereus polyrhizus (Weber) Britton & Rose, Cactaceae] could be indirectly obtained by gHSQC- and gHMQC-NMR experiments.

  16. Correlation of Process Data and Electrochemical Noise to Assess Kraft Digester Corrosion: Kamloops Experiment

    SciTech Connect

    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.

  17. Measuring skin penetration by confocal Raman microscopy (CRM): correlation to results from conventional experiments

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

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

  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.

    PubMed

    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. Neural correlates of an illusory touch experience investigated with fMRI.

    PubMed

    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.

  1. Event-related potential P2 correlates of implicit aesthetic experience.

    PubMed

    Wang, Xiaoyi; Huang, Yujing; Ma, Qingguo; Li, Nan

    2012-10-03

    Using event-related potential measures, the present study investigated the affective responses to aesthetic experience. To differentiate the objective aesthetic value from subjective aesthetic evaluation, an amended oddball task was used in which pendant pictures were presented as frequent nontarget stimuli, whereas the landscape pictures were presented as a rare target. The pendant pictures were chosen from the largest online store in China and divided into beautiful and less beautiful conditions by the sales ranking. A positive component, P2, was recorded for each condition on the participants' frontal, central and parietal scalp areas. Less beautiful pendants elicited greater amplitudes of P2 than the beautiful ones. This indicates that emotion arousal seems to occur at the early stage of processing of aesthetics and can be detected by the P2 component, implying that the event-related potential methodology may be a more sensitive measure of the beauty-related attention bias. From the perspective of artwork design and marketing, our finding also shows that P2 can potentially be used as a reference measure in consumer aesthetic experience.

  2. NMR screening and crystal quality of bacterially expressed prokaryotic and eukaryotic proteins in a structural genomics pipeline

    PubMed Central

    Page, Rebecca; Peti, Wolfgang; Wilson, Ian A.; Stevens, Raymond C.; Wüthrich, Kurt

    2005-01-01

    In the Joint Center for Structural Genomics, one-dimensional (1D) 1H NMR spectroscopy is routinely used to characterize the folded state of protein targets and, thus, serves to guide subsequent crystallization efforts and to identify proteins for NMR structure determination. Here, we describe 1D 1H NMR screening of a group of 79 mouse homologue proteins, which correlates the NMR data with the outcome of subsequent crystallization experiments and crystallographic structure determination. Based on the 1D 1H NMR spectra, the proteins are classified into four groups, “A” to “D.” A-type proteins are candidates for structure determination by NMR or crystallography; “B”-type are earmarked for crystallography; “C” indicates folded globular proteins with broadened line shapes; and “D” are nonglobular, “unfolded” polypeptides. The results obtained from coarse- and fine-screen crystallization trials imply that only A- and B-type proteins should be used for extensive crystallization trials in the future, with C and D proteins subjected only to coarse-screen crystallization trials. Of the presently studied 79 soluble protein targets, 63% yielded A- or B-quality 1D 1H NMR spectra. Although similar yields of crystallization hits were obtained for all four groups, A to D, crystals from A- and B-type proteins diffracted on average to significantly higher resolution than crystals produced from C- or D-type proteins. Furthermore, the output of refined crystal structures from this test set of proteins was 4-fold higher for A- and B-type than for C- and D-type proteins. PMID:15677718

  3. Noninferiority tests based on concordance correlation coefficient for assessment of the agreement for gene expression data from microarray experiments.

    PubMed

    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.

  4. Fluid-Rock Characterization and Interactions in NMR Well Logging

    SciTech Connect

    George J. Hirasaki; Kishore K. Mohanty

    2005-09-05

    The objective of this report is to characterize the fluid properties and fluid-rock interactions that are needed for formation evaluation by NMR well logging. The advances made in the understanding of NMR fluid properties are summarized in a chapter written for an AAPG book on NMR well logging. This includes live oils, viscous oils, natural gas mixtures, and the relation between relaxation time and diffusivity. Oil based drilling fluids can have an adverse effect on NMR well logging if it alters the wettability of the formation. The effect of various surfactants on wettability and surface relaxivity are evaluated for silica sand. The relation between the relaxation time and diffusivity distinguishes the response of brine, oil, and gas in a NMR well log. A new NMR pulse sequence in the presence of a field gradient and a new inversion technique enables the T{sub 2} and diffusivity distributions to be displayed as a two-dimensional map. The objectives of pore morphology and rock characterization are to identify vug connectivity by using X-ray CT scan, and to improve NMR permeability correlation. Improved estimation of permeability from NMR response is possible by using estimated tortuosity as a parameter to interpolate between two existing permeability models.

  5. Synthesis and complete assignment of the 1H and 13C NMR spectra of 6-substituted and 2,6-disubstituted pyridazin-3(2H)-ones.

    PubMed

    Besada, Pedro; Costas, Tamara; Vila, Noemi; Chessa, Carla; Terán, Carmen

    2011-07-01

    Several pyridazin-3(2H)-one derivatives were synthesized starting from alkyl furans using oxidation with singlet oxygen to give 4-methoxy or 4-hydroxybutenolides, key intermediates of the synthetic strategy followed. For all pyridazinones reported, a complete assignment of the (1)H and (13)C NMR spectra using one- and two-dimensional NMR spectroscopic methods, which included NOE, DEPT, COSY, HSQC and HMBC experiments, was accomplished. Correlations between the chemical shifts of the heterocyclic ring atoms and substituents at N-2 and C-6 were analyzed.

  6. Multi-dimensional NMR without coherence transfer: Minimizing losses in large systems

    NASA Astrophysics Data System (ADS)

    Liu, Yizhou; Prestegard, James H.

    2011-10-01

    Most multi-dimensional solution NMR experiments connect one dimension to another using coherence transfer steps that involve evolution under scalar couplings. While experiments of this type have been a boon to biomolecular NMR the need to work on ever larger systems pushes the limits of these procedures. Spin relaxation during transfer periods for even the most efficient 15N- 1H HSQC experiments can result in more than an order of magnitude loss in sensitivity for molecules in the 100 kDa range. A relatively unexploited approach to preventing signal loss is to avoid coherence transfer steps entirely. Here we describe a scheme for multi-dimensional NMR spectroscopy that relies on direct frequency encoding of a second dimension by multi-frequency decoupling during acquisition, a technique that we call MD-DIRECT. A substantial improvement in sensitivity of 15N- 1H correlation spectra is illustrated with application to the 21 kDa ADP ribosylation factor (ARF) labeled with 15N in all alanine residues. Operation at 4 °C mimics observation of a 50 kDa protein at 35 °C.

  7. Mutagenic potential of nitrenium ions of nitrobenzanthrones: correlation between theory and experiment.

    PubMed

    Reynisson, Jóhannes; Stiborová, Marie; Martínek, Václav; Gamboa da Costa, Gonçalo; Phillips, David H; Arlt, Volker M

    2008-10-01

    The mutagenic activity of nine substituted nitrobenzanthrone (NBA) derivatives was recently established in the Ames assay and ranged from near inactivity to extremely high mutagenic activity (Takamura-Enya et al. 2006: Mutagenesis 21:399-404). Using thermochemical and molecular modeling techniques, the activation pathway of these NBA derivatives, namely 1-nitro-, 2-nitro-, 3-nitro-, 9-nitro-, 11-nitro-, 1,9-dinitro-, 3,9-dinitro-, 3,11-dinitro-, and 3,9,11-trinitrobenzanthrone, and the formation of the corresponding aryl-nitrenium ions, were investigated using density functional theory calculations. The calculated properties of the NBA derivatives were systematically compared with their bacterial mutagenic potency. Accommodation of the ligand substrates into the binding pocket of the bacterial nitroreductases was not sterically inhibited for the NBAs. Moreover, electron affinities, water elimination energies, esterification, and solvolysis energies did not reveal any possible links with the observed mutagenic potency of the NBAs. However, a strong negative linear correlation was found when the relative energies of the nitrenium ions of the mono and disubstituted NBAs were plotted against the logarithm of the mutagenic potency of the NBAs found in the different Salmonella typhimurium strains. Therefore, our data clearly indicate that the stability of the nitrenium ions is one critical determinant of the mutagenic potency of NBAs in Salmonella tester strains.

  8. A closed form for fluorescence correlation spectroscopy experiments in submicrometer structures.

    PubMed

    Sanguigno, Luigi; De Santo, Ilaria; Causa, Filippo; Netti, Paolo

    2010-12-01

    Fluorescence correlation spectroscopy (FCS) is a powerful technique for measuring low concentrations of fluorescent molecules and their diffusion coefficients in an open detection volume. However, in several practical cases, when FCS measurements are carried out in small compartments like microchannels, neglecting boundary effects could lead to erroneous results. Here, a close form solution is proposed to explicitly account for the presence of walls located at a distance comparable with the characteristic detection volume lengths. We derive a one-dimensional diffusion constrained model and then generalize the solution to the two- and the three-dimensional constrained cases. We further indicate within which limits the standard autocorrelation function (ACF) model gives reliable results in microconfinement. Our model relies just on the assumption of elastic hits at the system walls and succeeds in describing the ACF of fluorescent probes confined along one direction. Through the analysis of FCS experimental data, we are able to predict the correct shape of the ACF in channels of micrometric and submicrometric width and measure the extent of lateral confinement. In addition, it permits the investigation of microstructured material features such as cages and cavities having dimensions on the micrometric range. On the basis of the proposed model, we also show in which conditions confinement could generate an apparent time dependent probe mobility, thus allowing a proper interpretation of the transport process taking place in submicrometric compartments.

  9. Correlates of perceptual awareness in human primary auditory cortex revealed by an informational masking experiment.

    PubMed

    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.

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

    PubMed

    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.

  11. Quantum mechanical NMR simulation algorithm for protein-size spin systems.

    PubMed

    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.

  12. Structure, Vibrational Spectra and (11)B-NMR Chemical Shift of Na8[AlSiO4]6(B(OH)4)2: Comparison of Theory and Experiment.

    PubMed

    Schneider, Alexander G; Schomborg, Lars; Ulpe, Anna C; Rüscher, Claus H; Bredow, Thomas

    2016-09-29

    Density functional theory (DFT) calculations at generalized gradient approximation (GGA) level were performed to interpret experimental IR and Raman vibrational spectra, to assign (11)B-NMR chemical shifts, and to calculate the structure of the tetrahydroxyborate sodalite Na8[AlSiO4]6(B(OH)4)2. Full optimization of the intercalated compound gave the following structural parameters of B(OH)4(-): B-O-B (105.3-115.3°) and B-O-H (111.5-115.4°) angles, B-O (1.476 Å, 1.491 Å) and O-H (0.98 Å) distances. The calculated normal modes were assigned to experimental IR and Raman spectra. In general, close agreement between theory and experiment was obtained. The mean absolute deviation (MAD) is below 11 cm(-1). We also calculate the thermodynamical stability of Na8[AlSiO4]6(B(OH)4)2 with respect to Na8[AlSiO4]6(BH4)2 in the context of the tetrahydroborate hydration reaction.

  13. NMR Studies of Peroxidases.

    NASA Astrophysics Data System (ADS)

    Veitch, Nigel Charles

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

  14. NMR imaging of materials

    SciTech Connect

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

    1988-03-01

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

  15. Hierarchical alignment and full resolution pattern recognition of 2D NMR spectra: application to nematode chemical ecology.

    PubMed

    Robinette, Steven L; Ajredini, Ramadan; Rasheed, Hasan; Zeinomar, Abdulrahman; Schroeder, Frank C; Dossey, Aaron T; Edison, Arthur S

    2011-03-01

    Nuclear magnetic resonance (NMR) is the most widely used nondestructive technique in analytical chemistry. In recent years, it has been applied to metabolic profiling due to its high reproducibility, capacity for relative and absolute quantification, atomic resolution, and ability to detect a broad range of compounds in an untargeted manner. While one-dimensional (1D) (1)H NMR experiments are popular in metabolic profiling due to their simplicity and fast acquisition times, two-dimensional (2D) NMR spectra offer increased spectral resolution as well as atomic correlations, which aid in the assignment of known small molecules and the structural elucidation of novel compounds. Given the small number of statistical analysis methods for 2D NMR spectra, we developed a new approach for the analysis, information recovery, and display of 2D NMR spectral data. We present a native 2D peak alignment algorithm we term HATS, for hierarchical alignment of two-dimensional spectra, enabling pattern recognition (PR) using full-resolution spectra. Principle component analysis (PCA) and partial least squares (PLS) regression of full resolution total correlation spectroscopy (TOCSY) spectra greatly aid the assignment and interpretation of statistical pattern recognition results by producing back-scaled loading plots that look like traditional TOCSY spectra but incorporate qualitative and quantitative biological information of the resonances. The HATS-PR methodology is demonstrated here using multiple 2D TOCSY spectra of the exudates from two nematode species: Pristionchus pacificus and Panagrellus redivivus. We show the utility of this integrated approach with the rapid, semiautomated assignment of small molecules differentiating the two species and the identification of spectral regions suggesting the presence of species-specific compounds. These results demonstrate that the combination of 2D NMR spectra with full-resolution statistical analysis provides a platform for chemical and

  16. Photodissociation of OCS: Deviations between theory and experiment, and the importance of higher order correlation effects

    SciTech Connect

    Schmidt, J. A.; Olsen, J. M. H.

    2014-11-14

    The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 2{sup 1}A{sup ′} (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 1{sup 1}A{sup ″} (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO.

  17. NMR studies of metallic tin confined within porous matrices

    SciTech Connect

    Charnaya, E. V.; Tien, Cheng; Lee, M. K.; Kumzerov, Yu. A.

    2007-04-01

    {sup 119}Sn NMR studies were carried out for metallic tin confined within synthetic opal and porous glass. Tin was embedded into nanoporous matrices in the melted state under pressure. The Knight shift for liquid confined tin was found to decrease with decreasing pore size. Correlations between NMR line shapes, Knight shift, and pore filling were observed. The melting and freezing phase transitions of tin under confinement were studied through temperature dependences of NMR signals upon warming and cooling. Melting of tin within the opal matrix agreed well with the liquid skin model suggested for small isolated particles. The influence of the pore filling on the melting process was shown.

  18. NMR studies on polyphosphide Ce6Ni6P17

    NASA Astrophysics Data System (ADS)

    Koyama, T.; Yamada, H.; Ueda, K.; Mito, T.; Aoyama, Y.; Nakano, T.; Takeda, N.

    2016-02-01

    We report the result of 31P nuclear magnetic resonance (NMR) studies on Ce6Ni6P17. The observed NMR spectra show a Lorentzian-type and an asymmetric shapes, reflecting the local symmetry around each P site in the cubic unit cell. We have identified the observed NMR lines corresponding to three inequivalent P sites and deduced the temperature dependence of the Knight shift for each site. The Knight shifts increase with decreasing temperature down to 1.5 K, indicating a localized spin system of Ce6Ni6P17. Antiferromagnetic correlation between 4f spins is suggested from the negative sign of the Weiss-temperature.

  19. NMR Crystallography of Enzyme Active Sites: Probing Chemically-Detailed, Three-Dimensional Structure in Tryptophan Synthase

    PubMed Central

    Dunn, Michael F.

    2013-01-01

    Conspectus 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. From its initial role in refining diffraction data of organic and inorganic solids, NMR crystallography is now being developed for application to active sites in biomolecules, where it reveals chemically-rich detail concerning the interactions between enzyme site residues and the reacting substrate that is not achievable when X-ray, NMR, or computational methodologies are applied in isolation. For example, typical X-ray crystal structures (1.5 to 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 state of either. 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 rely on chemical details that must be specified. 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 models of the active site can be developed using computational chemistry; these models can be distinguished by comparison of their 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 highest resolution. In this Account, we detail our first steps in the development of NMR

  20. High-resolution, high-pressure NMR studies of proteins.

    PubMed Central

    Jonas, J; Ballard, L; Nash, D

    1998-01-01

    Advanced high-resolution NMR spectroscopy, including two-dimensional NMR techniques, combined with high pressure capability, represents a powerful new tool in the study of proteins. This contribution is organized in the following way. First, the specialized instrumentation needed for high-pressure NMR experiments is discussed, with specific emphasis on the design features and performance characteristics of a high-sensitivity, high-resolution, variable-temperature NMR probe operating at 500 MHz and at pressures of up to 500 MPa. An overview of several recent studies using 1D and 2D high-resolution, high-pressure NMR spectroscopy to investigate the pressure-induced reversible unfolding and pressure-assisted cold denaturation of lysozyme, ribonuclease A, and ubiquitin is presented. Specifically, the relationship between the residual secondary structure of pressure-assisted, cold-denatured states and the structure of early folding intermediates is discussed. PMID:9649405

  1. Dynamics of Antibody Domains Studied by Solution NMR

    PubMed Central

    Vu, Bang K.; Walsh, Joseph D.; Dimitrov, Dimiter S.; Ishima, Rieko

    2012-01-01

    Information on local dynamics of antibodies is important to evaluate stability, to rationally design variants, and to clarify conformational disorders at the epitope binding sites. Such information may also be useful for improved understanding of antigen recognition. NMR can be used for characterization of local protein dynamics at the atomic level through relaxation measurements. Due to the complexity of the NMR spectra, an extensive use of this method is limited to small protein molecules, for example, antibody domains and some scFv. Here, we describe a protocol that was used to study the dynamics of an antibody domain in solution using NMR. We describe protein preparation for NMR studies, NMR sample optimization, signal assignments, and dynamics experiments. PMID:19252840

  2. Interpretive Experiments

    ERIC Educational Resources Information Center

    DeHaan, Frank, Ed.

    1977-01-01

    Describes an interpretative experiment involving the application of symmetry and temperature-dependent proton and fluorine nmr spectroscopy to the solution of structural and kinetic problems in coordination chemistry. (MLH)

  3. Hydration dynamics of the collagen triple helix by NMR.

    PubMed

    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.

  4. An NMR determination of CO diffusion on platinum electrocatalysts.

    PubMed

    Kobayashi, Takeshi; Babu, Panakkattu K; Gancs, Lajos; Chung, Jong Ho; Oldfield, Eric; Wieckowski, Andrzej

    2005-10-19

    We report the first direct measurement of CO diffusion on nanoparticle Pt electrocatalysts at the solid/liquid interface, carried out using 13C nuclear magnetic resonance (NMR) with a spin-labeling pulse sequence. Diffusion parameters were measured in the temperature range of 253-293 K for CO adsorbed on commercial Pt-black under saturation coverage. 2H NMR of the same system indicates that the electrolyte remains in the liquid state at temperatures where the CO diffusion experiments were performed. The CO diffusion parameters follow typical Arrhenius behavior with an activation energy of 6.0 +/- 0.4 kcal/mol and a pre-exponential factor of (1.1 +/- 0.6) x 10-8 cm2/s. Exchange between different CO populations, driven by a chemical potential gradient, is suggested to be the main mechanism for CO diffusion. The presence of the electrolyte medium considerably slows down the diffusion of CO as compared to that seen on surfaces of bulk metals under UHV conditions. This work opens up a new approach to the study of surface diffusion of adsorbed molecules on nanoparticle electrode catalysts, including the possibility of correlating diffusion parameters to catalytic activity in real world applications of broad general interest.

  5. Planetary gear modal vibration experiments and correlation against lumped-parameter and finite element models

    NASA Astrophysics Data System (ADS)

    Ericson, Tristan M.; Parker, Robert G.

    2013-04-01

    Experimental modal analysis techniques are applied to characterize the planar dynamic behavior of two spur planetary gears. Rotational and translational vibrations of the sun gear, carrier, and planet gears are measured. Experimentally obtained natural frequencies, mode shapes, and dynamic response are compared to the results from lumped-parameter and finite element models. Two qualitatively different classes of mode shapes in distinct frequency ranges are observed in the experiments and confirmed by the lumped-parameter model, which considers the accessory shafts and fixtures in the system to capture all of the natural frequencies and modes. The finite element model estimates the high-frequency modes that have significant tooth mesh deflection without considering the shafts and fixtures. The lumped-parameter and finite element models accurately predict the natural frequencies and modal properties established by experimentation. Rotational, translational, and planet mode types presented in published mathematical studies are confirmed experimentally. The number and types of modes in the low-frequency and high-frequency bands depend on the degrees of freedom in the central members and planet gears, respectively. The accuracy of natural frequency prediction is improved when the planet bearings have differing stiffnesses in the tangential and radial directions, consistent with the bearing load direction.

  6. Keeping an eye on the conductor: neural correlates of visuo-motor synchronization and musical experience

    PubMed Central

    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. PMID:25883561

  7. Learning from experience: Event-related potential correlates of reward processing, neural adaptation, and behavioral choice

    PubMed Central

    Walsh, Matthew M.; Anderson, John R.

    2012-01-01

    To behave adaptively, we must learn from the consequences of our actions. Studies using event-related potentials (ERPs) have been informative with respect to the question of how such learning occurs. These studies have revealed a frontocentral negativity termed the feedback-related negativity (FRN) that appears after negative feedback. According to one prominent theory, the FRN tracks the difference between the values of actual and expected outcomes, or reward prediction errors. As such, the FRN provides a tool for studying reward valuation and decision making. We begin this review by examining the neural significance of the FRN. We then examine its functional significance. To understand the cognitive processes that occur when the FRN is generated, we explore variables that influence its appearance and amplitude. Specifically, we evaluate four hypotheses: (1) the FRN encodes a quantitative reward prediction error; (2) the FRN is evoked by outcomes and by stimuli that predict outcomes; (3) the FRN and behavior change with experience; and (4) the system that produces the FRN is maximally engaged by volitional actions. PMID:22683741

  8. Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

    SciTech Connect

    Alam, Todd M.; Liao, Zuolei; Nyman, May; Yates, Jonathan

    2016-04-27

    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. Furthermore, 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.

  9. Combining insights from solid-state NMR and first principles calculation: applications to the 19F NMR of octafluoronaphthalene.

    PubMed

    Robbins, Andrew J; Ng, William T K; Jochym, Dominik; Keal, Thomas W; Clark, Stewart J; Tozer, David J; Hodgkinson, Paul

    2007-05-21

    Advances in solid-state NMR methodology and computational chemistry are applied to the (19)F NMR of solid octafluoronaphthalene. It is demonstrated experimentally, and confirmed by density functional theory (DFT) calculations, that the spectral resolution in the magic-angle spinning spectrum is limited by the anisotropy of the bulk magnetic susceptibility (ABMS). This leads to the unusual observation that the resolution improves as the sample is diluted. DFT calculations provide assignments of each of the peaks in the (19)F spectrum, but the predictions are close to the limits of accuracy and correlation information from 2-D NMR is invaluable in confirming the assignments. The effects of non-Gaussian lineshapes on the use of 2-D NMR for mapping correlations of spectral frequencies (e.g. due to the ABMS) are also discussed.

  10. Evidence for strong electron correlations in graphene molecular fragments: Theory and experiments on two-photon absorptions

    NASA Astrophysics Data System (ADS)

    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.

  11. Nuclear Spin-Lattice Relaxation Times from Continuous Wave NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Wooten, Jan B.; And Others

    1979-01-01

    The experiment described, suitable for undergraduate physical chemistry laboratories, illustrates the general principles of relaxation and introduces the nmr concepts of saturation and spin-inversion. (BB)

  12. An analysis of the AVE-SESAME I period using statistical structure and correlation functions. [Atmospheric Variability Experiment-Severe Environmental Storm and Mesoscale Experiment

    NASA Technical Reports Server (NTRS)

    Fuelberg, H. E.; Meyer, P. J.

    1984-01-01

    Structure and correlation functions are used to describe atmospheric variability during the 10-11 April day of AVE-SESAME 1979 that coincided with the Red River Valley tornado outbreak. The special mesoscale rawinsonde data are employed in calculations involving temperature, geopotential height, horizontal wind speed and mixing ratio. Functional analyses are performed in both the lower and upper troposphere for the composite 24 h experiment period and at individual 3 h observation times. Results show that mesoscale features are prominent during the composite period. Fields of mixing ratio and horizontal wind speed exhibit the greatest amounts of small-scale variance, whereas temperature and geopotential height contain the least. Results for the nine individual times show that small-scale variance is greatest during the convective outbreak. The functions also are used to estimate random errors in the rawinsonde data. Finally, sensitivity analyses are presented to quantify confidence limits of the structure functions.

  13. NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR.

    PubMed

    Schreckenbach, Georg

    2002-12-16

    In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

  14. 13C NMR of tunnelling methyl groups

    NASA Astrophysics Data System (ADS)

    Detken, A.

    The dipolar interactions between the protons and the central 13C nucleus of a 13CH3 group are used to study rotational tunnelling and incoherent dynamics of such groups in molecular solids. Single-crystal 13C NMR spectra are derived for arbitrary values of the tunnel frequency upsilon t. Similarities to ESR and 2H NMR are pointed out. The method is applied to three different materials. In the hydroquinone/acetonitrile clathrate, the unique features in the 13C NMR spectra which arise from tunnelling with a tunnel frequency that is much larger than the dipolar coupling between the methyl protons and the 13C nucleus are demonstrated, and the effects of incoherent dynamics are studied. The broadening of the 13C resonances is related to the width of the quasi-elastic line in neutron scattering. Selective magnetization transfer experiments for studying slow incoherent dynamics are proposed. For the strongly hindered methyl groups of L-alanine, an upper limit for upsilon is derived from the 13C NMR spectrum. In aspirinTM (acetylsalicylic acid), incoherent reorientations dominate the spectra down to the lowest temperatures studied; their rate apparently increases with decreasing temperature below 25K.

  15. Structural Studies of Biological Solids Using NMR

    NASA Astrophysics Data System (ADS)

    Ramamoorthy, Ayyalusamy

    2011-03-01

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

  16. Hydrate Shell Growth Measured Using NMR.

    PubMed

    Haber, Agnes; Akhfash, Masoumeh; Loh, Charles K; Aman, Zachary M; Fridjonsson, Einar O; May, Eric F; Johns, Michael L

    2015-08-18

    Benchtop nuclear magnetic resonance (NMR) pulsed field gradient (PFG) and relaxation measurements were used to monitor the clathrate hydrate shell growth occurring in water droplets dispersed in a continuous cyclopentane phase. These techniques allowed the growth of hydrate inside the opaque exterior shell to be monitored and, hence, information about the evolution of the shell's morphology to be deduced. NMR relaxation measurements were primarily used to monitor the hydrate shell growth kinetics, while PFG NMR diffusion experiments were used to determine the nominal droplet size distribution (DSD) of the unconverted water inside the shell core. A comparison of mean droplet sizes obtained directly via PFG NMR and independently deduced from relaxation measurements showed that the assumption of the shell model-a perfect spherical core of unconverted water-for these hydrate droplet systems is correct, but only after approximately 24 h of shell growth. Initially, hydrate growth is faster and heat-transfer-limited, leading to porous shells with surface areas larger than that of spheres with equivalent volumes. Subsequently, the hydrate growth rate becomes mass-transfer-limited, and the shells become thicker, spherical, and less porous.

  17. Structural biology applications of solid state MAS DNP NMR.

    PubMed

    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.

  18. Structural biology applications of solid state MAS DNP NMR

    NASA Astrophysics Data System (ADS)

    Akbey, Ümit; Oschkinat, Hartmut

    2016-08-01

    Dynamic Nuclear Polarization (DNP) has long been an aim for increasing sensitivity of nuclear magnetic resonance (NMR) spectroscopy, delivering spectra in shorter experiment times or of smaller sample amounts. In recent years, it has been applied in magic angle spinning (MAS) solid-state NMR to a large range of samples, including biological macromolecules and functional materials. New research directions in structural biology can be envisaged by DNP, facilitating investigations on very large complexes or very heterogeneous samples. Here we present a summary of state of the art DNP MAS NMR spectroscopy and its applications to structural biology, discussing the technical challenges and factors affecting DNP performance.

  19. Magic Angle Spinning NMR Metabolomics

    SciTech Connect

    Zhi Hu, Jian

    2016-01-01

    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. Protein-Observed Fluorine NMR Is a Complementary Ligand Discovery Method to (1)H CPMG Ligand-Observed NMR.

    PubMed

    Urick, Andrew K; Calle, Luis Pablo; Espinosa, Juan F; Hu, Haitao; Pomerantz, William C K

    2016-11-18

    To evaluate its potential as a ligand discovery tool, we compare a newly developed 1D protein-observed fluorine NMR (PrOF NMR) screening method with the well-characterized ligand-observed (1)H CPMG NMR screen. We selected the first bromodomain of Brd4 as a model system to benchmark PrOF NMR because of the high ligandability of Brd4 and the need for small molecule inhibitors of related epigenetic regulatory proteins. We compare the two methods' hit sensitivity, triaging ability, experiment speed, material consumption, and the potential for false positives and negatives. To this end, we screened 930 fragment molecules against Brd4 in mixtures of five and followed up these studies with mixture deconvolution and affinity characterization of the top hits. In selected examples, we also compare the environmental responsiveness of the (19)F chemical shift to (1)H in 1D-protein observed (1)H NMR experiments. To address concerns of perturbations from fluorine incorporation, ligand binding trends and affinities were verified via thermal shift assays and isothermal titration calorimetry. We conclude that for the protein understudy here, PrOF NMR and (1)H CPMG have similar sensitivity, with both being effective tools for ligand discovery. In cases where an unlabeled protein can be used, 1D protein-observed (1)H NMR may also be effective; however, the (19)F chemical shift remains significantly more responsive.