WorldWideScience

Sample records for cycling nmr experiments

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

    Science.gov (United States)

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

    2015-03-01

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

  2. An Inversion Recovery NMR Kinetics Experiment

    Science.gov (United States)

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

    2011-01-01

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

  3. Field-cycling-NMR: A new magnet design for reduced energy consumption

    Energy Technology Data Exchange (ETDEWEB)

    Plendl, Dirk; Privalov, Alexei F.; Fujara, Franz [Institut fuer Festkoerperphysik, TU Darmstadt (Germany)

    2010-07-01

    Field-cycling-NMR is an established method for the investigation of field dependent spin phenomena, like relaxation dispersion, polarization transfer, enhanced NQR etc. In contrast to normal NMR, the magnetic field in a field-cycling experiment is switched between several distinct levels within milliseconds. This can only be achieved with specially designed, low inductive magnets. Today, nearly all FC-spectrometers utilize air core coils made of copper or silver. Producing strong magnetic fields with normal-conducting magnets results in a large energy dissipation (tens of kW) so that the maximum field strength is limited by the amount of heat that can be extracted by the cooling system. We present a new magnet design for fast field-cycling-NMR which uses a magnet with an iron core for field amplification, thus generating the same field with significantly reduced energy consumption and system complexity.

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

    OpenAIRE

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

    2013-01-01

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

  5. Graphical programming for pulse automated NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Luiz H. K. Queiroz Júnior

    2013-01-01

    Full Text Available Ultrafast 2D NMR is a powerful methodology that allows recording of a 2D NMR spectrum in a fraction of second. However, due to the numerous non-conventional parameters involved in this methodology its implementation is no trivial task. Here, an optimized experimental protocol is carefully described to ensure efficient implementation of ultrafast NMR. The ultrafast spectra resulting from this implementation are presented based on the example of two widely used 2D NMR experiments, COSY and HSQC, obtained in 0.2 s and 41 s, respectively.

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

    Energy Technology Data Exchange (ETDEWEB)

    Queiroz Junior, Luiz H. K., E-mail: professorkeng@gmail.com [Universidade Federal de Sao Carlos (UFSC), SP (Brazil). Departamento de Quimica; Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Inst. de Quimica; Ferreira, Antonio G. [Universidade Federal de Sao Carlos (UFSC), SP (Brazil). Departamento de Quimica; Giraudeau, Patrick [Universite de Nantes (France). CNRS, Chimie et Interdisciplinarite: Synthese, Analyse, Modelisation

    2013-09-01

    Ultrafast 2D NMR is a powerful methodology that allows recording of a 2D NMR spectrum in a fraction of second. However, due to the numerous non-conventional parameters involved in this methodology its implementation is no trivial task. Here, an optimized experimental protocol is carefully described to ensure efficient implementation of ultrafast NMR. The ultrafast spectra resulting from this implementation are presented based on the example of two widely used 2D NMR experiments, COSY and HSQC, obtained in 0.2 s and 41 s, respectively. (author)

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

    Science.gov (United States)

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

    2010-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-08-15

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

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

    Science.gov (United States)

    Smith, Robert L.; And Others

    1988-01-01

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

  11. Dry-cured ham tissue characterization by fast field cycling NMR relaxometry and quantitative magnetization transfer.

    Science.gov (United States)

    Bajd, Franci; Gradišek, Anton; Apih, Tomaž; Serša, Igor

    2016-05-31

    Fast field cycling (FFC) and quantitative magnetization transfer (qMT) NMR methods are two powerful tools in NMR analysis of biological tissues. The qMT method is well established in biomedical NMR applications, while the FFC method is often used in investigations of molecular dynamics on which longitudinal NMR relaxation times of the investigated material critically depend. Despite their proven analytical potential, these two methods were rarely used in NMR studies of food, especially when combined together. In our study, we demonstrate the feasibility of a combined FFC/qMT-NMR approach for the fast and nondestructive characterization of dry-curing ham tissues differing by protein content. The characterization is based on quantifying the pure quadrupolar peak area (area under the quadrupolar contribution of dispersion curve obtained by FFC-NMR) and the restricted magnetization pool size (obtained by qMT-NMR). Both quantities correlate well with concentration of partially immobilized, nitrogen-containing and proton magnetization exchanging muscle proteins. Therefore, these two quantities could serve as potential markers for dry-curing process monitoring. Copyright © 2016 John Wiley & Sons, Ltd.

  12. Amide-Exchange-Rate-Edited NMR (AERE-NMR) Experiment:A Novel Method for Resolving Overlapping Resonances

    Institute of Scientific and Technical Information of China (English)

    LIU Xue-Hui; LIN Dong-Hai

    2007-01-01

    This paper describes an amide-exchange-rate-edited (AERE) NMR method that can effectively alleviate the problem of resonance overlap for proteins and peptides. This method exploits the diversity of amide proton exchange rates and consists of two complementary experiments: (1) SEA (solvent exposed amide)-type NMR experiments to map exchangeable surface residues whose amides are not involved in hydrogen bonding, and (2) presat-type NMR experiments to map solvent inaccessibly buried residues or nonexchangeable residues located in hydrogen-bonded secondary structures with properly controlled saturation transfer via amide proton exchanges with the solvent. This method separates overlapping resonances in a spectrum into two complementary spectra. The AERE-NMR method was demonstrated with a sample of 15N/13C/2H(70%) labeled ribosome-inactivating protein trichosanthin of 247 residues.

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

    Science.gov (United States)

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

    2012-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Arash Bahrami

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

  15. Dynamic processes and chemical composition of Lepidium sativum seeds determined by means of field-cycling NMR relaxometry and NMR spectroscopy.

    Science.gov (United States)

    Rachocki, A; Latanowicz, L; Tritt-Goc, J

    2012-12-01

    Proton nuclear magnetic resonance (NMR) techniques, such as field-cycling relaxometry, wide-line NMR spectroscopy, and magic angle spinning NMR spectroscopy, were applied to study the seeds of cress, Lepidium sativum. Field-cycling NMR relaxometry was used for the first time to investigate the properties of the whole molecular system of dry cress seeds. This method not only allowed the dynamics to be studied, but was also successful in the differentiation among the solid (i.e., carbohydrates, proteins, or fats forming a solid form of lipids) and liquid-like (oil compounds) components of the seeds. The (1)H NMR relaxation dispersion of oils was interpreted as a superposition of intramolecular and intermolecular contributions. The intramolecular part was described in terms of a Lorentzian spectral density function, whereas a log-Gaussian distribution of correlation times was applied for the intermolecular dipole-dipole contribution. The models applied led to very good agreement with the experimental data and demonstrate that the contribution of the intermolecular relaxation to the overall relaxation should not be disregarded, especially at low frequencies. A power-law frequency dependence of the proton relaxation dispersion was used for the interpretation of the solid components. From the analysis of the (1)H wide-line NMR spectra of the liquid-like component of hydrated cress seeds, we can conclude that the contribution of oil protons should always be taken into account when evaluating the spin-lattice relaxation times values or measuring the moisture and oil content. The application of (1)H magic angle spinning NMR significantly improves resolution in the liquid-like spectrum of seeds and allows the determination of the chemical composition of cress seeds.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Jian Zhi [Pacific Northwest National Laboratory

    2014-08-19

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

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

    Science.gov (United States)

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

    2016-01-01

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

  18. Solid state field-cycling NMR relaxometry: instrumental improvements and new applications.

    Science.gov (United States)

    Fujara, Franz; Kruk, Danuta; Privalov, Alexei F

    2014-10-01

    The paper reviews recent progress in field cycling (FC) NMR instrumentation and its application to solid state physics. Special emphasis is put on our own work during the last 15years on instrumentation, theory and applications. As far as instrumentation is concerned we report on our development of two types of electronical FC relaxometers, a mechanical FC relaxometer and a combination of FC and one-dimensional microimaging. Progress has been achieved with respect to several parameters such as the accessible field and temperature range as well as the incorporation of sample spinning. Since an appropriate analysis of FC data requires a careful consideration of relaxation theory, we include a theory section discussing the most relevant aspects of relaxation in solids which are related to residual dipolar and quadrupolar interactions. The most important limitations of relaxation theory are also discussed. With improved instrumentation and with the help of relaxation theory we get access to interesting new applications such as ionic motion in solid electrolytes, structure determination in molecular crystals, ultraslow polymer dynamics and rotational resonance phenomena.

  19. Air core notch-coil magnet with variable geometry for fast-field-cycling NMR.

    Science.gov (United States)

    Kruber, S; Farrher, G D; Anoardo, E

    2015-10-01

    In this manuscript we present details on the optimization, construction and performance of a wide-bore (71 mm) α-helical-cut notch-coil magnet with variable geometry for fast-field-cycling NMR. In addition to the usual requirements for this kind of magnets (high field-to-power ratio, good magnetic field homogeneity, low inductance and resistance values) a tunable homogeneity and a more uniform heat dissipation along the magnet body are considered. The presented magnet consists of only one machined metallic cylinder combined with two external movable pieces. The optimal configuration is calculated through an evaluation of the magnetic flux density within the entire volume of interest. The magnet has a field-to-current constant of 0.728 mT/A, allowing to switch from zero to 0.125 T in less than 3 ms without energy storage assistance. For a cylindrical sample volume of 35 cm(3) the effective magnet homogeneity is lower than 130 ppm.

  20. Fast field cycling NMR relaxometry characterization of biochars obtained from an industrial thermochemical process

    Energy Technology Data Exchange (ETDEWEB)

    De Pasquale, Claudio; Marsala, Valentina; Alonzo, Giuseppe; Conte, Pellegrino [Universita degli Studi di Palermo (Italy). Dipt. dei Sistemi Agro-Ambientali; Berns, Anne E. [Forschungszentrum Juelich GmbH (Germany). Inst. of Bio- and Geosciences (IBG-3); Valagussa, Massimo [M.A.C. Minoprio Analisi e Certificazioni S.r.l., Vertemate con Minoprio, CO (Italy); Pozzi, Alessandro [A.G.T. Advanced Gasification Technology S.r.l., Arosio, CO (Italy)

    2012-09-15

    Purpose: Biochar has unique properties which make it a powerful tool to increase soil fertility and to contribute to the decrease of the amount of atmospheric carbon dioxide through the mechanisms of C sequestration in soils. Chemical and physical biochar characteristics depend upon the technique used for its production and the biomass nature. For this reason, biochar characterization is very important in order to address its use either for agricultural or environmental purposes. Materials and methods: Three different biochars obtained from an industrial gasification process were selected in order to establish their chemical and physical peculiarities for a possible use in agronomical practices. They were obtained by charring residues from the wine-making industry (marc) and from poplar and conifer forests. Routine analyses such as pH measurements, elemental composition, and ash and metal contents were performed together with the evaluation of the cross-polarization magic angle spinning (CPMAS) {sup 13}C NMR spectra of all the biochar samples. Finally, relaxometry properties of water-saturated biochars were retrieved in order to obtain information on pore size distribution. Results and discussion: All the biochars revealed basic pH values due to their large content of alkaline metals. The quality of CPMAS {sup 13}C NMR spectra, which showed the typical signal pattern for charred systems, was not affected by the presence of paramagnetic centers. Although paramagnetism was negligible for the acquisition of solid state spectra, it was effective in some of the relaxometry experiments. For this reason, no useful information could be retrieved about water dynamics in marc char. Conversely, both relaxograms and nuclear magnetic resonance dispersion profiles of poplar and conifer chars indicated that poplar char is richer in small-sized pores, while larger pores appear to be characteristic for the conifer char. Conclusions: This study showed the potential of relaxometry in

  1. A simple mathematical model and practical approach for evaluating citric acid cycle fluxes in perfused rat hearts by 13C-NMR and 1H-NMR spectroscopy.

    Science.gov (United States)

    Tran-Dinh, S; Hoerter, J A; Mateo, P; Bouet, F; Herve, M

    1997-04-15

    We propose a simple mathematical model and a practical approach for evaluating the flux constant and the absolute value of flux in the citric acid cycle in perfused organs by 13C-NMR and 1H-NMR spectroscopy. We demonstrate that 13C-NMR glutamate spectra are independent of the relative sizes of the mitochondrial and cytosolic compartments and the exchange rates of glutamates, unless there is a difference in 13C chemical shifts of glutamate carbons between the two compartments. Wistar rat hearts (five beating and four KCl-arrested hearts) were aerobically perfused with 100% enriched [2-(13)C]acetate and the kinetics of glutamate carbon labeling from perchloric acid extracts were studied at various perfusion times. Under our experimental conditions, the citric acid cycle flux constant, which represents the fraction of glutamate in exchange with the citric acid cycle per unit time, is about 0.350 +/- 0.003 min(-1) for beating hearts and 0.0741 +/- 0.004 min(-1) for KCl-arrested hearts. The absolute values of the citric acid flux for beating hearts and for KCl-arrested hearts are 1.06 +/- 0.06 micromol x min(-1) x mg(-1) and 0.21 +/- 0.02 micromol x min(-1) x g(-1), respectively. The fraction of unlabeled acetate determined from the proton signal of the methyl group is small and essentially the same in beating and arrested hearts (7.4 +/- 1.7% and 8.8 +/- 2.1%, respectively). Thus, the large difference in the Glu C2/C4 between beating and arrested hearts is not due to the important contribution from anaplerotic sources in arrested hearts but simply to a substantial difference in citric acid cycle fluxes. Our model fits the experimental data well, indicating a fast exchange between 2-oxoglutarate and glutamate in the mitochondria of rat hearts. Analysis of the flux constant, calculated from the half-time of glutamate C4 labeling given in the literature, allows for a comparison of the citric acid flux for various working conditions in different animal species.

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

    Science.gov (United States)

    Ishima, Rieko

    2015-09-01

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

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

    Science.gov (United States)

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

    2015-01-01

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

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

    Science.gov (United States)

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

    2015-01-01

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

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

    Science.gov (United States)

    Allnér, Olof; Foloppe, Nicolas; Nilsson, Lennart

    2015-01-22

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

  6. Metabolic Profiling of Intact Arabidopsis thaliana Leaves during Circadian Cycle Using 1H High Resolution Magic Angle Spinning NMR

    Science.gov (United States)

    van Schadewijk, R.; de Groot, H. J. M.; Alia, A.

    2016-01-01

    Arabidopsis thaliana is the most widely used model organism for research in plant biology. While significant advances in understanding plant growth and development have been made by focusing on the molecular genetics of Arabidopsis, extracting and understanding the functional framework of metabolism is challenging, both from a technical perspective due to losses and modification during extraction of metabolites from the leaves, and from the biological perspective, due to random variation obscuring how well the function is performed. The purpose of this work is to establish the in vivo metabolic profile directly from the Arabidopsis thaliana leaves without metabolite extraction, to reduce the complexity of the results by multivariate analysis, and to unravel the mitigation of cellular complexity by predominant functional periodicity. To achieve this, we use the circadian cycle that strongly influences metabolic and physiological processes and exerts control over the photosynthetic machinery. High resolution-magic angle spinning nuclear magnetic resonance (HR-MAS NMR) was applied to obtain the metabolic profile directly from intact Arabidopsis leaves. Combining one- and two-dimensional 1H HR-MAS NMR allowed the identification of several metabolites including sugars and amino acids in intact leaves. Multivariate analysis on HR-MAS NMR spectra of leaves throughout the circadian cycle revealed modules of primary metabolites with significant and consistent variations of their molecular components at different time points of the circadian cycle. Since robust photosynthetic performance in plants relies on the functional periodicity of the circadian rhythm, our results show that HR-MAS NMR promises to be an important non-invasive method that can be used for metabolomics of the Arabidopsis thaliana mutants with altered physiology and photosynthetic efficiency. PMID:27662620

  7. Metabolic Profiling of Intact Arabidopsis thaliana Leaves during Circadian Cycle Using 1H High Resolution Magic Angle Spinning NMR.

    Science.gov (United States)

    Augustijn, D; Roy, U; van Schadewijk, R; de Groot, H J M; Alia, A

    Arabidopsis thaliana is the most widely used model organism for research in plant biology. While significant advances in understanding plant growth and development have been made by focusing on the molecular genetics of Arabidopsis, extracting and understanding the functional framework of metabolism is challenging, both from a technical perspective due to losses and modification during extraction of metabolites from the leaves, and from the biological perspective, due to random variation obscuring how well the function is performed. The purpose of this work is to establish the in vivo metabolic profile directly from the Arabidopsis thaliana leaves without metabolite extraction, to reduce the complexity of the results by multivariate analysis, and to unravel the mitigation of cellular complexity by predominant functional periodicity. To achieve this, we use the circadian cycle that strongly influences metabolic and physiological processes and exerts control over the photosynthetic machinery. High resolution-magic angle spinning nuclear magnetic resonance (HR-MAS NMR) was applied to obtain the metabolic profile directly from intact Arabidopsis leaves. Combining one- and two-dimensional 1H HR-MAS NMR allowed the identification of several metabolites including sugars and amino acids in intact leaves. Multivariate analysis on HR-MAS NMR spectra of leaves throughout the circadian cycle revealed modules of primary metabolites with significant and consistent variations of their molecular components at different time points of the circadian cycle. Since robust photosynthetic performance in plants relies on the functional periodicity of the circadian rhythm, our results show that HR-MAS NMR promises to be an important non-invasive method that can be used for metabolomics of the Arabidopsis thaliana mutants with altered physiology and photosynthetic efficiency.

  8. Dynamics of water solutions of natural polysaccharides by fast field cycling nmr relaxometry

    Science.gov (United States)

    Prusova, Alena; Conte, Pellegrino; Kucerik, Jiri; de Pasquale, Claudio; Alonzo, Giuseppe

    2010-05-01

    Cryobiology studies the effect of low temperatures on living systems such as microorganisms and plants. In particular, plants growing in cold or frozen environments can survive such extreme conditions due to the cold hardening process. Hardening is a three step process during which, first, translocation of polysaccharides to the plant roots affects water structure in the cell-soil surface. For this reason, increase of cell-membrane permeability and resistance to temperatures from -5°C to -10°C is achieved. In a second step, chemical alteration of cell membrane arises and resistance to temperatures up to -20°C is obtained. The last hardening step consists in the vitrification of the plant tissues which allow plants to survive at temperatures as low as -50°C. Since polysaccharides play a very important role in the initial part of the cold hardening process, it is of paramount importance to study the effect of such natural biopolymers on water structure. Here, we present preliminary data obtained by fast field cycling NMR relaxometry on the effect of hyaluronan (an anionic, non-sulfated glycosaminoglycan) on water structure at different concentrations of the polysaccharide. Although hyaluronan is a polysaccharide found exceptionally in animal, human or bacterial bodies, in the present work it was used as a model "pilot" compound. In fact, it has an unique ability to hold water and it contains both polysaccharide and protein-like acetamido functionalities. For this reason, hyaluronan promotes the future research on other plant biopolymers such as, for instance, starch and other very specific proteins. Results revealed that different water-structure systems surround the molecule of hyaluronan in diluted and semidiluted systems. Namely, at the lowest hyaluronan concentration, three hydration shells can be recognized. The first hydration shell is made by bound water (BW) which is strongly fixed to the hyaluronan surface mainly through electrostatic interactions. A

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

    Science.gov (United States)

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

    2015-04-01

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

  10. Complete determination of the Pin1 catalytic domain thermodynamic cycle by NMR lineshape analysis.

    Science.gov (United States)

    Greenwood, Alexander I; Rogals, Monique J; De, Soumya; Lu, Kun Ping; Kovrigin, Evgenii L; Nicholson, Linda K

    2011-09-01

    The phosphorylation-specific peptidyl-prolyl isomerase Pin1 catalyzes the isomerization of the peptide bond preceding a proline residue between cis and trans isomers. To best understand the mechanisms of Pin1 regulation, rigorous enzymatic assays of isomerization are required. However, most measures of isomerase activity require significant constraints on substrate sequence and only yield rate constants for the cis isomer, [Formula: see text] and apparent Michaelis constants, [Formula: see text]. By contrast, NMR lineshape analysis is a powerful tool for determining microscopic rates and populations of each state in a complex binding scheme. The isolated catalytic domain of Pin1 was employed as a first step towards elucidating the reaction scheme of the full-length enzyme. A 24-residue phosphopeptide derived from the amyloid precurser protein intracellular domain (AICD) phosphorylated at Thr668 served as a biologically-relevant Pin1 substrate. Specific (13)C labeling at the Pin1-targeted proline residue provided multiple reporters sensitive to individual isomer binding and on-enzyme catalysis. We have performed titration experiments and employed lineshape analysis of phosphopeptide (13)C-(1)H constant time HSQC spectra to determine [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] for the catalytic domain of Pin1 acting on this AICD substrate. The on-enzyme equilibrium value of [E·trans]/[E·cis] = 3.9 suggests that the catalytic domain of Pin1 is optimized to operate on this substrate near equilibrium in the cellular context. This highlights the power of lineshape analysis for determining the microscopic parameters of enzyme catalysis, and demonstrates the feasibility of future studies of Pin1-PPIase mutants to gain insights on the catalytic mechanism of this important enzyme.

  11. Complete determination of the Pin1 catalytic domain thermodynamic cycle by NMR lineshape analysis

    Energy Technology Data Exchange (ETDEWEB)

    Greenwood, Alexander I.; Rogals, Monique J.; De, Soumya [Cornell University, Department of Molecular Biology and Genetics (United States); Lu, Kun Ping [Cancer Biology Program and Biology of Aging Program, Beth Israel Deaconess Medical Center, Harvard Medical School (United States); Kovrigin, Evgenii L. [Marquette University, Chemistry Department (United States); Nicholson, Linda K., E-mail: lkn2@cornell.edu [Cornell University, Department of Molecular Biology and Genetics (United States)

    2011-09-15

    The phosphorylation-specific peptidyl-prolyl isomerase Pin1 catalyzes the isomerization of the peptide bond preceding a proline residue between cis and trans isomers. To best understand the mechanisms of Pin1 regulation, rigorous enzymatic assays of isomerization are required. However, most measures of isomerase activity require significant constraints on substrate sequence and only yield rate constants for the cis isomer, k{sub cat}{sup cis} and apparent Michaelis constants, K{sub M}{sup App}. By contrast, NMR lineshape analysis is a powerful tool for determining microscopic rates and populations of each state in a complex binding scheme. The isolated catalytic domain of Pin1 was employed as a first step towards elucidating the reaction scheme of the full-length enzyme. A 24-residue phosphopeptide derived from the amyloid precurser protein intracellular domain (AICD) phosphorylated at Thr668 served as a biologically-relevant Pin1 substrate. Specific {sup 13}C labeling at the Pin1-targeted proline residue provided multiple reporters sensitive to individual isomer binding and on-enzyme catalysis. We have performed titration experiments and employed lineshape analysis of phosphopeptide {sup 13}C-{sup 1}H constant time HSQC spectra to determine k{sub cat}{sup cis}, k{sub cat}{sup trans}, K{sub D}{sup cis}, and K{sub D}{sup trans} for the catalytic domain of Pin1 acting on this AICD substrate. The on-enzyme equilibrium value of [E{center_dot}trans]/[E{center_dot}cis] = 3.9 suggests that the catalytic domain of Pin1 is optimized to operate on this substrate near equilibrium in the cellular context. This highlights the power of lineshape analysis for determining the microscopic parameters of enzyme catalysis, and demonstrates the feasibility of future studies of Pin1-PPIase mutants to gain insights on the catalytic mechanism of this important enzyme.

  12. Resonances in field-cycling NMR on molecular crystals. (reversible) Spin dynamics or (irreversible) relaxation?; Resonanzen in Field-Cycling-NMR an Molekuelkristallen. (reversible) Spindynamik oder (irreversible) Relaxation?

    Energy Technology Data Exchange (ETDEWEB)

    Tacke, Christian

    2015-07-01

    Multi spin systems with spin 1/2 nuclei and dipolar coupled quadrupolar nuclei can show so called ''quadrupolar dips''. There are two main reasons for this behavior: polarization transfer and relaxation. They look quite alike and without additional research cannot be differentiated easily in most cases. These two phenomena have quite different physical and theoretical backgrounds. For no or very slow dynamics, polarization transfer will take place, which is energy conserving inside the spin system. This effect can entirely be described using quantum mechanics on the spin system. Detailed knowledge about the crystallography is needed, because this affects the relevant hamiltonians directly. For systems with fast enough dynamics, relaxation takes over, and the energy flows from the spin system to the lattice; thus a more complex theoretical description is needed. This description has to include a dynamic model, usually in the form of a spectral density function. Both models should include detailed modelling of the complete spin system. A software library was developed to be able to model complex spin systems. It allows to simulate polarization transfer or relaxation effects. NMR measurements were performed on the protonic conductor K{sub 3}H(SO{sub 4}){sub 2}. A single crystal shows sharp quadrupolar dips at room temperature. Dynamics could be excluded using relaxation measurements and literature values. Thus, a polarization transfer analysis was used to describe those dips with good agreement. As a second system, imidazolium based molecular crystals were analyzed. The quadrupolar dips were expected to be caused by polarization transfer; this was carefully analyzed and found not to be true. A relaxation based analysis shows good agreement with the measured data in the high temperature area. It leverages a two step spectral density function, which indicates two distinct dynamic processes happening in this system.

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

    Institute of Scientific and Technical Information of China (English)

    杨晓冬; 缪希茄

    2002-01-01

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

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

    Science.gov (United States)

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

    2008-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-07-01

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

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

    Science.gov (United States)

    Blechta, Vratislav; Schraml, Jan

    2015-06-01

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

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

    Indian Academy of Sciences (India)

    Shivanand M Pudakalakatti; Abhinav Dubey; Hanudatta S Atreya

    2015-06-01

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

  18. Enhancing the revenue cycle experience for patients.

    Science.gov (United States)

    Consolver, Patti; Phillips, Scott

    2014-09-01

    In 2013, Texas Health Resources began to record discussions with patients at each revenue cycle touch point, from scheduling through registration. The recordings give leaders insight on the accuracy and consistency of information communicated at each touch point and provide a tool for improving customer service. The initiative has improved patient satisfaction and increased point-of-service collections.

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

    Science.gov (United States)

    Cacciatore, Stefano; Saccenti, Edoardo; Piccioli, Mario

    2015-03-01

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

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

    Science.gov (United States)

    Manu, V. S.; Veglia, Gianluigi

    2016-12-01

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

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

    Science.gov (United States)

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

    2014-09-01

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

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

    Science.gov (United States)

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

    2014-09-01

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

  3. Applying design of experiments to a compression refrigeration cycle

    OpenAIRE

    Nuno Ricardo Costa; João Garcia

    2015-01-01

    Refrigeration cycles are used in a large diversity of industrial and domestic (residential and non-residential) equipment and their efficiency depend on several variables. To better understanding of how controllable variables impact on a compression refrigeration cycle efficiency, statistically designed experiments were conducted and data were analyzed. A quadratic polynomial model was fitted to Coefficient of Performance and variable settings to maximize cycle efficiency identified. Results ...

  4. Applying design of experiments to a compression refrigeration cycle

    Directory of Open Access Journals (Sweden)

    Nuno Ricardo Costa

    2015-12-01

    Full Text Available Refrigeration cycles are used in a large diversity of industrial and domestic (residential and non-residential equipment and their efficiency depend on several variables. To better understanding of how controllable variables impact on a compression refrigeration cycle efficiency, statistically designed experiments were conducted and data were analyzed. A quadratic polynomial model was fitted to Coefficient of Performance and variable settings to maximize cycle efficiency identified. Results give confidence to use the illustrated approach for refrigeration cycle design and operation improvement purposes.

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

    Science.gov (United States)

    Simorellis, Alana K.; Flynn, Peter F.

    2004-10-01

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

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

    Science.gov (United States)

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

    2009-03-14

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

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

    Science.gov (United States)

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

    2015-11-01

    on how motional reorientation experiments can be applied to current problems in chemistry, molecular biology, and materials science, given the many advances in high-field NMR magnets, fast spinning, and sample preparation realized in recent years.

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

    Science.gov (United States)

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

    2017-07-01

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

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

    Science.gov (United States)

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

    2010-08-01

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

  10. CycleBase.org - a comprehensive multi-organism online database of cell-cycle experiments

    DEFF Research Database (Denmark)

    Gauthier, Nicholas Paul; Larsen, Malene Erup; Wernersson, Rasmus

    2007-01-01

    .org, for viewing and downloading these data. The user interface facilitates searches for genes of interest as well as downloads of genome-wide results. Individual genes are displayed with graphs of expression profiles throughout the cell cycle from all available experiments. These expression profiles...

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

    Science.gov (United States)

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

    2014-01-01

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

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

    Science.gov (United States)

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

    2016-05-09

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

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

    Science.gov (United States)

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

    2015-01-01

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

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

    Science.gov (United States)

    Hartel, Aaron M.; Moore, Amy C.

    2014-01-01

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

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

    Science.gov (United States)

    Isaac-Lam, Meden F.

    2014-01-01

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

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

    Science.gov (United States)

    Hartel, Aaron M.; Moore, Amy C.

    2014-01-01

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

  17. Adverse childhood event experiences, fertility difficulties and menstrual cycle characteristics.

    Science.gov (United States)

    Jacobs, Marni B; Boynton-Jarrett, Renee D; Harville, Emily W

    2015-01-01

    Increased childhood adversity may be affect adult fertility, however, the mechanism through which this occurs is unclear. Menstrual cycle abnormalities are predictive of fertility difficulties, and stress influences menstrual cycle characteristics. Here, we assess whether adverse childhood experiences (ACEs) are associated with fertility difficulties and menstrual cycle dysregulation, offering a plausible mechanism for the link between lifetime stress and fertility. From April 2012 to February 2014, 742 pregnant and non-pregnant women aged 18-45 years residing in southeastern Louisiana provided information on childhood adversity and reproductive history. Associations between ACEs and fertility difficulties and menstrual cycle patterns were evaluated. As the number of ACEs increased, risk of fertility difficulties and amenorrhea increased (RR = 1.09, 95% CI 1.05-1.13 and RR = 1.07, 95% CI 1.04-1.10, respectively), while fecundability decreased [fecundability ratio (FR) = 0.97, 95% CI 0.95-1.00]. Compared to women with no adversity, women in the high adversity group were more likely to experience both infertility and amenorrhea (RR = 2.75, 95% CI 1.45-5.21 and RR = 2.54, 95% CI 1.52-4.25, respectively), and reduced fecundability (FR = 0.75, 95% CI 0.56-1.00). Although similar patterns were seen for menstrual cycle irregularity, associations were diminished. Associations did not materially change following adjustment for age, body mass index, race, education, smoking and income. Results are constrained by the self-report nature of the study and the limited generalizability of the study population. To our knowledge, this is the first study to present evidence of a link between childhood stressors, menstrual cycle disruption and fertility difficulties. The effect of childhood stress on fertility may be mediated through altered functioning of the HPA axis, acting to suppress fertility in response to less than optimal reproductive circumstances.

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

    Science.gov (United States)

    Mak, Kendrew K. W.

    2004-01-01

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

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

    Science.gov (United States)

    Mak, Kendrew K. W.

    2004-01-01

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

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

    Science.gov (United States)

    Hilty, Christian; Bowen, Sean

    2010-01-01

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

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

    NARCIS (Netherlands)

    Cacciatore, S.; Saccenti, E.; Piccioli, M.

    2015-01-01

    We present here an innovative hypothesis and report preliminary evidence that the sound of NMR signals could provide an alternative to the current representation of the individual metabolic fingerprint and supply equally significant information. The NMR spectra of the urine samples provided by four

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

    KAUST Repository

    Straasø, Lasse Arnt

    2016-02-02

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

  3. Mathematical models for determining metabolic fluxes through the citric acid and the glyoxylate cycles in Saccharomyces cerevisiae by 13C-NMR spectroscopy.

    Science.gov (United States)

    Tran-Dinh, S; Bouet, F; Huynh, Q T; Herve, M

    1996-12-15

    We propose, first, a practical method for studying the isotopic transformation of glutamate or any other metabolite isotopomers in the citric acid and the glyoxylate cycles; second, two mathematical models, one for evaluating the flux through the citric acid cycle and the other for evaluating the flux through the latter coupled to the glyoxylate cycle in yeast. These models are based on the analysis of 13C-NMR spectra of glutamate obtained from Saccharomyces cerevisiae, NCYC strain, fed with 100% enriched [2-13C]acetate. The population of each glutamate isotopomer, the change in intensity of each multiplet component or the enrichment of any glutamate carbon is expressed by a specific analytical equation from which the flux in the citric acid and the glyoxylate cycles can be deduced. The aerobic metabolism of 100% [2-13C]acetate in acetate-grown S. cerevisiae cells was studied as a function of time using 13C-NMR. 1H-NMR and biochemical techniques. The C1 and C6 doublet and singlet of labeled trehalose increase continuously with time indicating that there is no isotopic transformation between trehalose isotopomers even though the corresponding formation rates are different. By contrast, the glutamate C4 singlet increases then decreases with time. The C4 doublet, which is lower than the singlet for t 90 min. A similar observation was made for the C2 resonance singlet and doublet. In addition, the glutamate C2 multiplet consists of only seven instead of nine peaks as in random labeling. These results agree well with our models and demonstrate that, in the presence of acetate, anaplerotic carbon sources involved in the synthesis of acetyl-CoA are negligible in yeast. The flux in the citric acid cycle was deduced from a plot of the C4 area versus incubation time, while the flux within the glyoxylate cycle was determined from the relative intensity of the glutamate C4 doublet and singlet. The fluxes in the citric acid and the glyoxylate cycles were found to be comparable

  4. 13C-NMR spectroscopic evaluation of the citric acid cycle flux in conditions of high aspartate transaminase activity in glucose-perfused rat hearts.

    Science.gov (United States)

    Tran-Dinh, S; Hoerter, J A; Mateo, P; Gyppaz, F; Herve, M

    1998-12-01

    A new mathematical model, based on the observation of 13C-NMR spectra of two principal metabolites (glutamate and aspartate), was constructed to determine the citric acid cycle flux in the case of high aspartate transaminase activity leading to the formation of large amounts of labeled aspartate and glutamate. In this model, the labeling of glutamate and aspartate carbons by chemical and isotopic exchange with the citric acid cycle are considered to be interdependent. With [U-13C]Glc or [1,2-(13)C]acetate as a substrate, all glutamate and aspartate carbons can be labeled. The isotopic transformations of 32 glutamate isotopomers into 16 aspartate isotopomers or vice versa were studied using matrix operations; the results were compiled in two matrices. We showed how the flux constants of the citric acid cycle and the 13C-enrichment of acetyl-CoA can be deduced from 13C-NMR spectra of glutamate and/or aspartate. The citric acid cycle flux in beating Wistar rat hearts, aerobically perfused with [U-13C]glucose in the absence of insulin, was investigated by 13C-NMR spectroscopy. Surprisingly, aspartate instead of glutamate was found to be the most abundantly-labeled metabolite, indicating that aspartate transaminase (which catalyses the reversible reaction: (glutamate + oxaloacetate 2-oxoglutarate + aspartate) is highly active in the absence of insulin. The amount of aspartate was about two times larger than glutamate. The quantities of glutamate (G0) or aspartate (A0) were approximately the same for all hearts and remained constant during perfusion: G0 = (0.74 +/- 0.03) micromol/g; A0 = (1.49 +/- 0.05) micromol/g. The flux constants, i.e., the fraction of glutamate and aspartate in exchange with the citric acid cycle, were about 1.45 min(-1) and 0.72 min(-1), respectively; the flux of this cycle is about (1.07 +/- 0.02) micromol min(-1) g(-1). Excellent agreement between the computed and experimental data was obtained, showing that: i) in the absence of insulin, only 41

  5. Metabolic cycles in primary metabolism of cell suspensions of Daucus carota L. analysed by C-NMR

    NARCIS (Netherlands)

    Krook, J.

    1999-01-01

    In the work described in this thesis, uptake and conversion of sugar by cells of batch-grown suspensions of Daucus carota L. were studied. Invasive techniques (measurements of enzyme activities and sugar and starch levels) and non-invasive techniques ( 13C-NMR) were used to

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

    Indian Academy of Sciences (India)

    Samanwita Pal

    2010-07-01

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

  7. Diurnal cycle of convection during the CAIPEEX 2011 experiment

    Science.gov (United States)

    Resmi, EA; Malap, Neelam; Kulkarni, Gayatri; Murugavel, P.; Nair, Sathy; Burger, Roelof; Prabha, Thara V.

    2016-10-01

    The diurnal cycle of convective storm events is investigated in the study with the help of C-band radar reflectivity data during the Cloud Aerosol Interaction and Precipitation Enhancement Experiment (CAIPEEX 2011) in combination with other ground-based observations. A threshold reflectivity of 25 dBZ is used to identify the initiation of storms. Observations from collocated sensors such as a microwave radiometer profiler, water vapor measurement from eddy covariance system, and wind lidar measurements are used to investigate the characteristic features and diurnal cycle of convectively initiated storms from 21st September to 5th November 2011. The maximum reflectivity follows a normal distribution with a mean value of 40 dBZ. The cloud depth over the domain varied between 5 and 15 km corresponding to a range of reflectivity of 30-50 dBZ values. In the diurnal cycle, double maximum in the precipitation flux is noted—one during the afternoon hours associated with the diurnal heating and the other in the nocturnal periods. The nocturnal precipitation maximum is attributed to initiation of several single-cell storms (of congestus type) with a duration that is larger than the storms initiated during the daytime. The convective available potential energy (CAPE) showed a diurnal variation and was directly linked with the surface level water vapor content. The high CAPE favored single storms with a reflectivity >40 dBZ and higher echo top heights. In the evening or late night hours, a nocturnal low-level jet present over the location together with the reduced stability above the cloud base favored enhancement of low-level moisture, CAPE, and further initiation of new convection. The study illustrated how collocated observations could be used to study storm initiation and associated thermodynamic features.

  8. Mathematical model for evaluating the Krebs cycle flux with non-constant glutamate-pool size by 13C-NMR spectroscopy. Evidence for the existence of two types of Krebs cycles in cells.

    Science.gov (United States)

    Tran-Dinh, S; Beganton, F; Nguyen, T T; Bouet, F; Herve, M

    1996-12-01

    A practical method using matrix operations is proposed for studying the isotopic transformation of glutamate, or any other metabolite isotopomers, in the Krebs cycle. Two mathematical models were constructed for evaluating the Krebs cycle flux where the enrichment of [2-13C]acetyl-CoA is not 100% and the total glutamate concentration remains constant or varies during incubation. A comparative study of [1-13C]glucose metabolism was subsequently carried out using Saccharomyces cerevisiae cells from two different strains (ATCC-9763 and NCYC-239) by 13C-NMR spectroscopy and biochemical techniques. The results show that there are two types of Krebs cycles in cells. The first is represented by the ATCC cells which contain a small amount of 2-oxoglutarate dehydrogenase and hence the flux in the Krebs cycle is negligible. With [1-13C]glucose as a carbon source, the 13C-NMR spectra of glutamate exhibit the C2 and C4 resonances that are almost equivalent and much greater than that of the C3. Labeled metabolites derived from [1-13C]glucose enter the Krebs cycle at two points: oxaloacetate and citrate. The second cell type is represented by NCYC-239. The C2 and C3 areas are equivalent and smaller than the C4 resonance. The results suggest that labeled metabolites enter the Krebs cycle only at the citrate level via acetyl-CoA, 2-oxoglutarate dehydrogenase is present but pyruvate carboxylase is virtually absent or inactivated. When both are incubated with glucose, the total concentration of glutamate was found to decrease with the incubation time. The fraction of glutamate in isotopic exchange with the Krebs cycle in NCYC-239 cells is about 2.6% and the reduction in glutamate concentration is about 0.5%/min. Using our model, with a variable glutamate pool size, good agreement between the theoretical and experimental data is obtained.

  9. Abuse experiences, perceptions, and associated decisions during the childbearing cycle.

    Science.gov (United States)

    Lutz, Kristin F

    2005-11-01

    The study purpose was to generate a theoretical understanding of women's experiences and perceptions of intimate partner abuse during the childbearing cycle. Dimensional analysis, a grounded theory method, was used. Twenty-one interviews were conducted with 12 women who were (a) currently in an abusive relationship with an intimate male partner and pregnant or postpartum (n = 5) or who had (b) experienced abuse by an intimate male partner during a past pregnancy or postpartum (n = 7). Disparities between the two concurrent phenomena of abuse and pregnancy led women to feel as though they were living two separate lives. Pregnancy provided the impetus for reinvesting in the partnered relationship and constructing a family. Leaving an abusive relationship was not considered unless the partner ended the relationship first or the woman perceived an increased risk of danger. Postpartum up to 2 years after birth was a critical transitional time for women.

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

    Science.gov (United States)

    2007-11-02

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

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

    NARCIS (Netherlands)

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

    1998-01-01

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

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

    NARCIS (Netherlands)

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

    1998-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Meier, R.; Schneider, E.; Rössler, E. A. [Experimentalphysik II, Universität Bayreuth, D-95440 Bayreuth (Germany)

    2015-01-21

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

  14. NMR GHZ

    CERN Document Server

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

    1998-01-01

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

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

    DEFF Research Database (Denmark)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2013-10-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-10-15

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

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

    Science.gov (United States)

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

    2009-05-01

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

  19. Magnetoreception in birds: II. Behavioural experiments concerning the cryptochrome cycle.

    Science.gov (United States)

    Wiltschko, Roswitha; Gehring, Dennis; Denzau, Susanne; Nießner, Christine; Wiltschko, Wolfgang

    2014-12-01

    Behavioural tests of the magnetic compass of birds and corresponding immunohistological studies on the activation of retinal cryptochrome 1a, the putative receptor molecule, showed oriented behaviour and activated Cry1a under 373 nm UV, 424 nm blue, 502 nm turquoise and 565 nm green light, although the last wavelength does not allow the first step of photoreduction of cryptochrome to the semiquinone form. The tested birds had been kept under 'white' light before, hence we suggested that there was a supply of semiquinone present at the beginning of the exposure to green light that could be further reduced and then re-oxidized. To test the hypothesis in behavioural experiments, we tested robins, Erithacus rubecula, under various wavelengths (1) after 1 h pre-exposure to total darkness and (2) after 1 h pre-exposure to the same light as used in the test. The birds were oriented under blue and turquoise light, where the full cryptochrome cycle can run, but not under green light. This finding is in agreement with the hypothesis. Orientation under green light appears to be a transient phenomenon until the supply of semiquinone is depleted.

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

    CERN Document Server

    Kumar, Dinesh

    2013-01-01

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

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

    Science.gov (United States)

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

    2006-09-01

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

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

    OpenAIRE

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

    2017-01-01

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

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

    Science.gov (United States)

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

    2016-07-01

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

  4. Effects of organic amendments on natural organic matter in bulk soils from an italian agricultural area as assessed by Fast Field Cycling NMR relaxometry

    Science.gov (United States)

    Scotti, Riccardo; Conte, Pellegrino; Alonzo, Giuseppe; Rao, Maria A.

    2010-05-01

    Losses of soil organic carbon often occur in soil because of intensive agricultural practices. This is due both to removal of organic carbon following harvest production and to insufficient inputs of organic amendments. Natural organic matter (NOM) can be a very appropriate material for enhancing organic carbon content in very stressed agricultural soils. In general, NOM plays an important role in environmental matrices due, for example, to its capacity in retaining water, in interacting with organic and inorganic pollutants, and in enhancing nutrient availability to plants. For this reason, the understanding of the mechanisms with which NOM interacts with other chemicals in the environment is of paramount importance. Structural and conformational NOM characteristics can be analysed by high field (HF) nuclear magnetic resonance (NMR) spectroscopy either in the solid or in the liquid state. In both cases, information on the chemical nature of NOM can be achieved. Moreover, relaxometry studies can be also conducted to provide information on the molecular dynamics of natural organic matter. However, HF-NMR relaxometry limitations are related to the strength of the magnetic fields which limits the range of relaxation rates that can be investigated. In fact, high magnetic fields (e.g. ≥108 Hz) reduce the possibilities to observe molecular dynamics at very low frequencies such as those between 106 and 103 Hz. To this aim, nuclear magnetic resonance relaxometry at low fields and in the fast field cycling (FFC) setup is the most powerful way to retrieve information on the dynamics at low frequencies. Here, FFC-NMR relaxometry studies on soils subjected to different organic amendements are presented. Two farms, in an important agricultural area of Campania Region, Italy, were selected in order to study the effect of different organic amendments on bulk soils. Namely, a compost from municipal solid wastes and wood-wastes (scraps of poplars pruning) were applied in

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

    Science.gov (United States)

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

    2011-03-24

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

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

    Science.gov (United States)

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

    2005-01-01

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

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

    Science.gov (United States)

    Cook, A. Gilbert; Feltman, Paul M.

    2007-01-01

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

  8. Magnetic field-cycling NMR and (14)N, (17)O quadrupole resonance in the explosive pentaerythritol tetranitrate (PETN).

    Science.gov (United States)

    Smith, John A S; Rayner, Timothy J; Rowe, Michael D; Barras, Jamie; Peirson, Neil F; Stevens, Andrew D; Althoefer, Kaspar

    2010-05-01

    The explosive pentaerythritol tetranitrate (PETN) C(CH(2)-O-NO(2))(4) has been studied by (1)H NMR and (14)N NQR. The (14)N NQR frequency and spin-lattice relaxation time T(1Q) for the nu(+) line have been measured at temperatures from 255 to 325K. The (1)H NMR spin-lattice relaxation time T(1) has been measured at frequencies from 1.8kHz to 40MHz and at temperatures from 250 to 390K. The observed variations are interpreted as due to hindered rotation of the NO(2) group about the bond to the oxygen atom of the CH(2)-O group, which produces a transient change in the dipolar coupling of the CH(2) protons, generating a step in the (1)H T(1) at frequencies between 2 and 100kHz. The same mechanism could also explain the two minima observed in the temperature variation of the (14)N NQR T(1Q) near 284 and 316K, due in this case to the transient change in the (14)N...(1)H dipolar interaction, the first attributed to hindered rotation of the NO(2) group and the second to an increase in torsional amplitude of the NO(2) group due to molecular distortion of the flexible CH(2)-O-NO(2) chain which produces a 15% increase in the oscillational amplitude of the CH(2) group. The correlation times governing the (1)H T(1) values are approximately 25 times longer than those governing the (14)N NQR T(1Q), explained by the slow spin-lattice cross-coupling between the two spin systems. At higher frequencies, the (1)H T(1) dispersion results show well-resolved dips between 200 and 904kHz assigned to level crossing with (14)N and weaker features between 3 and 5MHz tentatively assigned to level crossing with (17)O. Copyright 2010 Elsevier Inc. All rights reserved.

  9. 14 CFR 121.434 - Operating experience, operating cycles, and consolidation of knowledge and skills.

    Science.gov (United States)

    2010-01-01

    ... consolidation of knowledge and skills. 121.434 Section 121.434 Aeronautics and Space FEDERAL AVIATION... Qualifications § 121.434 Operating experience, operating cycles, and consolidation of knowledge and skills. (a... operating experience, operating cycles, and line operating flight time for consolidation of knowledge and...

  10. High-resolution NMR field-cycling device for full-range relaxation and structural studies of biopolymers on a shared commercial instrument

    Energy Technology Data Exchange (ETDEWEB)

    Redfield, Alfred G., E-mail: redfield@brandeis.edu [Brandeis University, Biochemistry Department (United States)

    2012-02-15

    Improvements are described in a shuttling field-cycling device (Redfield in Magn Reson Chem 41:753-768, 2003), designed to allow widespread access to this useful technique by configuring it as a removable module to a commercial 500 MHz NMR instrument. The main improvements described here, leading to greater versatility, high reliability and simple construction, include: shuttling provided by a linear motor driven by an integrated-control servomotor; provision of automated bucking magnets to allow fast two-stage cycling to nearly zero field; and overall control by a microprocessor. A brief review of history and publications that have used the system is followed by a discussion of topics related to such a device including discussion of some future applications. A description of new aspects of the shuttling device follows. The minimum round trip time to 1T and above is less than 0.25 s and to 0.002 T is 0.36 s. Commercial probes are used and sensitivity is that of the host spectrometer reduced only by relaxation during travel. A key element is development of a linkage that prevents vibration of the linear motor from reaching the probe.

  11. High-resolution NMR field-cycling device for full-range relaxation and structural studies of biopolymers on a shared commercial instrument.

    Science.gov (United States)

    Redfield, Alfred G

    2012-02-01

    Improvements are described in a shuttling field-cycling device (Redfield in Magn Reson Chem 41:753-768, 2003), designed to allow widespread access to this useful technique by configuring it as a removable module to a commercial 500 MHz NMR instrument. The main improvements described here, leading to greater versatility, high reliability and simple construction, include: shuttling provided by a linear motor driven by an integrated-control servomotor; provision of automated bucking magnets to allow fast two-stage cycling to nearly zero field; and overall control by a microprocessor. A brief review of history and publications that have used the system is followed by a discussion of topics related to such a device including discussion of some future applications. A description of new aspects of the shuttling device follows. The minimum round trip time to 1T and above is less than 0.25 s and to 0.002 T is 0.36 s. Commercial probes are used and sensitivity is that of the host spectrometer reduced only by relaxation during travel. A key element is development of a linkage that prevents vibration of the linear motor from reaching the probe.

  12. Teaching NMR Using Online Textbooks

    Directory of Open Access Journals (Sweden)

    Joseph P. Hornak

    1999-12-01

    Full Text Available Nuclear magnetic resonance (NMR spectroscopy has almost become an essential analytical tool for the chemist. High-resolution one- and multi-dimensional NMR, timedomain NMR, and NMR microscopy are but a few of the NMR techniques at a chemist's disposal to determine chemical structure and dynamics. Consequently, even small chemistry departments are finding it necessary to provide students with NMR training and experience in at least some of these techniques. The hands-on experience is readily provided with access to state-of-the-art commercial spectrometers. Instruction in the principles of NMR is more difficult to achieve as most instructors try to teach NMR using single organic or analytical chemistry book chapters with static figures. This paper describes an online textbook on NMR spectroscopy called The Basics of NMR (http://www.cis.rit.edu/htbooks/nmr/ suitable for use in teaching the principles of NMR spectroscopy. The book utilizes hypertext and animations to present the principles of NMR spectroscopy. The book can be used as a textbook associated with a lecture or as a stand-alone teaching tool. Conference participants are encouraged to review the textbook and evaluate its suitability for us in teaching NMR spectroscopy to undergraduate chemistry majors.

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

    Energy Technology Data Exchange (ETDEWEB)

    Millar, J.M.

    1986-02-01

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

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

    Science.gov (United States)

    Chevelkov, Veniamin; Fink, Uwe; Reif, Bernd

    2009-10-01

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

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

    Science.gov (United States)

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

    2011-01-01

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

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

    Science.gov (United States)

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

    2011-01-01

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

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

    Science.gov (United States)

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

    2011-01-01

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

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

    Science.gov (United States)

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

    2016-12-01

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

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

    Science.gov (United States)

    Latouche, Camille; Barone, Vincenzo

    2014-12-09

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

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

    Science.gov (United States)

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

    2012-01-01

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

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

    Science.gov (United States)

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

    2012-01-01

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

  2. A Molecular Reaction Cycle with a Solvatochromic Merocyanine Dye: An Experiment in Photochemistry, Kinetics, and Catalysis.

    Science.gov (United States)

    Abdel-Kader, M. H.; Steiner, U.

    1983-01-01

    Three experiments using merocyanine M suitable as an integrated laboratory experience for undergraduates are described. Experiments demonstrate: complete molecular cycle composed of photochemical, thermal, and protolytic reaction steps; kinetics of cis-trans isomerization of the dye; and mechanism of base catalysis for thermal isomerization of the…

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

    Science.gov (United States)

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

    2016-05-06

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

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

    Science.gov (United States)

    Huang, Hao; Milojevic, Julijana; Melacini, Giuseppe

    2008-05-08

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

  5. Automated management of life cycle for future network experiment based on description language

    Science.gov (United States)

    Niu, Hongxia; Liang, Junxue; Lin, Zhaowen; Ma, Yan

    2016-12-01

    Future network is a complex resources pool including multiple physical resources and virtual resources. Establishing experiment on future network is complicate and tedious. That achieving the automated management of future network experiments is so important. This paper brings forward the way for researching and managing the life cycle of experiment based on the description language. The description language uses the framework, which couples with a low hierarchical structure and a complete description of the network experiment. In this way, the experiment description template can be generated by this description framework accurately and completely. In reality, we can also customize and reuse network experiment by modifying the description template. The results show that this method can achieve the aim for managing the life cycle of network experiment effectively and automatically, which greatly saves time, reduces the difficulty, and implements the reusability of services.

  6. T2-Filtered T2 - T2 Exchange NMR

    Science.gov (United States)

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

    2016-05-01

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

  7. Identifying Multiple Potential Metabolic Cycles in Time-Series from Biolog Experiments

    OpenAIRE

    Shubin, Mikhail; Schaufler, Katharina; Tedin, Karsten; Vehkala, Minna; Corander, Jukka

    2016-01-01

    Biolog Phenotype Microarray (PM) is a technology allowing simultaneous screening of the metabolic behaviour of bacteria under a large number of different conditions. Bacteria may often undergo several cycles of metabolic activity during a Biolog experiment. We introduce a novel algorithm to identify these metabolic cycles in PM experimental data, thus increasing the potential of PM technology in microbiology. Our method is based on a statistical decomposition of the time-series measurements i...

  8. An Oral Load of [13C3]Glycerol and Blood NMR Analysis Detect Fatty Acid Esterification, Pentose Phosphate Pathway, and Glycerol Metabolism through the Tricarboxylic Acid Cycle in Human Liver.

    Science.gov (United States)

    Jin, Eunsook S; Sherry, A Dean; Malloy, Craig R

    2016-09-01

    Drugs and other interventions for high impact hepatic diseases often target biochemical pathways such as gluconeogenesis, lipogenesis, or the metabolic response to oxidative stress. However, traditional liver function tests do not provide quantitative data about these pathways. In this study, we developed a simple method to evaluate these processes by NMR analysis of plasma metabolites. Healthy subjects ingested [U-(13)C3]glycerol, and blood was drawn at multiple times. Each subject completed three visits under differing nutritional states. High resolution (13)C NMR spectra of plasma triacylglycerols and glucose provided new insights into a number of hepatic processes including fatty acid esterification, the pentose phosphate pathway, and gluconeogenesis through the tricarboxylic acid cycle. Fasting stimulated pentose phosphate pathway activity and metabolism of [U-(13)C3]glycerol in the tricarboxylic acid cycle prior to gluconeogenesis or glyceroneogenesis. Fatty acid esterification was transient in the fasted state but continuous under fed conditions. We conclude that a simple NMR analysis of blood metabolites provides an important biomarker of pentose phosphate pathway activity, triacylglycerol synthesis, and flux through anaplerotic pathways in mitochondria of human liver.

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

    Science.gov (United States)

    Chesick, John P.

    1989-01-01

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

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

    Science.gov (United States)

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

    2017-08-01

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

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

    Science.gov (United States)

    Cavaleiro, Jose A. S.

    1987-01-01

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

  12. Introduction of Huaihe River Basin Energy and Water Cycle Experiment and Research

    Institute of Scientific and Technical Information of China (English)

    Zhou X.G.; Luo Y.F.

    2004-01-01

    @@ Huaihe River Basin Energy and Water Cycle Experiment and Research (HUBEX), as one of the Ninth Five-Year Plan (1996-2000) Major Programs supported by the National Natural Science Foundation of China (NSFC), successfully passed the check-up and won high appraisement from the experts.

  13. Introduction of Huaihe River Basin Energy and Water Cycle Experiment and Research

    Institute of Scientific and Technical Information of China (English)

    Zhou; X.G.; Luo; Y.F.

    2004-01-01

      Huaihe River Basin Energy and Water Cycle Experiment and Research (HUBEX), as one of the Ninth Five-Year Plan (1996-2000) Major Programs supported by the National Natural Science Foundation of China (NSFC), successfully passed the check-up and won high appraisement from the experts.……

  14. Modeling and Depletion Simulations for a High Flux Isotope Reactor Cycle with a Representative Experiment Loading

    Energy Technology Data Exchange (ETDEWEB)

    Chandler, David [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Reactor and Nuclear Systems Division; Betzler, Ben [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Reactor and Nuclear Systems Division; Hirtz, Gregory John [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Reactor and Nuclear Systems Division; Ilas, Germina [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Reactor and Nuclear Systems Division; Sunny, Eva [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Reactor and Nuclear Systems Division

    2016-09-01

    The purpose of this report is to document a high-fidelity VESTA/MCNP High Flux Isotope Reactor (HFIR) core model that features a new, representative experiment loading. This model, which represents the current, high-enriched uranium fuel core, will serve as a reference for low-enriched uranium conversion studies, safety-basis calculations, and other research activities. A new experiment loading model was developed to better represent current, typical experiment loadings, in comparison to the experiment loading included in the model for Cycle 400 (operated in 2004). The new experiment loading model for the flux trap target region includes full length 252Cf production targets, 75Se production capsules, 63Ni production capsules, a 188W production capsule, and various materials irradiation targets. Fully loaded 238Pu production targets are modeled in eleven vertical experiment facilities located in the beryllium reflector. Other changes compared to the Cycle 400 model are the high-fidelity modeling of the fuel element side plates and the material composition of the control elements. Results obtained from the depletion simulations with the new model are presented, with a focus on time-dependent isotopic composition of irradiated fuel and single cycle isotope production metrics.

  15. Soils, Pores, and NMR

    Science.gov (United States)

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

    2010-05-01

    Within Cluster A, Partial Project A1, the pore space exploration by means of Nuclear Magnetic Resonance (NMR) plays a central role. NMR is especially convenient since it probes directly the state and dynamics of the substance of interest: water. First, NMR is applied as relaxometry, where the degree of saturation but also the pore geometry controls the NMR signature of natural porous systems. Examples are presented where soil samples from the Selhausen, Merzenhausen (silt loams), and Kaldenkirchen (sandy loam) test sites are investigated by means of Fast Field Cycling Relaxometry at different degrees of saturation. From the change of the relaxation time distributions with decreasing water content and by comparison with conventional water retention curves we conclude that the fraction of immobile water is characterized by T1 samples (Haber-Pohlmeier et al. 2010). Third, relaxometric information forms the basis of understanding magnetic resonance imaging (MRI) results. The general difficulty of imaging in soils are the inherent fast T2 relaxation times due to i) the small pore sizes, ii) presence of paramagnetic ions in the solid matrix, and iii) diffusion in internal gradients. The last point is important, since echo times can not set shorter than about 1ms for imaging purposes. The way out is either the usage of low fields for imaging in soils or special ultra-short pulse sequences, which do not create echoes. In this presentation we will give examples on conventional imaging of macropore fluxes in soil cores (Haber-Pohlmeier et al. 2010), and the combination with relaxometric imaging, as well as the advantages and drawbacks of low-field and ultra-fast pulse imaging. Also first results on the imaging of soil columns measured by SIP in Project A3 are given. Haber-Pohlmeier, S., S. Stapf, et al. (2010). "Waterflow Monitored by Tracer Transport in Natural Porous Media Using MRI." Vadose Zone J.: submitted. Haber-Pohlmeier, S., S. Stapf, et al. (2010). "Relaxation in a

  16. NMR in pulsed magnetic field

    KAUST Repository

    Abou-Hamad, Edy

    2011-09-01

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

  17. Compact NMR

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-01

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

  18. Prior experience does not alter modulation of cutaneous reflexes during manual wheeling and symmetrical arm cycling.

    Science.gov (United States)

    MacGillivray, Megan K; Klimstra, Marc; Sawatzky, Bonita; Zehr, E Paul; Lam, Tania

    2013-05-01

    Previous research has reported that training and experience influence H-reflex amplitude during rhythmic activity; however, little research has yet examined the influence of training on cutaneous reflexes. Manual wheelchair users (MWUs) depend on their arms for locomotion. We postulated that the daily dependence and high amount of use of the arms for mobility in MWUs would show differences in cutaneous reflex modulation during upper limb cyclic movements compared with able-bodied control subjects. We hypothesized that MWUs would demonstrate increased reflex response amplitudes for both manual wheeling and symmetrical arm cycling tasks. The superficial radial nerve was stimulated randomly at different points of the movement cycle of manual wheeling and symmetrical arm cycling in MWUs and able-bodied subjects naive to wheeling. Our results showed that there were no differences in amplitude modulation of early- or middle-latency cutaneous reflexes between the able-bodied group and the MWU group. However, there were several differences in amplitude modulation of cutaneous reflexes between tasks (manual wheeling and symmetrical arm cycling). Specifically, differences were observed in early-latency responses in the anterior and posterior deltoid muscles and biceps and triceps brachii as well as in middle-latency responses in the anterior and posterior deltoid. These data suggest that manual wheeling experience does not modify the pattern of cutaneous reflex amplitude modulation during manual wheeling. The differences in amplitude modulation of cutaneous reflexes between tasks may be a result of mechanical differences (i.e., hand contact) between tasks.

  19. Education and training in LCA and life-cycle thinking experience and needs

    DEFF Research Database (Denmark)

    Jørgensen, Michael Søgaard; Bey, Niki; Hauschild, Michael Zwicky

    2003-01-01

    was gathered by means of a survey among providers and users of education and training in this field, while the qualitative data was established in the course of a dialogue meeting to which particular interested individuals, selected among those who had returned the questionnaire, were invited....... The questionnaire for providers was returned by 20 institutions, describing 47 educational offers and the questionnaire for users of education was filled by 41 companies and 16 consultancies. Most of the companies and consultancies that participated in the survey have experience with LCA and/or life cycle thinking......This paper discusses experience and needs for education and training in LCA and life-cycle thinking based on project carried out for the Environmental Protection Agency in Denmark. An approach was chosen where both quantitative and qualitative facts and records were collected. The quantitative data...

  20. Education and training in LCA and life-cycle thinking experience and needs

    DEFF Research Database (Denmark)

    Jørgensen, Michael Søgaard; Bey, Niki; Hauschild, Michael Zwicky

    2003-01-01

    was gathered by means of a survey among providers and users of education and training in this field, while the qualitative data was established in the course of a dialogue meeting to which particular interested individuals, selected among those who had returned the questionnaire, were invited......This paper discusses experience and needs for education and training in LCA and life-cycle thinking based on project carried out for the Environmental Protection Agency in Denmark. An approach was chosen where both quantitative and qualitative facts and records were collected. The quantitative data....... The questionnaire for providers was returned by 20 institutions, describing 47 educational offers and the questionnaire for users of education was filled by 41 companies and 16 consultancies. Most of the companies and consultancies that participated in the survey have experience with LCA and/or life cycle thinking...

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

    Science.gov (United States)

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

    2003-04-01

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

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

    CERN Document Server

    Segnorile, H H

    2013-01-01

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

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

    Science.gov (United States)

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

    2014-05-01

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

  4. Fundamentals of Protein NMR Spectroscopy

    CERN Document Server

    Rule, Gordon S

    2006-01-01

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

  5. Identifying Multiple Potential Metabolic Cycles in Time-Series from Biolog Experiments.

    Science.gov (United States)

    Shubin, Mikhail; Schaufler, Katharina; Tedin, Karsten; Vehkala, Minna; Corander, Jukka

    Biolog Phenotype Microarray (PM) is a technology allowing simultaneous screening of the metabolic behaviour of bacteria under a large number of different conditions. Bacteria may often undergo several cycles of metabolic activity during a Biolog experiment. We introduce a novel algorithm to identify these metabolic cycles in PM experimental data, thus increasing the potential of PM technology in microbiology. Our method is based on a statistical decomposition of the time-series measurements into a set of growth models. We show that the method is robust to measurement noise and captures accurately the biologically relevant signals from the data. Our implementation is made freely available as a part of an R package for PM data analysis and can be found at www.helsinki.fi/bsg/software/Biolog_Decomposition.

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

    Science.gov (United States)

    Kempgens, Pierre; Rosé, Jacky

    2011-03-01

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

  7. Developing a data life cycle for carbon and greenhouse gas measurements: challenges, experiences and visions

    Science.gov (United States)

    Kutsch, W. L.

    2015-12-01

    Environmental research infrastructures and big data integration networks require common data policies, standardized workflows and sophisticated e-infrastructure to optimise the data life cycle. This presentation summarizes the experiences in developing the data life cycle for the Integrated Carbon Observation System (ICOS), a European Research Infrastructure. It will also outline challenges that still exist and visions for future development. As many other environmental research infrastructures ICOS RI built on a large number of distributed observational or experimental sites. Data from these sites are transferred to Thematic Centres and quality checked, processed and integrated there. Dissemination will be managed by the ICOS Carbon Portal. This complex data life cycle has been defined in detail by developing protocols and assigning responsibilities. Since data will be shared under an open access policy there is a strong need for common data citation tracking systems that allow data providers to identify downstream usage of their data so as to prove their importance and show the impact to stakeholders and the public. More challenges arise from interoperating with other infrastructures or providing data for global integration projects as done e.g. in the framework of GEOSS or in global integration approaches such as fluxnet or SOCAt. Here, common metadata systems are the key solutions for data detection and harvesting. The metadata characterises data, services, users and ICT resources (including sensors and detectors). Risks may arise when data of high and low quality are mixed during this process or unexperienced data scientists without detailed knowledge on the data aquisition derive scientific theories through statistical analyses. The vision of fully open data availability is expressed in a recent GEO flagship initiative that will address important issues needed to build a connected and interoperable global network for carbon cycle and greenhouse gas

  8. Developing the User Experience for a Next Generation Nuclear Fuel Cycle Simulator (NGFCS)

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Paul H. [Univ. of Wisconsin, Madison, WI (United States); Schneider, Erich [Univ. of Texas, Austin, TX (United States); Pascucci, Valerio [Univ. of Utah, Salt Lake City, UT (United States); Livnat, Yarden [Univ. of Utah, Salt Lake City, UT (United States); Hiromoto, Robert [Univ. of Idaho, Moscow, ID (United States); Scopatz, Anthony [Univ. of Wisconsin, Madison, WI (United States); Brossard, Dominique [Univ. of Wisconsin, Madison, WI (United States); Scheufele, Dietram [Univ. of Wisconsin, Madison, WI (United States)

    2017-07-30

    This project made substantial progress on its original aim for providing a modern user experience for nuclear fuel cycle analysis while also creating a robust and functional next- generation fuel cycle simulator. The Cyclus kernel experienced a dramatic clari cation of its interfaces and data model, becoming a full- edged agent-based framework, with strong support for third party developers of novel archetypes. The most important contribution of this project to the the development of Cyclus was the introduction of tools to facilitate archetype development. These include automated code generation of routine archetype components, metadata annotations to provide re ection and rich description of each data member's purpose, and mechanisms for input validation and output of complex data. A comprehensive social science investigation of decision makers' interests in nuclear fuel cycles, and speci cally their interests in nuclear fuel cycle simulators (NFCSs) as tools for understanding nuclear fuel cycle options, was conducted. This included document review and analysis, stakeholder interviews, and a survey of decision makers. This information was used to study the role of visualization formats and features in communicating information about nuclear fuel cycles. A exible and user-friendly tool was developed for building Cyclus analysis models, featuring a drag-and-drop interface and automatic input form generation for novel archetypes. Cycic allows users to design fuel cycles from arbitrary collections of facilities for the rst time, with mechanisms that contribute to consistency within that fuel cycle. Interacting with some of the metadata capabilities introduced in the above-mentioned tools to support archetype development, Cycic also automates the generation of user input forms for novel archetypes with little to no special knowledge required by the archetype developers. Translation of the fundamental metrics of Cyclus into more interesting quantities is

  9. The Manuel Lujan, Jr. Neutron Scattering Center, LANSCE experiment reports: 1990 Run Cycle

    Energy Technology Data Exchange (ETDEWEB)

    DiStravolo, M.A. (comp.)

    1991-10-01

    This year was the third in which LANSCE ran a formal user program. A call for proposals was issued before the scheduled run cycles, and experiment proposals were submitted by scientists from universities, industry, and other research facilities around the world. An external program advisory committee, which LANSCE shares with the Intense Pulsed Neutron Source (IPNS), Argonne National Laboratory examined the proposals and made recommendations. At LANSCE, neutrons are produced by spallation when a pulsed, 800-MeV proton beam impinges on a tungsten target. The proton pulses are provided by the Clinton P. Anderson Meson Physics Facility (LAMPF) accelerator and an associated Proton Storage Ring (PSR), which can alter the intensity, time structure, and repetition rate of the pulses. The LAMPF protons of Line D are shared between the LANSCE target and the Weapons Neutron Research facility, which results in LANSCE spectrometers being available to external users for unclassified research about 80% of each six-month LAMPF run cycle. Measurements of interest to the Los Alamos National Laboratory may also be performed and may occupy up to an additional 20% of the available beam time. These experiments are reviewed by an internal program advisory committee. One hundred thirty-four proposals were submitted for unclassified research and twelve proposals for research of a programmatic nature to the Laboratory. Our definition of beam availability is when the proton current from the PSR exceeds 50% of the planned value. The PSR ran at 65{mu}A current (average) at 20 Hz for most of 1990. All of the scheduled experiments were performed and experiments in support of the LANSCE research program were accomplished during the discretionary periods.

  10. Combined Cycle Engine Large-Scale Inlet for Mode Transition Experiments: System Identification Rack Hardware Design

    Science.gov (United States)

    Thomas, Randy; Stueber, Thomas J.

    2013-01-01

    The System Identification (SysID) Rack is a real-time hardware-in-the-loop data acquisition (DAQ) and control instrument rack that was designed and built to support inlet testing in the NASA Glenn Research Center 10- by 10-Foot Supersonic Wind Tunnel. This instrument rack is used to support experiments on the Combined-Cycle Engine Large-Scale Inlet for Mode Transition Experiment (CCE? LIMX). The CCE?LIMX is a testbed for an integrated dual flow-path inlet configuration with the two flow paths in an over-and-under arrangement such that the high-speed flow path is located below the lowspeed flow path. The CCE?LIMX includes multiple actuators that are designed to redirect airflow from one flow path to the other; this action is referred to as "inlet mode transition." Multiple phases of experiments have been planned to support research that investigates inlet mode transition: inlet characterization (Phase-1) and system identification (Phase-2). The SysID Rack hardware design met the following requirements to support Phase-1 and Phase-2 experiments: safely and effectively move multiple actuators individually or synchronously; sample and save effector control and position sensor feedback signals; automate control of actuator positioning based on a mode transition schedule; sample and save pressure sensor signals; and perform DAQ and control processes operating at 2.5 KHz. This document describes the hardware components used to build the SysID Rack including their function, specifications, and system interface. Furthermore, provided in this document are a SysID Rack effectors signal list (signal flow); system identification experiment setup; illustrations indicating a typical SysID Rack experiment; and a SysID Rack performance overview for Phase-1 and Phase-2 experiments. The SysID Rack described in this document was a useful tool to meet the project objectives.

  11. 13C-detected NMR experiments for measuring chemical shifts and coupling constants in nucleic acid bases.

    Science.gov (United States)

    Fiala, Radovan; Sklenár, Vladimír

    2007-10-01

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

  12. Using Soil Incubation Experiments to Enhance Urban Elementary School Student Understanding of Carbon Cycling

    Science.gov (United States)

    Whittinghill, K. A.; van Vleck, H. E.; Dechaine, J. M.; Faber, N.

    2007-12-01

    Soil incubations provide a simple and low-cost way to introduce inquiry into the elementary school curriculum. As part of the University of Minnesota's NSF-funded GK-12 program, we used a replicated soil experiment to enhance a unit on global warming and carbon cycling for a 4th grade enrichment group at an urban elementary school. After completing several global warming related, inquiry based activities, the students designed an experiment to test their hypothesis that increasing temperature increases soil respiration. Students used soil from the playground placed at different temperatures within the school (computer server room, classroom, and refrigerator) to carry out their experiment. With the help of GK-12 graduate fellows, students used an infrared gas analyzer to quantify the production of carbon dioxide by the soil within mason jars. The students analyzed their data and discussed the relevance of their findings to previous lessons on global climate change. We will discuss the incubation experiment in the context of our collaboration between scientists and elementary school classrooms, inquiry based science education, and our 4th grade unit on global climate change.

  13. The relativity experiment of MORE: Global full-cycle simulation and results

    Science.gov (United States)

    Schettino, Giulia

    2015-07-01

    BepiColombo is a joint ESA/JAXA mission to Mercury with challenging objectives regarding geophysics, geodesy and fundamental physics. In particular, the Mercury Orbiter Radio science Experiment (MORE) intends, as one of its goals, to perform a test of General Relativity. This can be done by measuring and constraining the parametrized post-Newtonian (PPN) parameters to an accuracy significantly better than current one. In this work we perform a global numerical full-cycle simulation of the BepiColombo Radio Science Experiments (RSE) in a realistic scenario, focussing on the relativity experiment, solving simultaneously for all the parameters of interest for RSE in a global least squares fit within a constrained multiarc strategy. The results on the achievable accuracy for each PPN parameter will be presented and discussed, confirming the significant improvement to the actual knowledge of gravitation theory expected for the MORE relativity experiment. In particular, we will show that, including realistic systematic effects in the range observables, an accuracy of the order of 10-6 can still be achieved in the Eddington parameter β and in the parameter α1, which accounts for preferred frame effects, while the only poorly determined parameter turns out to be ζ, which describes the temporal variations of the gravitational constant and the Sun mass.

  14. The Manuel Lujan, Jr. Neutron Scattering Center (LANSCE) experiment reports 1992 run cycle. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    DiStravolo, M.A. [comp.

    1993-09-01

    This year was the fifth in which LANSCE ran a formal user program. A call for proposals was issued before the scheduled run cycles, and experiment proposals were submitted by scientists from universities, industry, and other research facilities around the world. An external program advisory committee, which LANSCE shares with the Intense Pulsed Neutron Source (IPNS), Argonne National Laboratory, examined the proposals and made recommendations. At LANSCE, neutrons are produced by spallation when a pulsed, 800-MeV proton beam impinges on a tungsten target. The proton pulses are provided by the Clinton P. Anderson Meson Physics Facility (LAMPF) accelerator and an associated Proton Storage Ring (PSR), which can alter the intensity, time structure, and repetition rate of the pulses. The LAMPF protons of Line D are shared between the LANSCE target and the Weapons Neutron Research (WNR) facility, which results in LANSCE spectrometers being available to external users for unclassified research about 80% of each annual LAMPF run cycle. Measurements of interest to the Los Alamos National Laboratory may also be performed and may occupy up to an additional 20% of the available beam time. These experiments are reviewed by an internal program advisory committee. One hundred sixty-seven proposals were submitted for unclassified research and twelve proposals for research of a programmatic interest to the Laboratory; six experiments in support of the LANSCE research program were accomplished during the discretionary periods. Oversubscription for instrument beam time by a factor of three was evident with 839 total days requested and only 371 available for allocation.

  15. Structural Characterization of Intrinsically Disordered Proteins by NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Peter Tompa

    2013-09-01

    Full Text Available Recent advances in NMR methodology and techniques allow the structural investigation of biomolecules of increasing size with atomic resolution. NMR spectroscopy is especially well-suited for the study of intrinsically disordered proteins (IDPs and intrinsically disordered regions (IDRs which are in general highly flexible and do not have a well-defined secondary or tertiary structure under functional conditions. In the last decade, the important role of IDPs in many essential cellular processes has become more evident as the lack of a stable tertiary structure of many protagonists in signal transduction, transcription regulation and cell-cycle regulation has been discovered. The growing demand for structural data of IDPs required the development and adaption of methods such as 13C-direct detected experiments, paramagnetic relaxation enhancements (PREs or residual dipolar couplings (RDCs for the study of ‘unstructured’ molecules in vitro and in-cell. The information obtained by NMR can be processed with novel computational tools to generate conformational ensembles that visualize the conformations IDPs sample under functional conditions. Here, we address NMR experiments and strategies that enable the generation of detailed structural models of IDPs.

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

    Science.gov (United States)

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

    2002-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-03-15

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

  18. The Manuel Lujan Jr. Neutron Scattering Center (LANSCE) experiment reports 1993 run cycle. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Farrer, R.; Longshore, A. [comps.

    1995-06-01

    This year the Manuel Lujan Jr. Neutron Scattering Center (LANSCE) ran an informal user program because the US Department of Energy planned to close LANSCE in FY1994. As a result, an advisory committee recommended that LANSCE scientists and their collaborators complete work in progress. At LANSCE, neutrons are produced by spallation when a pulsed, 800-MeV proton beam impinges on a tungsten target. The proton pulses are provided by the Clinton P. Anderson Meson Physics Facility (LAMPF) accelerator and a associated Proton Storage Ring (PSR), which can Iter the intensity, time structure, and repetition rate of the pulses. The LAMPF protons of Line D are shared between the LANSCE target and the Weapons Neutron Research (WNR) facility, which results in LANSCE spectrometers being available to external users for unclassified research about 80% of each annual LAMPF run cycle. Measurements of interest to the Los Alamos National Laboratory (LANL) may also be performed and may occupy up to an additional 20% of the available beam time. These experiments are reviewed by an internal program advisory committee. This year, a total of 127 proposals were submitted. The proposed experiments involved 229 scientists, 57 of whom visited LANSCE to participate in measurements. In addition, 3 (nuclear physics) participating research teams, comprising 44 scientists, carried out experiments at LANSCE. Instrument beam time was again oversubscribed, with 552 total days requested an 473 available for allocation.

  19. Cycling experiences and knowledge of the road code of nine-year-olds.

    Science.gov (United States)

    Langley, J; Silva, P A; Williams, S M

    1987-04-01

    Sex differences in cycling experience and knowledge of the road code were examined in a sample of eight-hundred and fifteen nine-year-old children. The results showed that there were not significant sex differences for those who had ridden on the road or ridden to school in the week preceding the interview. However, males were more likely to have ridden at night. There were no significant sex differences in self reported unsafe acts or in knowledge of various dimensions of the road code. The results show a relatively high level of ignorance of the give-way rules for uncontrolled intersections and a disturbing number of children who reported they had ridden at night without tail or headlights.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-08-15

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

  1. 3D H2BC: A novel experiment for small-molecule and biomolecular NMR at natural isotopic abundance

    DEFF Research Database (Denmark)

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

    2009-01-01

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

  2. Optical pumping and xenon NMR

    Energy Technology Data Exchange (ETDEWEB)

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

    1991-11-01

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

  3. Optical pumping and xenon NMR

    Energy Technology Data Exchange (ETDEWEB)

    Raftery, M.D.

    1991-11-01

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

  4. Multiplicative or t1 Noise in NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Granwehr, Josef

    2005-01-25

    The signal in an NMR experiment is highly sensitive to fluctuations of the environment of the sample. If, for example, the static magnetic field B{sub 0}, the amplitude and phase of radio frequency (rf) pulses, or the resonant frequency of the detection circuit are not perfectly stable and reproducible, the magnetic moment of the spins is altered and becomes a noisy quantity itself. This kind of noise not only depends on the presence of a signal, it is in fact proportional to it. Since all the spins at a particular location in a sample experience the same environment at any given time, this noise primarily affects the reproducibility of an experiment, which is mainly of importance in the indirect dimensions of a multidimensional experiment, when intense lines are suppressed with a phase cycle, or for difference spectroscopy techniques. Equivalently, experiments which are known to be problematic with regard to their reproducibility, like flow experiments or experiments with a mobile target, tend to be affected stronger by multiplicative noise. In this article it is demonstrated how multiplicative noise can be identified and characterized using very simple, repetitive experiments. An error estimation approach is developed to give an intuitive, yet quantitative understanding of its properties. The consequences for multidimensional NMR experiments are outlined, implications for data analysis are shown, and strategies for the optimization of experiments are summarized.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-15

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

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

    Science.gov (United States)

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

    2013-09-16

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

  7. Planning for hybrid-cycle OTEC experiments using the HMTSTA test facility at the Natural Energy Laboratory of Hawaii

    Science.gov (United States)

    Panchal, C.; Rabas, T.; Genens, L.

    The U.S. Department of Energy has built an experimental apparatus for studying the open-cycle Ocean Thermal Energy Conversion (OC-OTEC) system. Experiments using warm and cold seawater are currently underway to validate the performance predictions for an OC-TEC flash evaporator, surface condenser, and direct-contact condenser. The hybrid cycle is another OTEC option that produces both power and desalinated water, it is comparable in capital cost to OC-OTEC, and it eliminates the problems associated with the large steam turbine. Means are presented or modifying the existing apparatus to conduct similar experiments on hybrid-cycle OTEC heat exchangers. These data are required to validate predictive methods of the components and for the system integration that were identified in an earlier study of hybrid-cycle OTEC power plants.

  8. Analysis of HFIR Dosimetry Experiments Performed in Cycles 400 and 401

    Energy Technology Data Exchange (ETDEWEB)

    Remec, Igor [ORNL; Baldwin, Charles A [ORNL

    2008-09-01

    The High Flux Isotope Reactor (HFIR) has been in operation at Oak Ridge National Laboratory since 1966. To upgrade and enhance capabilities for neutron science research at the reactor, a larger HB-2 beam tube was installed in April of 2002. To assess, experimentally, the impact of this larger beam tube on radiation damage rates [i.e., displacement-per-atom (dpa) rates] used in vessel life extension studies, dosimetry experiments were performed from April to August 2004 during fuel cycles 400 and 401. This report documents the analysis of the dosimetry experiments and the determination of best-estimate dpa rates. These dpa rates are obtained by performing a least-squares adjustment of calculated neutron and gamma-ray fluxes and the measured responses of radiometric monitors and beryllium helium accumulation fluence monitors. The best-estimate dpa rates provided here will be used to update HFIR pressure vessel life extension studies, which determine the pressure/temperature limits for reactor operation and the HFIR pressure vessel's remaining life. All irradiation parameters given in this report correspond to a reactor power of 85 MW.

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

    Science.gov (United States)

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

    2008-01-01

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

  10. 3D H2BC: a novel experiment for small-molecule and biomolecular NMR at natural isotopic abundance.

    Science.gov (United States)

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

    2009-10-01

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

  11. Dynamic NMR study of dinitrophenyl derivatives of seven-membered cyclic ketals of pyridoxine.

    Science.gov (United States)

    Rakhmatullin, Ilfat Z; Galiullina, Leisan F; Garipov, Marsel' R; Strel'nik, Alexey D; Shtyrlin, Yurii G; Klochkov, Vladimir V

    2015-10-01

    Two pyridoxine derivatives containing a dinitrophenyl moiety were investigated by (1)H NMR spectroscopy. Conformational dynamics in solution were studied for each compound using dynamic NMR experiments. It was shown that both compounds studied are involved into two conformational exchange processes. The first process is a transformation of the seven-membered cycle conformation between the enantiomeric P-twist and M-twist forms, and the second is a rotation of the dinitrophenyl fragment of the molecules around the C-O bond. Energy barriers of both conformational transitions were determined.

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

    Science.gov (United States)

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

    2013-01-01

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

  13. Decontamination techniques for decommissioning nuclear cycle facilities COGEMA experience and R and R

    Energy Technology Data Exchange (ETDEWEB)

    Decobert, G.; Bordie, J. C. [COGEMA FCR/DSDP, St Quentin-en-Yvelines (France); Faury, M.; Fournel, B. [Commissariat aa l' Energie Atomique, CEN Cadarache DESD/SEP/LETD, Paul lez Durance (France)

    1999-07-01

    All industrial nuclear facilities have a limited life-time. Then, dismantling at different levels of these facilities occurs and has to be done without endangering decommissioning staff, public and environment. Decontamination is an important procedure and is often used ina dismantling operation. It doesn't noly reduce irradiation dose for workers during decommissioning operations, according to the ALARA (As Low As Reasonably Achievable) principle, but also has the potential for waste downgrading in order to achieve lower disposal costs. The COGEMA group which is world-leader in the nuclear fuel cycle from uranium prospecting to spent fuel reprocessing and recycling (including refining, conversion, enrichment of natural uranium, manufacturing of nuclear fuels and waste conditioning) has already been involved in nuclear clean-up and decommissioning programs and participates in several R and D projects with the CEA (Commissariat aa l'Energie Atomique). This paper will present first some example of the experience acquired on COGEMA and the CEA sites: - COGEMA La Hague reprocessing plant operating and heavy maintenance experience. - COGEMA Marcoule UP1 decommissioning feed-back experience. - Various CEA decommissioning operations. The experience acquired in the plant during operation clearly shows that, for most chemical equipment, conventional rinsing ensures sufficient internal decontamination to allow dismantling. Nevertheless, some specific equipment will require more aggressive reactants to lower the final dose rate. At this stage, the choice for a process is done step. Preliminary information is needed such as the physical state of the installation, the nature of the support, the radioactive inventory and its history whenever possible. After carrying inactive and active testing at a pilot level on the most promising processes, particular attention have to be put on the generated waste. (volume, treatment and final repository). COGEMA is developing a

  14. Preliminary culture and life-cycle experiments with the benthic amphipod Ampelisca abdita

    Energy Technology Data Exchange (ETDEWEB)

    Redmond, M.S.; Jones, J.K.P. (AScI Corp., Newport, OR (United States)); Scott, K.J. (Science Applications International Corp., Narragansett, RI (United States)); Swartz, R.C. (Environmental Protection Agency, Newport, OR (United States))

    1994-08-01

    The tube-dwelling amphipod Ampelisca abdita Mills 1964 has been used extensively in acute sediment toxicity tests and has been shown to be amenable to chronic testing. Ampelisca abdita was held in the lab through several generations when fed algal food in daily static renewals, although culturing success was not consistent. Algal food consisted of one or more of the following: the flagellate Pseudoisochrysis paradoxa Sutton, and the diatoms Phaeodactylum tricornutum Bohlin and Chaetoceros calcitrans (Paulsen) Tokano. Sensitivity of cultured animals to cadmium chloride in 96-h seawater-only tests was comparable to that of field-collected animals. A life-cycle test initiated with juveniles 8 to 10 d old resulted in production of young or fertilized broods in only two of the 12 sample containers in which young were expected. Amphipods were sexually mature at approximately 20 d of age at 25 C, and young were first produced at 34 to 36 d. Short-term tests were used to quantify growth of this species in 10 to 14 d. Results from a variety of experiments indicated that there are still one or more unresolved problems with the culture and chronic testing of Ampelisca abdita. Factors such as nutrition, flow rate, light, and temperature need to be examined further.

  15. Relation of short-range and long-range lithium ion dynamics in glass-ceramics: Insights from 7Li NMR field-cycling and field-gradient studies

    Science.gov (United States)

    Haaks, Michael; Martin, Steve W.; Vogel, Michael

    2017-09-01

    We use various 7Li NMR methods to investigate lithium ion dynamics in 70Li 2S-30 P 2S5 glass and glass-ceramic obtained from this glass after heat treatment. We employ 7Li spin-lattice relaxometry, including field-cycling measurements, and line-shape analysis to investigate short-range ion jumps as well as 7Li field-gradient approaches to characterize long-range ion diffusion. The results show that ceramization substantially enhances the lithium ion mobility on all length scales. For the 70Li 2S-30 P 2S5 glass-ceramic, no evidence is found that bimodal dynamics result from different ion mobilities in glassy and crystalline regions of this sample. Rather, 7Li field-cycling relaxometry shows that dynamic susceptibilities in broad frequency and temperature ranges can be described by thermally activated jumps governed by a Gaussian distribution of activation energies g (Ea) with temperature-independent mean value Em=0.43 eV and standard deviation σ =0.07 eV . Moreover, use of this distribution allows us to rationalize 7Li line-shape results for the local ion jumps. In addition, this information about short-range ion dynamics further explains 7Li field-gradient results for long-range ion diffusion. In particular, we quantitatively show that, consistent with our experimental results, the temperature dependence of the self-diffusion coefficient D is not described by the mean activation energy Em of the local ion jumps, but by a significantly smaller apparent value whenever the distribution of correlation times G (logτ ) of the jump motion derives from an invariant distribution of activation energies and, hence, continuously broadens upon cooling. This effect occurs because the harmonic mean, which determines the results of diffusivity or also conductivity studies, continuously separates from the peak position of G (logτ ) when the width of this distribution increases.

  16. Freeze-thaw cycles and their influence on marble deterioration: a long-term experiment

    Science.gov (United States)

    Ondrasina, J.; Kirchner, D.; Siegesmund, S.

    2003-04-01

    The deterioration of three marbles (Palissandro, Sterzing and Carrara) differing in composition and rock fabric has been studied using measurements of the thermal dilatation in the temperature range from -40°C up to 60°C. A long-term freeze-thaw experiment was performed to characterize the frost weathering via Youngs's modulus.The results shown that the combined effect of heating and cooling under dry and water-saturated conditions significantly influences the material properties. The thermal dilatation and its anisotropy can be explained by the crystallographic preferred orientation of calcite and dolomite as well as with the thermal expansion behaviour of these minerals. The residual strain, i.e. the permanent length change, after thermal treatment is different for the investigated samples and less pronounced for the dolomitic Palissandro marble. A hygric expansion is of only minor importance for marble. However, a weak hygric expansion was observed in the phlogopite-bearing Palissandro sample at a direction parallel to the foliation. Fresh and artificially weathered marbles were exposed to 204 freeze-thaw cycles. The Young's modulus for the Carrara marble decreases from 55GPa to 28GPa while the porosity increases from 0.25% to 0.62%. The effect on the Palissandro and the calcitic Sterzing marbles is less pronounced. However, artificially weathered marbles clearly exhibit a drastic reduction in Young's modulus. The progressive loss in strength is caused by progressive microfracturing or the loss of cohesion along grain boundaries due to the crystallization pressure of ice growth. The experimental data along with existing theoretical models lead to the conclusion that the physical weathering of marble is influenced by cooling and heating under mid-European climatic conditions.

  17. Tropopause inversion layer formation and stratosphere-troposphere exchange during idealized baroclinic wave life cycle experiments

    Science.gov (United States)

    Kunkel, Daniel; Wirth, Volkmar; Hoor, Peter

    2014-05-01

    Recent simulations of baroclinic wave life cycles revealed that the tropopause inversion layer (TIL), commonly situated just above the thermal tropopause, is evident in such experiments and emerges after the onset of wave breaking. Furthermore, bidirectional stratosphere-troposphere exchange (STE) occurs during this non-linear stage of the wave evolution and might be affected by the appearance of the TIL. We study the evolution and the impact of the TIL on STE by using the COSMO model in an idealized mid-latitude channel geometry configuration without physical sub-grid scale parameterizations. We initialize the model with a geostrophically balanced upper level jet stream which is disturbed by an anomaly of potential vorticity to trigger the evolution of the baroclinic waves. Moreover, we use passive tracers of tropospheric or stratospheric origin to identify regions of potential STE. Our results show that the static stability is low in regions of stratosphere to troposphere exchange (STT), while it is high in regions dominated by exchange in the opposite direction (TST). Furthermore, inertia gravity waves, originating from regions with strong ageostrophic wind components, modulate the static stability as well as the vertical shear of the horizontal wind near and above the tropopause. While propagating away from their source, the inertia gravity waves lead to large values of the squared Brunt Vaisala frequency in regions which are simultaneously characterized by low bulk Richardson numbers. Thus, these regions are statically stable and turbulent at the same time and might be crucial for TST, thereby explaining tropospheric mixing ratio changes of e.g. CO across the tropopause which commonly change from tropospheric to stratospheric values a few hundred meters above the local thermal tropopause.

  18. Interdisciplinary Coordinated Experiment of the Southern Ocean Carbon Cycle (ICESOCC) - A Field Campaign Scoping Project

    Science.gov (United States)

    Mitchell, B. G.

    2015-12-01

    Accurate estimates in time and space of organic carbon export to the ocean interior via plankton net community production (NCP) for the global oceans (the biological pump) are essential for understanding the feedback between NCP, atmospheric CO2 and climate. Since integrated, multi-sensor satellite and in situ observations of many ocean variables are required to estimate NCP from space, this is a complex, interdisciplinary challenge. Satellite ocean color sensors are a fundamental component in estimating spatial and temporal variations in NCP. Therefore, NASA's PACE mission (NASA-PACE 2012), a mission included in NASA's Climate Architecture Plan (NASA-CAP, 2010), specifies a need for field programs to improve satellite algorithms and models to reduce uncertainties in estimates of NCP. Diverse data from sediment and glacial cores, and climate models, indicate that the Southern Ocean plays a large role in the glacial-interglacial variations in the biological pump, with considerable implications for variations in atmospheric CO2. The "Interdisciplinary Coordinated Experiment of the Southern Ocean Carbon Cycle (ICESOCC)" project is a NASA-funded field campaign scoping (planning) effort. Over 18 months and many public meetings and workshops, the ICESOCC team of 13 interdisciplinary scientists has integrated the input from scientific experts in ocean, atmosphere, ice physics, biogeochemistry, advanced observational tools (ship, autonomous, atmospheric gases and dust, cryosphere dynamics, winds), and models, to create a draft recommendation to NASA for field observations required to constrain uncertainty of NCP for the Southern Ocean. The ICESOCC team requests and encourages careful review and comments of the draft to ensure the most robust final recommendations are submitted in early 2016 for NASA consideration.

  19. NMR Pore Structure and Dynamic Characteristics of Sandstone Caused by Ambient Freeze-Thaw Action

    Directory of Open Access Journals (Sweden)

    Bo Ke

    2017-01-01

    Full Text Available For a deeper understanding of the freeze-thaw weathering effects on the microstructure evolution and deterioration of dynamic mechanical properties of rock, the present paper conducted the nuclear magnetic resonance (NMR tests and impact loading experiments on sandstone under different freeze-thaw cycles. The results of NMR test show that, with the increase of freeze-thaw cycles, the pores expand and pores size tends to be uniform. The experimental results show that the stress-strain curves all go through four stages, namely, densification, elasticity, yielding, and failure. The densification curve is shorter, and the slope of elasticity curve decreases as the freeze-thaw cycles increase. With increasing freeze-thaw cycles, the dynamic peak stress decreases and energy absorption of sandstone increases. The dynamic failure form is an axial splitting failure, and the fragments increase and the size diminishes with increasing freeze-thaw cycles. The higher the porosity is, the more severe the degradation of dynamic characteristics is. An increase model for the relationships between the porosity or energy absorption and freeze-thaw cycles number was built to reveal the increasing trend with the freeze-thaw cycles increase; meanwhile, a decay model was built to predict the dynamic compressive strength degradation of rock after repeated freeze-thaw cycles.

  20. Fracture strength of micro-tubular solid oxide fuel cell anode in redox cycling experiments

    Energy Technology Data Exchange (ETDEWEB)

    Pusz, Jakub; Smirnova, Alevtina; Mohammadi, Alidad; Sammes, Nigel M. [Department of Chemical, Materials, and Biomolecular Engineering, University of Connecticut, 44 Weaver Road, Storrs, CT 06269 (United States)

    2007-01-01

    The maximum fracture strength of Ni/8YSZ anodes exposed to several redox cycles is compared. The anodes were fabricated using fine and coarse particle size powders. Fine-structured powders show a 77% increase in mechanical strength after exposure to three redox cycles. The coarse-structured material did not produce similar results and redox cycling resulted in gradual decrease in the mechanical stability of the supports. The impact of redox cycling on the microstructure was evaluated using SEM. Fine-structured anodes tend to agglomerate leading to decreased porosity. Coarse anodes did not show any significant changes in microstructure while exposed to redox cycling. The electrochemical performance evaluated under load conditions, and after the first redox cycle, indicates a 40% improvement for the cell fabricated using a fine-structured anode powder. The increase in performance is believed to be due to better adhesion between the anode material and the Ni current collector. The cell fabricated using a coarse-structured anode powder did not recover after the redox cycle. (author)

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

    Science.gov (United States)

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

    2017-09-14

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

  2. NMR of lignins

    Science.gov (United States)

    John Ralph; Larry L. Landucci

    2010-01-01

    This chapter will consider the basic aspects and findings of several forms of NMR spectroscopy, including separate discussions of proton, carbon, heteronuclear, and multidimensional NMR. Enhanced focus will be on 13C NMR, because of its qualitative and quantitative importance, followed by NMR’s contributions to our understanding of lignin...

  3. Direct 13C NMR Detection in HPLC Hyphenation Mode

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  4. Rainfall and wet and dry cycle's impact on ash thickness. A laboratory experiment

    Science.gov (United States)

    Pereira, Paulo; Keestra, Saskia; Peters, Piet; Cerdà, Artemi

    2016-04-01

    Ash is the most important and effective soil protection in the immediate period after the fire (Cerda and Doerr, 2008; Pereira et al., 2015a). This protection can last for days or weeks depending on the fire severity, topography of the burned area and post-fire meteorological conditions. In the initial period after the fire, ash is easily transported by wind. However after the first rainfalls, ash is eroded, or bind in soil surface (Pereira et al., 2013, 2015a). Ash thickness has implications on soil protection. The soil protection against the erosion and the ash capacity to retain water increases with the ash thickness (Bodi et al., 2014). Ash cover is very important after fire because store water and releases into soil a large amount of nutrients, fundamental to vegetation recuperation (Pereira et al., 2014). Despite the importance of ash thickness in post fire environments, little information is available about the effects of rainfall and wet and dry cycle's effects on ash thickness. This work aims to fill this gap. The objective of this study is to investigate the impacts of rainfall and wet and dry cycles in the ash thickness of two different under laboratory conditions. Litter from Oak (Quercus robur) and Spruce (Picea abis) were collected to and exposed during 2 hours to produce ash at 200 and 400 C. Subsequently a layer of 15 mm ash was spread on soil surface in small boxes (24x32 cm) and then subjected to rainfall simulation. Boxes were placed at a 17% of inclination and a rainfall intensity of 55 mm/h during 40 minutes was applied. After the rainfall simulation the plots were stored in an Oven at the temperature of 25 C during four days, in order to identify the effects of wet and dry cycles (Bodi et al., 2013). Ash thickness was measured after the first rainfall (AFR), before the second rainfall (BSR) - after the dry period of 4 days - and after the second rainfall (ASR). In each box a grid with 57 points was designed in order to analyse ash thickness

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

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

    Science.gov (United States)

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

    2009-01-01

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

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

    Science.gov (United States)

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

    2009-01-01

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

  8. Applied NMR spectroscopy for chemists and life scientists

    CERN Document Server

    Zerbe, Oliver

    2013-01-01

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

  9. COMBINED CYCLE GAS TURBINE FOR THERMAL POWER STATIONS: EXPERIENCE IN DESIGNING AND OPERATION, PROSPECTS IN APPLICATION

    Directory of Open Access Journals (Sweden)

    N. V. Karnitsky

    2014-01-01

    Full Text Available The paper has reviewed main world tendencies in power consumption and power system structure. Main schemes of combined cycle gas turbines have been considered in the paper. The paper contains an operational analysis of CCGT blocks that are operating within the Belarusian energy system. The analysis results have been given in tables showing main operational indices of power blocks

  10. Sport cycling crashes on public roads, the influence of bunch riding and experience.

    NARCIS (Netherlands)

    Wijlhuizen, G.J. Gent, P. van & Stipdonk, H.L.

    2014-01-01

    Cycling is a popular but unsafe mode of transport in the Netherlands and the number of seriously injured bicyclists has increased significantly since 2006. A special subgroup is the population of sport cyclists who perform their sport on public roads. The number of road crashes with sport cyclists s

  11. Project Description Advanced Fuel Cycle Initiative AFC-2A and AFC-2B Experiments

    Energy Technology Data Exchange (ETDEWEB)

    AFCI AFC-2A and AFC-2B Experiments Project Executi

    2007-03-01

    The proposed AFC-2A and AFC-2B irradiation experiments are a continuation of the AFC-1 fuel test series currently in progress in the ATR. This document discusses the experiments and the planned activities that will take place.

  12. Field experiments and numerical simulations of confined aquifer response to multi-cycle recharge-recovery process through a well

    Science.gov (United States)

    Wang, Jianxiu; Wu, Yuanbin; Zhang, Xingsheng; Liu, Yan; Yang, Tianliang; Feng, Bo

    2012-09-01

    SummaryShanghai is one of the cities suffering from land subsidence in China. Land subsidence has caused serious financial losses. Thus, artificial recharge measures have been adopted to compensate the drawdown in shallow, confined aquifers and thereby control land subsidence. In this study, a multi-cycle recharge-recovery field experiment was performed to investigate the response of a shallow, confined aquifer to artificial recharge through a well. In the experiment, a series of recharge-recovery cycles with different recharge volumes and durations, with and without artificial pressure, were performed. The water levels monitored in the recharge and observation wells indicated the response of the aquifer to the multi-cycle recharge-recovery process. Meanwhile, a finite-difference method (FDM) numerical model was established, and its parameters were obtained via a reversed numerical analysis on the experimental data. The responses of the shallow, confined aquifer to the multi-cycle recharge-recovery process were simulated in detail using the model. The calculation results showed that the water level dropped significantly when the recharge ended. Moreover, the efficiency of a multi-cycle recharge was found to be higher than that of a concentrated one under the same recharge volume and time. The relationship between recharge frequency and efficiency, expressed as H = 0.29498 f0.40163 and R2 = 0.97264, respectively, was obtained through the FDM numerical simulation. In the recharge intervals, the optimal recharge efficiency was achieved when the water level rose to 40% of the peak.

  13. A Guided Inquiry Approach to NMR Spectroscopy

    Science.gov (United States)

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

    1998-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-09-15

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

  15. NASA's Robotics Mining Competition Provides Undergraduates Full Life Cycle Systems Engineering Experience

    Science.gov (United States)

    Stecklein, Jonette

    2017-01-01

    NASA has held an annual robotic mining competition for teams of university/college students since 2010. This competition is yearlong, suitable for a senior university engineering capstone project. It encompasses the full project life cycle from ideation of a robot design to actual tele-operation of the robot in simulated Mars conditions mining and collecting simulated regolith. A major required element for this competition is a Systems Engineering Paper in which each team describes the systems engineering approaches used on their project. The score for the Systems Engineering Paper contributes 25% towards the team's score for the competition's grand prize. The required use of systems engineering on the project by this competition introduces the students to an intense practical application of systems engineering throughout a full project life cycle.

  16. NASA's Robotic Mining Competition Provides Undergraduates Full Life Cycle Systems Engineering Experience

    Science.gov (United States)

    Stecklein, Jonette

    2017-01-01

    NASA has held an annual robotic mining competition for teams of university/college students since 2010. This competition is yearlong, suitable for a senior university engineering capstone project. It encompasses the full project life cycle from ideation of a robot design, through tele-operation of the robot collecting regolith in simulated Mars conditions, to disposal of the robot systems after the competition. A major required element for this competition is a Systems Engineering Paper in which each team describes the systems engineering approaches used on their project. The score for the Systems Engineering Paper contributes 25% towards the team’s score for the competition’s grand prize. The required use of systems engineering on the project by this competition introduces the students to an intense practical application of systems engineering throughout a full project life cycle.

  17. [Ecological engineering experiment for Jinshan Lake in Zhenjiang base on techniques of immobilized nitrogen cycling bacteria].

    Science.gov (United States)

    Li, Zheng-Kui; Zhang, Xiao-Jiao; Yang, Zhu-You; Shi, Lu-Na; Wang, Yue-Ming; Feng, Lu-Lu; Lü, Yi-Xiu

    2009-06-15

    Nitrogen cycling bacteria, including ammonifying, nitrobacteria, nitrosobacteria and denitrifying bacteria were screened, carrier was made and immobilized nitrogen cycling bacteria (INCB) was prepared. The results demonstrated that ammonifying, nitrobacteria, nitrosobacteria and denitrifying bacteria were increased markedly in the experimental areas and root zone of aquatic plants by releasing of INCB. The results also showed that the average removal efficiencies for total N (TN), NH4(+) -N, NO3(-) -N and NO2(-) -N were 44.70%, 67.17%, 31.79% and 74.21%, respectively. Furthermore, NH4(+) -N, total N (TN) reached the National Standard II and IV for surface water, respectively. With INCB, local lake water quality could improve. Therefore, the technique of INCB could play an important role for remedying and rehabilitating in desertification water.

  18. Thermal Cycling and Isothermal Deformation Response of Polycrystalline NiTi: Simulations vs. Experiment

    Science.gov (United States)

    Manchiraju, Sivom; Gaydosh, Darrell; Benafan, Othmane; Noebe, Ronald; Vaidyanathan, Raj; Anderson, Peter M.

    2011-01-01

    A recent microstructure-based FEM model that couples crystal-based plasticity, the B2 MB190 phase transformation and anisotropic elasticity at the grain scale is calibrated to recent data for polycrystalline NiTi (49.9 at.% Ni). Inputs include anisotropic elastic properties, texture and differential scanning calorimetry data, as well as a subset of recent isothermal deformation and load-biased thermal cycling data. The model is assessed against additional experimental data. Several experimental trends are captured - in particular, the transformation strain during thermal cycling monotonically increases and reaches a peak with increasing bias stress. This is achieved, in part, by modifying the martensite hardening matrix proposed by Patoor et al. [Patoor E, Eberhardt A, Berveiller M. J Phys IV 1996;6:277]. Some experimental trends are underestimated - in particular, the ratcheting of macrostrain during thermal cycling. This may reflect a model limitation that transformation-plasticity coupling is captured on a coarse (grain) scale but not on a fine (martensitic plate) scale.

  19. Quantitative time- and frequency-domain analysis of the two-pulse COSY revamped by asymmetric Z-gradient echo detection NMR experiment: Theoretical and experimental aspects, time-zero data truncation artifacts, and radiation damping.

    Science.gov (United States)

    Kirsch, Stefan; Hull, William E

    2008-07-28

    The two-pulse COSY revamped by asymmetric Z-gradient echo detection (CRAZED) NMR experiment has the basic form 90 degrees -Gdelta-t(rec)-beta-nGdelta-t(rec)-FID, with a phase-encoding gradient pulse G of length delta applied during the evolution time tau for transverse magnetization, readout pulse beta, rephasing gradient nGdelta, and recovery time t(rec) prior to acquisition of the free-induction decay. Based on the classical treatment of the spatially modulated dipolar demagnetizing field and without invoking intermolecular multiple-quantum coherence, a new formulation of the first-order approximation for the theoretical solution of the nonlinear Bloch equations has been developed. The nth-order CRAZED signal can be expressed as a simple product of a scaling function C(n)(beta,tau) and a signal amplitude function A(n)(t), where the domain t begins immediately after the beta pulse. Using a single-quantum coherence model, a generalized rf phase shift function has also been developed, which explains all known phase behavior, including nth-order echo selection by phase cycling. Details of the derivations are provided in two appendices as supplementary material. For n>1, A(n)(t) increases from zero to a maximum value at t=t(max) before decaying and can be expressed as a series of n exponential decays with antisymmetric binomial coefficients. Fourier transform gives an antisymmetric binomial series of Lorentzians, where the composite lineshape exhibits negative wings, zero integral, and a linewidth that decreases with n. Analytical functions are presented for t(max) and A(n)(t(max)) and for estimating the maximal percent error incurred for A(n)(t(max)) when using the first-order model. The preacquisition delay Delta=delta+t(rec) results in the loss of the data points for t=0 to Delta. Conventional Fourier transformation produces time-zero truncation artifacts (reduced negative wing amplitude, nonzero integral, and reduced effective T(2) ( *)), which can be avoided by

  20. Timeslice experiments for understanding regional climate projections: applications to the tropical hydrological cycle and European winter circulation

    Science.gov (United States)

    Chadwick, Robin; Douville, Hervé; Skinner, Christopher B.

    2017-01-01

    A set of atmosphere-only timeslice experiments are described, designed to examine the processes that cause regional climate change and inter-model uncertainty in coupled climate model responses to CO_2 forcing. The timeslice experiments are able to reproduce the pattern of regional climate change in the coupled models, and are applied here to two cases where inter-model uncertainty in future projections is large: the tropical hydrological cycle, and European winter circulation. In tropical forest regions, the plant physiological effect is the largest cause of hydrological cycle change in the two models that represent this process. This suggests that the CMIP5 ensemble mean may be underestimating the magnitude of water cycle change in these regions, due to the inclusion of models without the plant effect. SST pattern change is the dominant cause of precipitation and circulation change over the tropical oceans, and also appears to contribute to inter-model uncertainty in precipitation change over tropical land regions. Over Europe and the North Atlantic, uniform SST increases drive a poleward shift of the storm-track. However this does not consistently translate into an overall polewards storm-track shift, due to large circulation responses to SST pattern change, which varies across the models. Coupled model SST biases influence regional rainfall projections in regions such as the Maritime Continent, and so projections in these regions should be treated with caution.

  1. Cyclebase.org: version 2.0, an updated comprehensive, multi-species repository of cell cycle experiments and derived analysis results

    DEFF Research Database (Denmark)

    Jensen, Lars Juhl; Wernersson, Rasmus; Brunak, Søren;

    2010-01-01

    Cell division involves a complex series of events orchestrated by thousands of molecules. To study this process, researchers have employed mRNA expression profiling of synchronously growing cell cultures progressing through the cell cycle. These experiments, which have been carried out in several...... organisms, are not easy to access, combine and evaluate. Complicating factors include variation in interdivision time between experiments and differences in relative duration of each cell-cycle phase across organisms. To address these problems, we created Cyclebase, an online resource of cell-cycle......-related experiments. This database provides an easy-to-use web interface that facilitates visualization and download of genome-wide cell-cycle data and analysis results. Data from different experiments are normalized to a common timescale and are complimented with key cell-cycle information and derived analysis...

  2. NMR reaction monitoring in flow synthesis

    Directory of Open Access Journals (Sweden)

    M. Victoria Gomez

    2017-02-01

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

  3. NMR at 900 MHz

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    @@ An important factor in the development of solutionstate NMR has always been th e ability to produce stable and homogeneous magnetic fields. As higher and higher field strengths are reached the pressure is growing on manufacturers to produce NMR systems with greatly improved spectral resolution and signal to noise ratio. The introduction of the Varian 900 MHz INOVA system in August 2000 featuring Oxford Instruments 21.1 T magnet represents the latest pioneering development in NMR technology.

  4. Applications of NMR spectroscopy to systems biochemistry.

    Science.gov (United States)

    Fan, Teresa W-M; Lane, Andrew N

    2016-02-01

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

  5. Direct 13C NMR Detection in HPLC Hyphenation Mode

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  6. Teenage Childbearing and Its Life Cycle Consequences: Exploiting a Natural Experiment

    OpenAIRE

    V. Joseph Hotz; Sanders, Seth G.; Susan Williams McElroy

    1999-01-01

    In this paper, we exploit a 'natural experiment' associated with human reproduction to identify the effect of teen childbearing on subsequent educational attainment, family structure, labor market outcomes and financial self-sufficiency. In particular, we exploit the fact that a substantial fraction of women who become pregnant experience a miscarriage (spontaneous abortion) and thus do not have a birth. If miscarriages were purely random and if miscarriages were the only way, other than by l...

  7. 40-Gbps vestigial sideband half-cycle Nyquist subcarrier modulation transmission experiment and its comparison with orthogonal frequency division multiplexing

    Science.gov (United States)

    Liu, Na; Chen, Xue; Ju, Cheng; Hui, Rongqing

    2014-09-01

    We experimentally demonstrate the superior performance of a 40-Gbps 16-QAM half-cycle Nyquist subcarrier modulation (SCM) transmission over a 100-km uncompensated standard single-mode fiber using dual-drive Mach-Zehnder modulator-based vestigial sideband intensity modulation and direct detection. The impact of modulator chirp on the system performance is experimentally evaluated. This Nyquist-SCM technique is compared with optical orthogonal frequency division multiplexing in both back-to-back and 100-km transmission experiments, and the results show that the Nyquist system has a better performance.

  8. Factors affecting {sup 223}Ra therapy: clinical experience after 532 cycles from a single institution

    Energy Technology Data Exchange (ETDEWEB)

    Etchebehere, Elba C. [The University of Texas MD Anderson Cancer Center, Department of Nuclear Medicine, Houston, TX (United States); Campinas State University (Unicamp), Department of Nuclear Medicine, Campinas (Brazil); Milton, Denai R. [The University of Texas MD Anderson Cancer Center, Department of Biostatistics, Houston, TX (United States); Araujo, John C. [The University of Texas MD Anderson Cancer Center, Department of Genitourinary Medical Oncology, Houston, TX (United States); Swanston, Nancy M.; Macapinlac, Homer A.; Rohren, Eric M. [The University of Texas MD Anderson Cancer Center, Department of Nuclear Medicine, Houston, TX (United States)

    2016-01-15

    The aim of this study was to identify baseline features that predict outcome in {sup 223}Ra therapy. We retrospectively reviewed 110 patients with metastatic castration-resistant prostate cancer treated with {sup 223}Ra. End points were overall survival (OS), progression-free survival (PFS), bone event-free survival (BeFS), and bone marrow failure (BMF). The following parameters were evaluated prior to the first {sup 223}Ra cycle: serum levels of hemoglobin (Hb), prostate-specific antigen (PSA), alkaline phosphatase (ALP), Eastern Cooperative Oncology Group (ECOG) status, pain score, use of chemotherapy, and external beam radiation therapy (EBRT). During/after {sup 223}Ra we evaluated: the total number of radium cycles (Ra{sub Tot}), the PSA doubling time (PSA{sub DT}), and the use of chemotherapy, EBRT, abiraterone, and enzalutamide. A significant reduction of ALP (p < 0.001) and pain score (p = 0.041) occurred throughout the {sup 223} Ra cycles. The risk of progression was associated with declining ECOG status [hazard ratio (HR) = 3.79; p < 0.001] and decrease in PSA{sub DT} (HR = 8.22; p < 0.001). Ra{sub Tot}, ALP, initial ECOG status, initial pain score, and use of abiraterone were associated with OS (p ≤ 0.008), PFS (p ≤ 0.003), and BeFS (p ≤ 0.020). Ra{sub Tot}, ALP, initial ECOG status, and initial pain score were significantly associated with BMF (p ≤ 0.001) as well as Hb (p < 0.001) and EBRT (p = 0.009). On multivariable analysis, only Ra{sub Tot} and abiraterone remained significantly associated with OS (p < 0.001; p = 0.033, respectively), PFS (p < 0.001; p = 0.041, respectively), and BeFS (p < 0.001; p = 0.019, respectively). Additionally, Ra{sub Tot} (p = 0.027) and EBRT (p = 0.013) remained significantly associated with BMF. Concomitant use of abiraterone and {sup 223}Ra seems to have a beneficial effect, while the EBRT may increase the risk of BMF. (orig.)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-10-31

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

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

    Science.gov (United States)

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

    2012-11-01

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

  11. Numerical analysis and experiment to identify origin of buckling in rapid cycling synchrotron core

    Energy Technology Data Exchange (ETDEWEB)

    Morita, Y., E-mail: yuichi.morita@kek.jp [High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki (Japan); Kageyama, T. [High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki (Japan); Akoshima, M. [The National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki (Japan); Torizuka, S.; Tsukamoto, M. [National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki (Japan); Yamashita, S. [International Center for Elementary Particle Physics (ICEPP), University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo (Japan); Yoshikawa, N. [Institute of Industrial Science (IIS), University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo (Japan)

    2013-11-11

    The accelerating cavities used in the rapid cycling synchrotron (RCS) of the Japan Proton Accelerator Research Complex (J-PARC) are loaded with magnetic alloy (MA) cores. Over lengthly periods of RCS operation, significant reductions in the impedance of the cavities resulting from the buckling of the cores were observed. A series of thermal structural simulations and compressive strength tests showed that the buckling can be attributed to the low-viscosity epoxy resin impregnation of the MA core that causes the stiffening of the originally flexible MA–ribbon–wound core. Our results showed that thermal stress can be effectively reduced upon using a core that is not epoxy-impregnated. -- Highlights: • Study to identify the origin of buckling in the MA cores is presented. • Thermal stress simulations and compressive strength tests were carried out. • Results show that thermal stress is the origin of core buckling. • Thermal stress can be reduced by using cores without epoxy impregnation.

  12. Wet-dry cycles effect on ash water repellency. A laboratory experiment.

    Science.gov (United States)

    Pereira, Paulo; Cerdà, Artemi; Oliva, Marc; Mataix, Jorge; Jordán, Antonio

    2014-05-01

    In the immediate period after the fire, the ash layer has a strong influence on soil hydrological processes, as runoff, infiltration and erosion. Ash is very dynamic in the space and time. Until the first rainfall periods, ash is (re)distributed by the wind. After it can cover the soil surface, infiltrate or transported to other areas by water transport (Pereira et al., 2013a, b). This will have strong implications on nutrient redistribution and vegetation recovery. Ash layer may affect soil water repellency in different ways, depending on fire severity, soil properties and vegetation. Ash produced at low temperatures after low-severity burning is usually hydrophobic (Bodi et al., 2011, 2012). Wet-dry cycles have implications on ash physical and chemical properties, changing their effects in space and time. The aim of this study is to analyse the effects of fire temperature and severity on ash water repellency. Pinus sylvestris needles were collected in a Lithuania forest in Dzukija National Park (53º 54' N and 24º 22' E), transported to laboratory and washed with deionized water to remove soil particles and other residues. Needle samples were dried during 24 hours and exposed to different temperatures: 200, 300, 400 and 500 ºC, during 2 hours. Ash colour was analysed according to the Munsell Soil Color charts. Ash was black (10 YR 2/1) at 200 ºC, very dark grey (10YR 3/1) at 300 ºC, gray (10YR 5/1) at 400 ºC and light gray (10YR 7/1) at 500 ºC. Ten samples of ash released after each treatment were placed in plastic dishes (50 mm in diameter) in an amount enough to form a 5 mm thick layer, and ash water repellency was measured according to the Water Drop Penetration Test. Later, ash was carefully wetted with 15 ml of deionized water and placed in an oven during 4 days (96 hours), as in Bodí et al. (2012). This procedure was repeated 5 times in order to observe the effects of wet-dry cycles in ash water repellency. The results showed significant differences

  13. Evaluation of the Diurnal Cycle in the Atmospheric Boundary Layer Over Land as Represented by a Variety of Single-Column Models: The Second GABLS Experiment

    NARCIS (Netherlands)

    Svensson, G.; Holtslag, A.A.M.; Kumar, V.; Mauritsen, T.; Steeneveld, G.J.; Angevine, W.M.; Bazile, E.; Beljaars, A.; Bruijn, de E.I.F.; Cheng, A.

    2011-01-01

    We present the main results from the second model intercomparison within the GEWEX (Global Energy andWater cycle EXperiment) Atmospheric Boundary Layer Study (GABLS). The target is to examine the diurnal cycle over land in today’s numerical weather prediction and climate models for operational and r

  14. NMR logging apparatus

    Energy Technology Data Exchange (ETDEWEB)

    Walsh, David O; Turner, Peter

    2014-05-27

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

  15. NMR logging apparatus

    Science.gov (United States)

    Walsh, David O; Turner, Peter

    2014-05-27

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

  16. NMR studies of metalloproteins.

    Science.gov (United States)

    Li, Hongyan; Sun, Hongzhe

    2012-01-01

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

  17. In situ NMR spectroscopy of supercapacitors: insight into the charge storage mechanism.

    Science.gov (United States)

    Wang, Hao; Forse, Alexander C; Griffin, John M; Trease, Nicole M; Trognko, Lorie; Taberna, Pierre-Louis; Simon, Patrice; Grey, Clare P

    2013-12-18

    Electrochemical capacitors, commonly known as supercapacitors, are important energy storage devices with high power capabilities and long cycle lives. Here we report the development and application of in situ nuclear magnetic resonance (NMR) methodologies to study changes at the electrode-electrolyte interface in working devices as they charge and discharge. For a supercapacitor comprising activated carbon electrodes and an organic electrolyte, NMR experiments carried out at different charge states allow quantification of the number of charge storing species and show that there are at least two distinct charge storage regimes. At cell voltages below 0.75 V, electrolyte anions are increasingly desorbed from the carbon micropores at the negative electrode, while at the positive electrode there is little change in the number of anions that are adsorbed as the voltage is increased. However, above a cell voltage of 0.75 V, dramatic increases in the amount of adsorbed anions in the positive electrode are observed while anions continue to be desorbed at the negative electrode. NMR experiments with simultaneous cyclic voltammetry show that supercapacitor charging causes marked changes to the local environments of charge storing species, with periodic changes of their chemical shift observed. NMR calculations on a model carbon fragment show that the addition and removal of electrons from a delocalized system should lead to considerable increases in the nucleus-independent chemical shift of nearby species, in agreement with our experimental observations.

  18. The Manuel Lujan, Jr. Neutron Scattering Center LANSCE experiment reports 1989 run cycle

    Energy Technology Data Exchange (ETDEWEB)

    Hyer, D.K.; DiStravolo, M.A. (comps.)

    1990-10-01

    This report contains a listing and description of experiments carried on at the LANSCE neutron scattering facility in the following areas: High Density Powder Diffraction; Neutron Powder Diffractometer, (NPD); Single Crystal Diffractometer, (SCD); Low-Q Diffractometer, (LQD); Surface Profile Analysis Reflectometer, (SPEAR); Filter Difference Spectrometer, (FDS); and Constant-Q Spectrometer.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-15

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

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

    Science.gov (United States)

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

    2015-12-01

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

  1. UC Merced NMR Instrumentation Acquisition

    Science.gov (United States)

    2015-06-18

    UC Merced NMR Instrumentation Acquisition For the UC Merced NMR Instrumentation Acquisition proposal, a new 400 MHz and an upgraded 500 MHz NMR ...UC Merced NMR Instrumentation Acquisition Report Title For the UC Merced NMR Instrumentation Acquisition proposal, a new 400 MHz and an upgraded 500...MHz NMR have been delivered, installed, and incorporated into research and two lab courses. While no results from these instruments have been

  2. Attitudes towards doping and related experience in Spanish national cycling teams according to different Olympic disciplines.

    Science.gov (United States)

    Morente-Sánchez, Jaime; Mateo-March, Manuel; Zabala, Mikel

    2013-01-01

    Attitudes towards doping are considered an influence of doping intentions. The aims of the present study were 1) to discover and compare the attitudes towards doping among Spanish national team cyclists from different Olympic disciplines, as well as 2) to get some complementary information that could better explain the context. The sample was comprised of seventy-two cyclists: mean age 19.67±4.72 years; 70.8% males (n = 51); from the different Olympic disciplines of Mountain bike -MTB- (n = 18), Bicycle Moto Cross -BMX- (n = 12), Track -TRA- (n = 9) and Road -ROA- (n = 33). Descriptive design was carried out using a validated scale (PEAS). To complement this, a qualitative open-ended questionnaire was used. Overall mean score (17-102) was 36.12±9.39. For different groups, the data were: MTB: 30.28±6.92; BMX: 42.46±10.74; TRA: 43.22±12.00; ROA: 34.91±6.62, respectively. In relation to overall score, significant differences were observed between MTB and BMX (p = 0.002) and between MTB and TRA (p = 0.003). For the open-ended qualitative questionnaire, the most mentioned word associated with "doping" was "cheating" (48.83% of total sample), with "responsible agents of doping" the word "doctor" (52,77%), and with the "main reason for the initiation in doping" the words "sport achievement" (45.83%). The major proposed solution was "doing more doping controls" (43.05%). Moreover, 48.67% stated that there was "a different treatment between cycling and other sports". This study shows that Spanish national team cyclists from Olympic cycling disciplines, in general, are not tolerant in relation to doping. BMX and Track riders are a little more permissive towards the use of banned substances than MTB and Road. Results from the qualitative open-ended questionnaire showed interesting data in specific questions. These results empower the idea that, apart from maintaining doping controls and making them more efficient, anti-doping education

  3. Attitudes towards doping and related experience in Spanish national cycling teams according to different Olympic disciplines.

    Directory of Open Access Journals (Sweden)

    Jaime Morente-Sánchez

    Full Text Available Attitudes towards doping are considered an influence of doping intentions. The aims of the present study were 1 to discover and compare the attitudes towards doping among Spanish national team cyclists from different Olympic disciplines, as well as 2 to get some complementary information that could better explain the context. The sample was comprised of seventy-two cyclists: mean age 19.67±4.72 years; 70.8% males (n = 51; from the different Olympic disciplines of Mountain bike -MTB- (n = 18, Bicycle Moto Cross -BMX- (n = 12, Track -TRA- (n = 9 and Road -ROA- (n = 33. Descriptive design was carried out using a validated scale (PEAS. To complement this, a qualitative open-ended questionnaire was used. Overall mean score (17-102 was 36.12±9.39. For different groups, the data were: MTB: 30.28±6.92; BMX: 42.46±10.74; TRA: 43.22±12.00; ROA: 34.91±6.62, respectively. In relation to overall score, significant differences were observed between MTB and BMX (p = 0.002 and between MTB and TRA (p = 0.003. For the open-ended qualitative questionnaire, the most mentioned word associated with "doping" was "cheating" (48.83% of total sample, with "responsible agents of doping" the word "doctor" (52,77%, and with the "main reason for the initiation in doping" the words "sport achievement" (45.83%. The major proposed solution was "doing more doping controls" (43.05%. Moreover, 48.67% stated that there was "a different treatment between cycling and other sports". This study shows that Spanish national team cyclists from Olympic cycling disciplines, in general, are not tolerant in relation to doping. BMX and Track riders are a little more permissive towards the use of banned substances than MTB and Road. Results from the qualitative open-ended questionnaire showed interesting data in specific questions. These results empower the idea that, apart from maintaining doping controls and making them more efficient, anti-doping education

  4. Effect of Biochar on Greenhouse Gas Emissions and Nitrogen Cycling in Laboratory and Field Experiments

    Science.gov (United States)

    Hagemann, Nikolas; Harter, Johannes; Kaldamukova, Radina; Ruser, Reiner; Graeff-Hönninger, Simone; Kappler, Andreas; Behrens, Sebastian

    2014-05-01

    The extensive use of nitrogen (N) fertilizers in agriculture is a major source of anthropogenic N2O emissions contributing 8% to global greenhouse gas emissions. Soil biochar amendment has been suggested as a means to reduce both CO2 and non-CO2 greenhouse gas emissions. The reduction of N2O emissions by biochar has been demonstrated repeatedly in field and laboratory experiments. However, the mechanisms of the reduction remain unclear. Further it is not known how biochar field-weathering affects GHG emissions and how agro-chemicals, such as the nitrification inhibitor 3,4-dimethylpyrazole phosphate (DMPP), that is often simultaneously applied together with commercial N-fertilizers, impact nitrogen transformation and N2O emissions from biochar amended soils. In order investigate the duration of the biochar effect on soil N2O emissions and its susceptibility to DMPP application we performed a microcosm and field study with a high-temperature (400 ° C) beech wood derived biochar (60 t ha-1 and 5 % (w/w) biochar in the field and microcosms, respectively). While the field site contained the biochar already for three years, soil and biochar were freshly mixed for the laboratory microcosm experiments. In both studies we quantified GHG emissions and soil nitrogen speciation (nitrate, nitrite, ammonium). While the field study was carried out over the whole vegetation period of the sunflower Helianthus annuus L., soil microcosm experiments were performed for up to 9 days at 28° C. In both experiments a N-fertilizer containing DMPP was applied either before planting of the sunflowers or at the beginning of soil microcosms incubation. Laboratory microcosm experiments were performed at 60% water filled pore space reflecting average field conditions. Our results show that biochar effectively reduced soil N2O emissions by up to 60 % in the field and in the soil microcosm experiments. No significant differences in N2O emission mitigation potential between field-aged and fresh

  5. Introduction to NMR Quantum Information Processing

    CERN Document Server

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

    2002-01-01

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

  6. Operational energy in the life cycle of residential dwellings: The experience of Spain and Colombia

    Energy Technology Data Exchange (ETDEWEB)

    Ortiz, Oscar [University of Rovira i Virgili, Environmental and Analysis Management Group (AGA), Department of Chemical Engineering, Av. Paisos Catalanes 26, 43007 Tarragona (Spain); University of Pamplona, Department of Industrial Engineering, Km 1 Via Bucaramanga, Pamplona, N de S (Colombia); Castells, Francesc [University of Pamplona, Department of Industrial Engineering, Km 1 Via Bucaramanga, Pamplona, N de S (Colombia); Sonnemann, Guido [University of Rovira i Virgili, Visiting Senior Research Fellow, AGA Group (AGA) (Spain)

    2010-02-15

    Life Cycle Assessment (LCA) has been applied within the residential building sector of two buildings, one in each a developed (Spain) and a developing (Colombia) country. The main goal of this paper involves the environmental loads and also brings together the operational energy for activities during the operation phase such as HVAC, domestic hot water, electrical appliances, cooking and illumination. The present research compares two real scenarios: Situation 1, where 100% of the dwelling's energy is supplied with electricity only and Situation 2, where dwellings can be operated with natural gas plus electricity. The results for the environmental impacts using natural gas plus electricity show that of the Spanish environmental impacts air conditioning had the highest impact with approximately 27-42% due to the electricity used to power it. In Colombian results showed that electrical appliances had the highest environmental impacts in the same order of magnitude with approximately 60% and cooking had the best reduction of emissions due to the use of natural gas, from 10% down to less than 2%. The origin of the energy source used in each Country plays an important role to minimize environmental impacts, as was demonstrated by the environmental impacts of its use in Colombia where 78% of the electricity came from hydroelectric plants whereas in Spain it is more mixed, fossil fuels represented 55%, nuclear 18% and wind 9%. In summary, LCA has been applied because this methodology supports the decision making to concern environmental sustainability. (author)

  7. Experiments on water detritiation and cryogenic distillation at TLK; Impact on ITER fuel cycle subsystems interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Cristescu, I.; Cristescu, I. R.; Doerr, L.; Hellriegel, G.; Michling, R. [Forschungszentrum Karlsruhe, Inst. for Technical Physics, Tritium Laboratory Karlsruhe, P.O. Box 3640, D- 76021 Karlsruhe (Germany); Murdoch, D. [EFDA CSU, MPI fuer Plasmaphysik, Garching (Germany); Schaefer, P.; Welte, S.; Wurster, W. [Forschungszentrum Karlsruhe, Inst. for Technical Physics, Tritium Laboratory Karlsruhe, P.O. Box 3640, D- 76021 Karlsruhe (Germany)

    2008-07-15

    The ITER Isotope Separation System (ISS) and Water Detritiation System (WDS) should be integrated in order to reduce potential chronic tritium emissions from the ISS. This is achieved by routing the top (protium) product from the ISS to a feed point near the bottom end of the WDS Liquid Phase Catalytic Exchange (LPCE) column. This provides an additional barrier against ISS emissions and should mitigate the memory effects due to process parameter fluctuations in the ISS. To support the research activities needed to characterize the performances of various components for WDS and ISS processes under various working conditions and configurations as needed for ITER design, an experimental facility called TRENTA representative of the ITER WDS and ISS protium separation column, has been commissioned and is in operation at TLK The experimental program on TRENTA facility is conducted to provide the necessary design data related to the relevant ITER operating modes. The operation availability and performances of ISS-WDS have impact on ITER fuel cycle subsystems with consequences on the design integration. The preliminary experimental data on TRENTA facility are presented. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-02-15

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

  9. Entanglement witness derived from NMR superdense coding

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-03-03

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

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

    Science.gov (United States)

    Mills, Nancy S.

    1998-06-01

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

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

    Science.gov (United States)

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

    2017-01-01

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

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

    Science.gov (United States)

    2017-01-01

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

  13. Benford distributions in NMR

    CERN Document Server

    Bhole, Gaurav; Mahesh, T S

    2014-01-01

    Benford's Law is an empirical law which predicts the frequency of significant digits in databases corresponding to various phenomena, natural or artificial. Although counter intuitive at the first sight, it predicts a higher occurrence of digit 1, and decreasing occurrences to other larger digits. Here we report the Benford analysis of various NMR databases and draw several interesting inferences. We observe that, in general, NMR signals follow Benford distribution in time-domain as well as in frequency domain. Our survey included NMR signals of various nuclear species in a wide variety of molecules in different phases, namely liquid, liquid-crystalline, and solid. We also studied the dependence of Benford distribution on NMR parameters such as signal to noise ratio, number of scans, pulse angles, and apodization. In this process we also find that, under certain circumstances, the Benford analysis can distinguish a genuine spectrum from a visually identical simulated spectrum. Further we find that chemical-sh...

  14. Carbon cycling and phytoplankton responses within highly-replicated shipboard carbonate chemistry manipulation experiments conducted around Northwest European Shelf Seas

    Science.gov (United States)

    Richier, S.; Achterberg, E. P.; Dumousseaud, C.; Poulton, A. J.; Suggett, D. J.; Tyrrell, T.; Zubkov, M. V.; Moore, C. M.

    2014-03-01

    The ongoing oceanic uptake of anthropogenic carbon dioxide (CO2) is significantly altering the carbonate chemistry of seawater, a phenomenon referred to as ocean acidification. Experimental manipulations have been increasingly used to gauge how continued ocean acidification will potentially impact marine ecosystems and their associated biogeochemical cycles in the future; however, results amongst studies, particularly when performed on natural communities, are highly variable, which in part likely reflects inconsistencies in experimental approach. To investigate the potential for identification of more generic responses and greater experimentally reproducibility, we devised and implemented a series of highly replicated (n = 8), short term (2-4 days) multi-level (≥ 4 conditions) carbonate chemistry/nutrient manipulation experiments on a range of natural microbial communities sampled in Northwest European shelf seas. Carbonate chemistry manipulations and resulting biological responses were found to be highly reproducible within individual experiments and to a lesser extent between geographically different experiments. Statistically robust reproducible physiological responses of phytoplankton to increasing pCO2, characterized by a suppression of net growth for small sized cells (ocean.

  15. Phytoplankton responses and associated carbon cycling during shipboard carbonate chemistry manipulation experiments conducted around Northwest European shelf seas

    Science.gov (United States)

    Richier, S.; Achterberg, E. P.; Dumousseaud, C.; Poulton, A. J.; Suggett, D. J.; Tyrrell, T.; Zubkov, M. V.; Moore, C. M.

    2014-09-01

    The ongoing oceanic uptake of anthropogenic carbon dioxide (CO2) is significantly altering the carbonate chemistry of seawater, a phenomenon referred to as ocean acidification. Experimental manipulations have been increasingly used to gauge how continued ocean acidification will potentially impact marine ecosystems and their associated biogeochemical cycles in the future; however, results amongst studies, particularly when performed on natural communities, are highly variable, which may reflect community/environment-specific responses or inconsistencies in experimental approach. To investigate the potential for identification of more generic responses and greater experimentally reproducibility, we devised and implemented a series (n = 8) of short-term (2-4 days) multi-level (≥4 conditions) carbonate chemistry/nutrient manipulation experiments on a range of natural microbial communities sampled in Northwest European shelf seas. Carbonate chemistry manipulations and resulting biological responses were found to be highly reproducible within individual experiments and to a lesser extent between geographically separated experiments. Statistically robust reproducible physiological responses of phytoplankton to increasing pCO2, characterised by a suppression of net growth for small-sized cells (ocean.

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

    Science.gov (United States)

    Helms, Eric; Arpaia, Nicholas; Widener, Melissa

    2007-01-01

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

  17. Solid-state NMR of polymers

    Energy Technology Data Exchange (ETDEWEB)

    Mirau, P

    2001-07-01

    Nuclear magnetic resonance (NMR) spectroscopy has emerged as one of the most important methods for the solid-state characterisation of polymers. The popularity of NMR is due to the fact that many molecular level features can be measured from the NMR spectra, including the polymer chain conformation, the morphology and the dynamics. The spectral features and relaxation times are affected by local interactions, so they provide information about the structure of polymers on a length scale (2-200 A) that is difficult to measure by other methods. In favourable cases, the NMR experiments provide a molecular-level explanation for the transitions observed by differential scanning calorimetry (DSC) and other methods, and the NMR properties can often be related to the bulk properties. Solid-state NMR has long been of interest in polymer science, and the first solid-state NMR studies of polymers were reported approximately a year after the discovery of nuclear resonance in bulk matter. It was reported in this initial study that the proton line width for natural rubber at room temperature is more like that of a mobile liquid than of a solid, but that the resonance broadens near the glass transition temperature (T{sub g}). This was recognised as being related to a change in chain dynamics above and below the T{sub g}. NMR methods developed rapidly after these initial observations, first for polymers in solution and, more recently, for polymers in the solid-state. Solid-state NMR studies of polymers were developed more slowly than their solution-state counterparts because solid-state NMR requires more specialised equipment. Solid-state NMR is now such an important tool that most modern spectrometers are capable of performing these studies. The interest in the NMR of solid polymers is due in part to the fact that most polymers are used in the solid state, and in many cases the NMR properties can be directly related to the macroscopic properties. Polymers have restricted mobility

  18. Design-of-experiments to Reduce Life-cycle Costs in Combat Aircraft Inlets

    Science.gov (United States)

    Anderson, Bernhard H.; Baust, Henry D.; Agrell, Johan

    2003-01-01

    It is the purpose of this study to demonstrate the viability and economy of Design- of-Experiments (DOE), to arrive at micro-secondary flow control installation designs that achieve optimal inlet performance for different mission strategies. These statistical design concepts were used to investigate the properties of "low unit strength" micro-effector installation. "Low unit strength" micro-effectors are micro-vanes, set a very low angle-of incidence, with very long chord lengths. They are designed to influence the neat wall inlet flow over an extended streamwise distance. In this study, however, the long chord lengths were replicated by a series of short chord length effectors arranged in series over multiple bands of effectors. In order to properly evaluate the performance differences between the single band extended chord length installation designs and the segmented multiband short chord length designs, both sets of installations must be optimal. Critical to achieving optimal micro-secondary flow control installation designs is the understanding of the factor interactions that occur between the multiple bands of micro-scale vane effectors. These factor interactions are best understood and brought together in an optimal manner through a structured DOE process, or more specifically Response Surface Methods (RSM).

  19. Direct-contact condensers for open-cycle OTEC applications: Model validation with fresh water experiments for structured packings

    Science.gov (United States)

    Bharathan, D.; Parsons, B. K.; Althof, J. A.

    1988-10-01

    The objective of the reported work was to develop analytical methods for evaluating the design and performance of advanced high-performance heat exchangers for use in open-cycle thermal energy conversion (OC-OTEC) systems. This report describes the progress made on validating a one-dimensional, steady-state analytical computer of fresh water experiments. The condenser model represents the state of the art in direct-contact heat exchange for condensation for OC-OTEC applications. This is expected to provide a basis for optimizing OC-OTEC plant configurations. Using the model, we examined two condenser geometries, a cocurrent and a countercurrent configuration. This report provides detailed validation results for important condenser parameters for cocurrent and countercurrent flows. Based on the comparisons and uncertainty overlap between the experimental data and predictions, the model is shown to predict critical condenser performance parameters with an uncertainty acceptable for general engineering design and performance evaluations.

  20. Direct-contact condensers for open-cycle OTEC applications: Model validation with fresh water experiments for structured packings

    Energy Technology Data Exchange (ETDEWEB)

    Bharathan, D.; Parsons, B.K.; Althof, J.A.

    1988-10-01

    The objective of the reported work was to develop analytical methods for evaluating the design and performance of advanced high-performance heat exchangers for use in open-cycle thermal energy conversion (OC-OTEC) systems. This report describes the progress made on validating a one-dimensional, steady-state analytical computer of fresh water experiments. The condenser model represents the state of the art in direct-contact heat exchange for condensation for OC-OTEC applications. This is expected to provide a basis for optimizing OC-OTEC plant configurations. Using the model, we examined two condenser geometries, a cocurrent and a countercurrent configuration. This report provides detailed validation results for important condenser parameters for cocurrent and countercurrent flows. Based on the comparisons and uncertainty overlap between the experimental data and predictions, the model is shown to predict critical condenser performance parameters with an uncertainty acceptable for general engineering design and performance evaluations. 33 refs., 69 figs., 38 tabs.

  1. Molecular motions in thermotropic liquid crystals studied by NMR spin-lattice relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Zamar, R.C.; Gonzalez, C.E.; Mensio, O. [Cordoba Univ. Nacional (Argentina). Facultad de Matematica, Astronomia y Fisica

    1998-12-01

    Nuclear magnetic resonance relaxation experiments with field cycling techniques proved to be a valuable tool for studying molecular motions in liquid crystals, allowing a very broad Larmor frequency variation, sufficient to separate the cooperative motions from the liquid like molecular diffusion. In new experiments combining NMR field cycling with the Jeener-Broekaert order-transfer pulse sequence, it is possible to measure the dipolar order relaxation time (T{sub 1D}), in addition to the conventional Zeeman relaxation time (T{sub 1Z}) in a frequency range of several decades. When applying this technique to nematic thermotropic liquid crystals, T{sub 1D} showed to depend almost exclusively on the order fluctuation of the director mechanism in the whole frequency range. This unique characteristic of T{sub 1D} makes dipolar order relaxation experiments specially useful for studying the frequency and temperature dependence of the spectral properties of the collective motions. (author)

  2. ABACUS, a direct method for protein NMR structure computation via assembly of fragments.

    Science.gov (United States)

    Grishaev, A; Steren, C A; Wu, B; Pineda-Lucena, A; Arrowsmith, C; Llinás, M

    2005-10-01

    The ABACUS algorithm obtains the protein NMR structure from unassigned NOESY distance restraints. ABACUS works as an integrated approach that uses the complete set of available NMR experimental information in parallel and yields spin system typing, NOE spin pair identities, sequence specific resonance assignments, and protein structure, all at once. The protocol starts from unassigned molecular fragments (including single amino acid spin systems) derived from triple-resonance (1)H/(13)C/(15)N NMR experiments. Identifications of connected spin systems and NOEs precede the full sequence specific resonance assignments. The latter are obtained iteratively via Monte Carlo-Metropolis and/or probabilistic sequence selections, molecular dynamics structure computation and BACUS filtering (A. Grishaev and M. Llinás, J Biomol NMR 2004;28:1-10). ABACUS starts from scratch, without the requirement of an initial approximate structure, and improves iteratively the NOE identities in a self-consistent fashion. The procedure was run as a blind test on data recorded on mth1743, a 70-amino acid genomic protein from M. thermoautotrophicum. It converges to a structure in ca. 15 cycles of computation on a 3-GHz processor PC. The calculated structures are very similar to the ones obtained via conventional methods (1.22 A backbone RMSD). The success of ABACUS on mth1743 further validates BACUS as a NOESY identification protocol.

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

    DEFF Research Database (Denmark)

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

    2009-01-01

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

  4. Zero-field NMR and NQR spectrometer

    Science.gov (United States)

    Bielecki, A.; Zax, D. B.; Zilm, K. W.; Pines, A.

    1986-03-01

    In comparison to high-field NMR, zero-field techniques offer advantages in terms of spectral interpretability in studies of polycrystalline or amorphous solids. This article describes a technique and apparatus for time-domain measurements of nuclear magnetism in the absence of applied fields (Fourier transform zero-field NMR and NQR). Magnetic field cycling and high field detection are employed to enhance sensitivity. The field cycling is accomplished with an air-driven shuttle system which moves the sample between regions of high and low magnetic field, in combination with switchable electromagnets in the low-field region. Sudden field steps or pulses are used to initiate coherent nuclear spin evolution in zero field and to monitor such evolution as a function of time. Experimental results are shown and analyzed. Possible variations on the basic method are described and their relative advantages are discussed.

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

    Science.gov (United States)

    Frydman, Lucio; Scherf, Tali; Lupulescu, Adonis

    2002-01-01

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

  6. Petrophysical properties of greensand as predicted from NMR measurements

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  7. NMR Based Quantum Information Processing Achievements and Prospects

    CERN Document Server

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

    2000-01-01

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

  8. Bringing NMR and IR Spectroscopy to High Schools

    Science.gov (United States)

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

    2017-01-01

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

  9. Bringing NMR and IR Spectroscopy to High Schools

    Science.gov (United States)

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

    2017-01-01

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

  10. Realization of quantum discrete Fourier transform with NMR

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

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

  11. In situ solid-state NMR spectroscopy of electrochemical cells: batteries, supercapacitors, and fuel cells.

    Science.gov (United States)

    Blanc, Frédéric; Leskes, Michal; Grey, Clare P

    2013-09-17

    Electrochemical cells, in the form of batteries (or supercapacitors) and fuel cells, are efficient devices for energy storage and conversion. These devices show considerable promise for use in portable and static devices to power electronics and various modes of transport and to produce and store electricity both locally and on the grid. For example, high power and energy density lithium-ion batteries are being developed for use in hybrid electric vehicles where they improve the efficiency of fuel use and help to reduce greenhouse gas emissions. To gain insight into the chemical reactions involving the multiple components (electrodes, electrolytes, interfaces) in the electrochemical cells and to determine how cells operate and how they fail, researchers ideally should employ techniques that allow real-time characterization of the behavior of the cells under operating conditions. This Account reviews the recent use of in situ solid-state NMR spectroscopy, a technique that probes local structure and dynamics, to study these devices. In situ NMR studies of lithium-ion batteries are performed on the entire battery, by using a coin cell design, a flat sealed plastic bag, or a cylindrical cell. The battery is placed inside the NMR coil, leads are connected to a potentiostat, and the NMR spectra are recorded as a function of state of charge. (7)Li is used for many of these experiments because of its high sensitivity, straightforward spectral interpretation, and relevance to these devices. For example, (7)Li spectroscopy was used to detect intermediates formed during electrochemical cycling such as LixC and LiySiz species in batteries with carbon and silicon anodes, respectively. It was also used to observe and quantify the formation and growth of metallic lithium microstructures, which can cause short circuits and battery failure. This approach can be utilized to identify conditions that promote dendrite formation and whether different electrolytes and additives can help

  12. Two cycles of adjuvant carboplatin in stage I seminoma: 8-year experience by the Hellenic Cooperative Oncology Group (HECOG).

    Science.gov (United States)

    Koutsoukos, Konstantinos; Tzannis, Kimon; Christodoulou, Christos; Karavasilis, Vasilios; Bakoyiannis, Charalambos; Makatsoris, Thomas; Papandreou, C N; Pectasides, Dimitrios; Dimopoulos, Meletios A; Bamias, Aristotelis

    2016-06-01

    Following the establishment of adjuvant carboplatin in stage I testicular seminoma as a standard, we adopted this treatment for all stage I seminoma patients. We report our 8-year experience and compare these results with our previous adjuvant etoposide/cisplatin (EP) strategy. Patients with stage I seminoma, treated with adjuvant carboplatin and with a minimum follow-up of 1 year, were included. Two cycles of carboplatin [area under the curve (AUC) 6] were administered. A total of 138 patients with median age of 34 years, treated from September 2003 to December 2011, were selected. There were 5 relapses [5-year relapse-free rate (RFR) 96.8 % (95 % confidence interval 91.6-98.8)]: 3 relapses at retroperitoneal lymph nodes, 1 relapse at the adrenal gland, and 1 isolated brain metastasis. Four patients with relapse were cured with salvage chemotherapy. All patients with relapse had tumor diameter ≥4 cm and/or age ≤34 years. Patients with at least 1 of the above risk factors (n = 111) had a significantly higher relapse rate compared with a similar population (n = 64) treated with 2 cycles of adjuvant EP: 5-year RFR was 95 % (SE 2 %) versus 100 % (SE 0 %), (p = 0.067). Age and tumor diameter were associated with relapse in stage I seminoma treated with adjuvant carboplatin. Although adjuvant carboplatin in patients with age ≤34 and/or tumor diameter ≥4 cm is associated with higher relapse rates than EP, the prognosis of these patients is excellent, and therefore, the use of less toxic treatment is justified.

  13. Dynamic NMR cardiac imaging in a piglet

    Energy Technology Data Exchange (ETDEWEB)

    Doyle, M.; Rzedzian, R.; Mansfield, P. (Nottingham Univ. (UK). Dept. of Physics); Coupland, R.E. (Nottingham Univ. (UK). Queen' s Medical Centre)

    1983-12-01

    NMR echo-planar imaging (EPI) has been used in a real-time mode to visualise the thorax of a live piglet. Moving pictures are available on an immediate image display system which demonstrates dynamic cardiac function. Frame rates vary from one per cardiac cycle in a prospective stroboscopic mode with immediate visual output to a maximum of 10 frames per second yielding up to six looks in one piglet heart cycle, but using a visual playback mode. A completely new system has been used to obtain these images, features of which include a probe assembly with 22 cm access and an AP400 array processor for real-time data processing.

  14. The Baltic Sea Experiment (BALTEX): A European contribution to the investigation of the energy and water cycle over a large drainage basin

    DEFF Research Database (Denmark)

    Raschke, E.; Meywerk, J.; Warrach, K.

    2001-01-01

    The Baltic Sea Experiment (BALTEX) is one of the five continental-scale experiments of the Global Energy and Water Cycle Experiment (GEWEX). More than 50 research groups from 14 European countries are participating in this project to measure and model the energy and water cycle over the large...... drainage basin of the Baltic Sea in northern Europe. BALTEX aims to provide a better understanding of the processes of the climate system and to improve and to validate the water cycle in regional numerical models for weather forecasting and climate studies. A major effort is undertaken to couple...... interactively the atmosphere with the vegetated continental surfaces and the Baltic Sea including its sea ice. The intensive observational and modeling phase BRIDGE, which is a contribution to the Coordinated Enhanced Observing Period of GEWEX, will provide enhanced datasets for the period October 1999-February...

  15. NMR analog of the quantum disentanglement eraser.

    Science.gov (United States)

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

    2001-06-25

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

  16. SIMPSON: a general simulation program for solid-state NMR spectroscopy.

    Science.gov (United States)

    Bak, M; Rasmussen, J T; Nielsen, N C

    2000-12-01

    A computer program for fast and accurate numerical simulation of solid-state NMR experiments is described. The program is designed to emulate a NMR spectrometer by letting the user specify high-level NMR concepts such as spin systems, nuclear spin interactions, RF irradiation, free precession, phase cycling, coherence-order filtering, and implicit/explicit acquisition. These elements are implemented using the Tcl scripting language to ensure a minimum of programming overhead and direct interpretation without the need for compilation, while maintaining the flexibility of a full-featured programming language. Basically, there are no intrinsic limitations to the number of spins, types of interactions, sample conditions (static or spinning, powders, uniaxially oriented molecules, single crystals, or solutions), and the complexity or number of spectral dimensions for the pulse sequence. The applicability ranges from simple 1D experiments to advanced multiple-pulse and multiple-dimensional experiments, series of simulations, parameter scans, complex data manipulation/visualization, and iterative fitting of simulated to experimental spectra. A major effort has been devoted to optimizing the computation speed using state-of-the-art algorithms for the time-consuming parts of the calculations implemented in the core of the program using the C programming language. Modification and maintenance of the program are facilitated by releasing the program as open source software (General Public License) currently at http://nmr.imsb.au.dk. The general features of the program are demonstrated by numerical simulations of various aspects for REDOR, rotational resonance, DRAMA, DRAWS, HORROR, C7, TEDOR, POST-C7, CW decoupling, TPPM, F-SLG, SLF, SEMA-CP, PISEMA, RFDR, QCPMG-MAS, and MQ-MAS experiments.

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

    Science.gov (United States)

    Mori, Yukie; Masuda, Yuichi

    2015-09-01

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

  18. Global energy and water cycle experiment (GEWEX) continental-scale international project (GCIP); reference data sets CD-ROM

    Science.gov (United States)

    Rea, Alan; Cederstrand, Joel R.

    1994-01-01

    The data sets on this compact disc are a compilation of several geographic reference data sets of interest to the global-change research community. The data sets were chosen with input from the Global Energy and Water Cycle Experiment (GEWEX) Continental-Scale International Project (GCIP) Data Committee and the GCIP Hydrometeorology and Atmospheric Subpanels. The data sets include: locations and periods of record for stream gages, reservoir gages, and meteorological stations; a 500-meter-resolution digital elevation model; grid-node locations for the Eta numerical weather-prediction model; and digital map data sets of geology, land use, streams, large reservoirs, average annual runoff, average annual precipitation, average annual temperature, average annual heating and cooling degree days, hydrologic units, and state and county boundaries. Also included are digital index maps for LANDSAT scenes, and for the U.S. Geological Survey 1:250,000, 1:100,000, and 1:24,000-scale map series. Most of the data sets cover the conterminous United States; the digital elevation model also includes part of southern Canada. The stream and reservoir gage and meteorological station files cover all states having area within the Mississippi River Basin plus that part of the Mississippi River Basin lying within Canada. Several data-base retrievals were processed by state, therefore many sites outside the Mississippi River Basin are included.

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

    NARCIS (Netherlands)

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

    2015-01-01

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

  20. NMR with Hyperpolarised Protons in Metals

    Energy Technology Data Exchange (ETDEWEB)

    Engelbertz, A., E-mail: engelbert@iskp.uni-bonn.de; Anbalagan, P.; Bommas, C.; Eversheim, P.-D.; Hartman, D. T.; Maier, K. [University of Bonn, Helmholtz- Institut fuer Strahlen und Kernphysik (Germany)

    2004-12-15

    Proton pulse NMR, established as a versatile method in Solid State Physics, Chemistry, Biology and Medical Science, requires on the order of 10{sup 18} nuclei to detect an electromagnetic signal in a free induction decay (FID). The main cause for this small sensitivity is the low polarisation in the order of a few ppm due to the Boltzmann distribution in the magnetic field. Thus, NMR experiments on hydrogen are limited to metals with extremely high hydrogen solubility like Pd near room temperature. Using a polarised proton beam, a NMR signal is possible with as few as 10{sup 13} implanted nuclei. For the first time spin-spin and spin-lattice relaxation times were measured in Au and W with this technique at the Bonn cyclotron.

  1. Theoretical NMR correlations based Structure Discussion

    Directory of Open Access Journals (Sweden)

    Junker Jochen

    2011-07-01

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

  2. Radiation damping in microcoil NMR probes.

    Science.gov (United States)

    Krishnan, V V

    2006-04-01

    Radiation damping arises from the field induced in the receiver coil by large bulk magnetization and tends to selectively drive this magnetization back to equilibrium much faster than relaxation processes. The demand for increased sensitivity in mass-limited samples has led to the development of microcoil NMR probes that are capable of obtaining high quality NMR spectra with small sample volumes (nL-microL). Microcoil probes are optimized to increase sensitivity by increasing either the sample-to-coil ratio (filling factor) of the probe or quality factor of the detection coil. Though radiation damping effects have been studied in standard NMR probes, these effects have not been measured in the microcoil probes. Here a systematic evaluation of radiation damping effects in a microcoil NMR probe is presented and the results are compared with similar measurements in conventional large volume samples. These results show that radiation-damping effects in microcoil probe is much more pronounced than in 5 mm probes, and that it is critically important to optimize NMR experiments to minimize these effects. As microcoil probes provide better control of the bulk magnetization, with good RF and B0 inhomogeneity, in addition to negligible dipolar field effects due to nearly spherical sample volumes, these probes can be used exclusively to study the complex behavior of radiation damping.

  3. Magic angle spinning NMR of paramagnetic proteins.

    Science.gov (United States)

    Knight, Michael J; Felli, Isabella C; Pierattelli, Roberta; Emsley, Lyndon; Pintacuda, Guido

    2013-09-17

    Metal ions are ubiquitous in biochemical and cellular processes. Since many metal ions are paramagnetic due to the presence of unpaired electrons, paramagnetic molecules are an important class of targets for research in structural biology and related fields. Today, NMR spectroscopy plays a central role in the investigation of the structure and chemical properties of paramagnetic metalloproteins, linking the observed paramagnetic phenomena directly to electronic and molecular structure. A major step forward in the study of proteins by solid-state NMR came with the advent of ultrafast magic angle spinning (MAS) and the ability to use (1)H detection. Combined, these techniques have allowed investigators to observe nuclei that previously were invisible in highly paramagnetic metalloproteins. In addition, these techniques have enabled quantitative site-specific measurement of a variety of long-range paramagnetic effects. Instead of limiting solid-state NMR studies of biological systems, paramagnetism provides an information-rich phenomenon that can be exploited in these studies. This Account emphasizes state-of-the-art methods and applications of solid-state NMR in paramagnetic systems in biological chemistry. In particular, we discuss the use of ultrafast MAS and (1)H-detection in perdeuterated paramagnetic metalloproteins. Current methodology allows us to determine the structure and dynamics of metalloenzymes, and, as an example, we describe solid-state NMR studies of microcrystalline superoxide dismutase, a 32 kDa dimer. Data were acquired with remarkably short times, and these experiments required only a few milligrams of sample.

  4. NMR, Water and Plants

    NARCIS (Netherlands)

    As, van H.

    1982-01-01

    This Thesis describes the application of a non-destructive pulsed proton NMR method mainly to measure water transport in the xylem vessels of plant stems and in some model systems. The results are equally well applicable to liquid flow in other biological objects than plants, e.g. flow of blood and

  5. Single-sided NMR

    CERN Document Server

    Casanova, Federico; Blümich, Bernhard

    2011-01-01

    Single-Sided NMR describes the design of the first functioning single-sided tomograph, the related measurement methods, and a number of applications. One of the key advantages to this method is the speed at which the images are obtained.

  6. Autonomous driving in NMR.

    Science.gov (United States)

    Perez, Manuel

    2017-01-01

    The automatic analysis of NMR data has been a much-desired endeavour for the last six decades, as it is the case with any other analytical technique. This need for automation has only grown as advances in hardware; pulse sequences and automation have opened new research areas to NMR and increased the throughput of data. Full automatic analysis is a worthy, albeit hard, challenge, but in a world of artificial intelligence, instant communication and big data, it seems that this particular fight is happening with only one technique at a time (let this be NMR, MS, IR, UV or any other), when the reality of most laboratories is that there are several types of analytical instrumentation present. Data aggregation, verification and elucidation by using complementary techniques (e.g. MS and NMR) is a desirable outcome to pursue, although a time-consuming one if performed manually; hence, the use of automation to perform the heavy lifting for users is required to make the approach attractive for scientists. Many of the decisions and workflows that could be implemented under automation will depend on the two-way communication with databases that understand analytical data, because it is desirable not only to query these databases but also to grow them in as much of an automatic manner as possible. How these databases are designed, set up and the data inside classified will determine what workflows can be implemented. Copyright © 2016 John Wiley & Sons, Ltd.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-09-08

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

  8. DMSP and DMS dynamics during a mesoscale iron fertilization experiment in the Northeast Pacific Part II: Biological cycling

    Science.gov (United States)

    Merzouk, Anissa; Levasseur, Maurice; Scarratt, Michael G.; Michaud, Sonia; Rivkin, Richard B.; Hale, Michelle S.; Kiene, Ronald P.; Price, Neil M.; Li, William K. W.

    2006-10-01

    Dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) biological cycling rates were determined during SERIES, a mesoscale iron-fertilization experiment conducted in the high-nutrient low-chlorophyll (HNLC) waters of the northeast subarctic Pacific. The iron fertilization resulted in the rapid development of a nanoplankton assemblage that persisted for 11 days before abruptly crashing. The nanoplankton bloom was followed by a diatom bloom, accompanied by an important increase in bacterial abundance and production. These iron-induced alterations of the plankton assemblage coincided with changes in the size and biological cycling of the DMSP and DMS pools. The initial nanoplankton bloom resulted in increases in particulate DMSP (DMSPp; 77-180 nmol L -1), dissolved DMSP (DMSPd; 1-24 nmol L -1), and biological gross (0.11-0.78 nmol L -1 h -1) and net (0.04-0.74 nmol L -1 h -1) DMS production rates. During the nanoplankton bloom, DMSPd consumption by bacteria exceeded their sulfur demand and the excess sulfur was probably released as DMS, consistent with the high gross DMS production rates observed during that period. The crash of the nanoplankton bloom was marked by the rapid decline of DMSPp, DMSPd, and gross DMS production to their initial values. Following the crash of the nanoplankton bloom, bacterial production and estimated sulfur demand reached transient maxima of 9.3 μg C L -1 d -1 and 14.2 nmol S L -1 d -1, respectively. During this period of high bacterial production, bacterial DMSPd consumption was also very high (6 nmol L -1 h -1), but none of the consumed DMSPd was converted into DMS and a net biological DMS consumption was measured. This transient period initiated a rapid decrease in DMS concentrations inside the iron-enriched patch, which persisted during the following diatom bloom due to low biological gross and net DMS production that prevented the replenishment of DMS. Our results show that the impact of Fe fertilization on DMS production in

  9. Direct Observation of Secondary Organic Aerosol Formation during Cloud Condensation-Evaporation Cycles (SOAaq) in Simulation Chamber Experiments

    Science.gov (United States)

    Doussin, J. F.; Bregonzio-Rozier, L.; Giorio, C.; Siekmann, F.; Gratien, A.; Temime-Roussel, B.; Ravier, S.; Pangui, E.; Tapparo, A.; Kalberer, M.; Monod, A.

    2014-12-01

    Biogenic volatile organic compounds (BVOCs) undergo many reactions in the atmosphere and form a wide range of oxidised and water-soluble compounds. These compounds can partition into atmospheric water droplets, and react within the aqueous phase producing higher molecular weight and/or less volatile compounds which can remain in the particle phase after water evaporation and thus increase the organic aerosol mass (Ervens et al., 2011; Altieri et al., 2008; Couvidat et al., 2013). While this hypothesis is frequently discussed in the literature, so far, almost no direct observations of such a process have been provided.The aim of the present work is to study SOA formation from isoprene photooxidation during cloud condensation-evaporation cycles.The experiments were performed during the CUMULUS project (CloUd MULtiphase chemistry of organic compoUndS in the troposphere), in the CESAM simulation chamber located at LISA. CESAM is a 4.2 m3 stainless steel chamber equipped with realistic irradiation sources and temperature and relative humidity (RH) controls (Wang et al., 2011). In each experiment, isoprene was allowed to oxidize during several hours in the presence on nitrogen oxides under dry conditions. Gas phase compounds were analyzed on-line by a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-ToF-MS), a Fourier Transform Infrared Spectrometer (FTIR), NOx and O3 analyzers. SOA formation was monitored on-line with a Scanning Mobility Particle Sizer (SMPS) and an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). The experimental protocol was optimised to generate cloud events in the simulation chamber, which allowed us to generate clouds lasting for ca. 10 minutes in the presence of light.In all experiments, we observed that during cloud formation, water-soluble gas-phase oxidation products (e.g., methylglyoxal, hydroxyacetone, acetaldehyde, formic acid, acetic acid and glycolaldehyde) readily partitioned into cloud

  10. Incorporation of FT-NMR into Research Infrastructure and Chemistry Curriculum at Bowie State University

    Science.gov (United States)

    2014-01-09

    data. The library of easily used 1D and 2D experiments includes, COSY, DEPT, HETCOR, T1, T2, and kinetics. ii. NUTS (Acorn NMR Inc.) - A NMR data...HBCU) - Incorporation of FT- NMR into Research Infrastructure and Chemistry Curriculum at Bowie State University ALAN ANDERSON BOWIE STATE...Award# FA9550-12-1-0448 (HBCU) Incorporation of FT- NMR into Research Infrastructure and Chemistry Curriculum at

  11. Modern solid-state NMR on functional polymers; Moderne Festkoerper-NMR an Funktionspolymeren

    Energy Technology Data Exchange (ETDEWEB)

    Wang, M.

    2004-07-01

    In this thesis the microscopic structures of natural caoutchouc, on silicic acid plugged polydimethylsiloxane (PDMS), and polyamide-clay-nanocomposite are studied. For natural caoutchouc it is shown how the network density can be characterized by the study of the dipole-dipole couplings between protons and carbon by means of the heteronuclear double-quantum NMR method and further double-resonance experiments. In PDMS homo- and heteronuclear multi-quantum NMR, spin-diffusion, relaxometry, and double-resonance experiments are used for the study of the dependence of the molecular motion on external influences. Finally the structural change of polyamides by addition of clay particles is studied.

  12. MEASURING VARIABILITY SOURCES IN NMR METABOLOMIC STUDIES

    OpenAIRE

    Rozet, Eric; de Tullio, Pascal; Hubert, Philippe; Govaerts., B.

    2013-01-01

    Due to the huge amount of information available in NMR spectra obtained from the analysis of metabolomic experiments, multivariate analysis such as Principal Component Analysis (PCA) are required to understand the influence of treatments over the metabolites [1]. However, many experiments in metabolomics studies have more complexes variability structures than simply comparing several treatments: they may include time effects, biological effects such as diet or hormonal status, and other bloc...

  13. Determination of the Rotational Barrier for Kinetically Stable Conformational Isomers via NMR and 2D TLC: An Introductory Organic Chemistry Experiment

    Science.gov (United States)

    Rushton, Gregory T.; Burns, William G.; Lavin, Judi M.; Chong, Yong S.; Pellechia, Perry; Shimizu, Ken D.

    2007-01-01

    An experiment to determine the rotational barrier about a C[subscript aryl]-N[subscript imide] single bond that is suitable for first-semester organic chemistry students is presented. The investigation begins with the one-step synthesis of a N,N'-diaryl naphthalene diimide, which exists as two room temperature-stable atropisomers (syn and anti).…

  14. Determination of Unknown Concentrations of Sodium Acetate Using the Method of Standard Addition and Proton NMR: An Experiment for the Undergraduate Analytical Chemistry Laboratory

    Science.gov (United States)

    Rajabzadeh, Massy

    2012-01-01

    In this experiment, students learn how to find the unknown concentration of sodium acetate using both the graphical treatment of standard addition and the standard addition equation. In the graphical treatment of standard addition, the peak area of the methyl peak in each of the sodium acetate standard solutions is found by integration using…

  15. Determination of Unknown Concentrations of Sodium Acetate Using the Method of Standard Addition and Proton NMR: An Experiment for the Undergraduate Analytical Chemistry Laboratory

    Science.gov (United States)

    Rajabzadeh, Massy

    2012-01-01

    In this experiment, students learn how to find the unknown concentration of sodium acetate using both the graphical treatment of standard addition and the standard addition equation. In the graphical treatment of standard addition, the peak area of the methyl peak in each of the sodium acetate standard solutions is found by integration using…

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-20

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

  17. NMR for chemists and biologists

    CERN Document Server

    Carbajo, Rodrigo J

    2013-01-01

    This book offers a concise introduction to the field of nuclear magnetic resonance or NMR. It presents the basic foundations of NMR in a non-mathematical way and provides an overview of both recent and important biological applications of NMR.

  18. NMR magnet technology at MIT

    Energy Technology Data Exchange (ETDEWEB)

    Williams, J.E.C.; Bobrov, E.S.; Iwasa, Y.; Punchard, W.F.B.; Wrenn, J.; Zhukovsky, A. (Massachusetts Inst. of Tech., Cambridge, MA (United States). Francis Bitter National Magnet Lab.)

    1992-01-01

    The design and construction of high field superconducting NMR magnets has much in common with other types of adiabatic superconducting magnets. However, two issues have a particular relevance to NMR magnets. They are field drift and homogeneity. In this paper the control of these factors in the particular context of high field NMR spectrometer magnets is examined.

  19. Metabolic pathway visualization in living yeast by DNP-NMR.

    Science.gov (United States)

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

    2011-10-01

    Central carbon metabolism of living Saccharomyces cerevisiae is visualized by DNP-NMR. Experiments are conducted as real time assays that detect metabolic bottlenecks, pathway use, reversibility of reactions and reaction mechanisms in vivo with subsecond time resolution.

  20. OPENCORE NMR: open-source core modules for implementing an integrated FPGA-based NMR spectrometer.

    Science.gov (United States)

    Takeda, Kazuyuki

    2008-06-01

    A tool kit for implementing an integrated FPGA-based NMR spectrometer [K. Takeda, A highly integrated FPGA-based nuclear magnetic resonance spectrometer, Rev. Sci. Instrum. 78 (2007) 033103], referred to as the OPENCORE NMR spectrometer, is open to public. The system is composed of an FPGA chip and several peripheral boards for USB communication, direct-digital synthesis (DDS), RF transmission, signal acquisition, etc. Inside the FPGA chip have been implemented a number of digital modules including three pulse programmers, the digital part of DDS, a digital quadrature demodulator, dual digital low-pass filters, and a PC interface. These FPGA core modules are written in VHDL, and their source codes are available on our website. This work aims at providing sufficient information with which one can, given some facility in circuit board manufacturing, reproduce the OPENCORE NMR spectrometer presented here. Also, the users are encouraged to modify the design of spectrometer according to their own specific needs. A home-built NMR spectrometer can serve complementary roles to a sophisticated commercial spectrometer, should one comes across such new ideas that require heavy modification to hardware inside the spectrometer. This work can lower the barrier of building a handmade NMR spectrometer in the laboratory, and promote novel and exciting NMR experiments.

  1. Structural investigations on betacyanin pigments by LC NMR and 2D NMR spectroscopy.

    Science.gov (United States)

    Stintzing, Florian C; Conrad, Jürgen; Klaiber, Iris; Beifuss, Uwe; Carle, Reinhold

    2004-02-01

    Four betacyanin pigments were analysed by LC NMR and subjected to extensive NMR characterisation after isolation. Previously, low pH values were applied for NMR investigations of betalains resulting in rapid degradation of the purified substances thus preventing extensive NMR studies. Consequently, up to now only one single (13)C NMR spectrum of a betalain pigment, namely that of neobetanin (=14,15-dehydrobetanin), was available. Because of its sufficient stability under highly acidic conditions otherwise detrimental for betacyanins, this pigment remained an exemption. Since betalains are most stable in the pH range of 5-7, a new solvent system has been developed allowing improved data acquisition through improved pigment stability at near neutral pH. Thus, not only (1)H, but for the first time also partial (13)C data of betanin, isobetanin, phyllocactin and hylocerenin isolated from red-purple pitaya [Hylocereus polyrhizus (Weber) Britton & Rose, Cactaceae] could be indirectly obtained by gHSQC- and gHMQC-NMR experiments.

  2. NMR CHARACTERIZATIONS OF PROPERTIES OF HETEROGENEOUS MEDIA

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-01-01

    A critical and long-standing need within the petroleum industry is the specification of suitable petrophysical properties for mathematical simulation of fluid flow in petroleum reservoirs (i.e., reservoir characterization). The development of accurate reservoir characterizations is extremely challenging. Property variations may be described on many scales, and the information available from measurements reflect different scales. In fact, experiments on laboratory core samples, well-log data, well-test data, and reservoir-production data all represent information potentially valuable to reservoir characterization, yet they all reflect information about spatial variations of properties at different scales. Nuclear magnetic resonance (NMR) spectroscopy and imaging (MRI) provide enormous potential for developing new descriptions and understandings of heterogeneous media. NMR has the rare capability to probe permeable media non-invasively, with spatial resolution, and it provides unique information about molecular motions and interactions that are sensitive to morphology. NMR well-logging provides the best opportunity ever to resolve permeability distributions within petroleum reservoirs. We develop MRI methods to determine, for the first time, spatially resolved distributions of porosity and permeability within permeable media samples that approach the intrinsic scale: the finest resolution of these macroscopic properties possible. To our knowledge, this is the first time that the permeability is actually resolved at a scale smaller than the sample. In order to do this, we have developed a robust method to determine of relaxation distributions from NMR experiments and a novel implementation and analysis of MRI experiments to determine the amount of fluid corresponding to imaging regions, which are in turn used to determine porosity and saturation distributions. We have developed a novel MRI experiment to determine velocity distributions within flowing experiments, and

  3. Leaf δ15N as a temporal integrator of nitrogen-cycling processes at the Mojave Desert FACE experiment

    Science.gov (United States)

    Sonderegger, D.; Koyama, A.; Jin, V.; Billings, S. A.; Ogle, K.; Evans, R. D.

    2011-12-01

    Ecosystem response to elevated carbon dioxide (CO2) in arid environments is regulated primarily by water, which may interact with nitrogen availability. Leaf nitrogen isotope composition (δ15N) can serve as an important indicator of changes in nitrogen dynamics by integrating changes in plant physiology and ecosystem biogeochemical processes. Because of this temporal integration, careful modeling of the antecedent conditions is necessary for understanding the processes driving variation in leaf δ15N. We measured leaf δ15N of Larrea tridentata (creosotebush) over the 10-year lifetime of the Nevada Desert Free-Air CO2 Enrichment (FACE) experiment. Leaf δ15N exhibited two patterns. First, elevated atmospheric CO2 significantly increased Larrea leaf δ15N by approximately 2 to 3 % compared to plants exposed to ambient CO2 concentrations Second, plants in both CO2 treatments exhibited significant seasonal cycles in leaf δ15N, with higher values during the fall and winter seasons. We modeled leaf δ15N using a hierarchical Bayesian framework that incorporated soil moisture, temperature, and the Palmer Drought Severity Index (PDSI) covariates in addition to a CO2 treatment effect and plot random effects. Antecedent moisture effects were modeled by using a combination of the previous season's aggregated conditions and a smoothly varying weighted average of the months or weeks directly preceding the observation. The time lag between the driving antecedent condition and the observed change in leaf δ15N indicates a significant and unobserved process mechanism. Preliminary results suggest a CO2 treatment interaction with the lag effect, indicating a treatment effect on the latent process.

  4. Fully automated system for pulsed NMR measurements

    Energy Technology Data Exchange (ETDEWEB)

    Cantor, David Milton

    1977-01-01

    A system is described which places many of the complex, tedious operations for pulsed NMR experiments under computer control. It automatically optimizes the experiment parameters of pulse length and phase, and precision, accuracy, and measurement speed are improved. The hardware interface between the computer and the NMR instrument is described. Design features, justification of the choices made between alternative design strategies, and details of the implementation of design goals are presented. Software features common to all the available experiments are discussed. Optimization of pulse lengths and phases is performed via a sequential search technique called Uniplex. Measurements of the spin-lattice and spin-spin relaxation times and of diffusion constants are automatic. Options for expansion of the system are explored along with some of the limitations of the system.

  5. Engineering out motion: a surface disulfide bond alters the mobility of tryptophan 22 in cytochrome b5 as probed by time-resolved fluorescence and 1H NMR experiments.

    Science.gov (United States)

    Storch, E M; Grinstead, J S; Campbell, A P; Daggett, V; Atkins, W M

    1999-04-20

    In the accompanying paper [Storch et al. (1999) Biochemistry 38, 5054-5064] equilibrium denaturation studies and molecular dynamics (MD) simulations were used to investigate localized dynamics on the surface of cytochrome b5 (cyt b5) that result in the formation of a cleft. In those studies, an S18C:R47C disulfide mutant was engineered to inhibit cleft mobility. Temperature- and urea-induced denaturation studies revealed significant differences in Trp 22 fluorescence between the wild-type and mutant proteins. On the basis of the results, it was proposed that wild type populates a conformational ensemble that is unavailable to the disulfide mutant and is mediated by cleft mobility. As a result, the solvent accessibility of Trp 22 is decreased in S18C:R47C, suggesting that the local environment of this residue is less mobile due to the constraining effects of the disulfide on cleft dynamics. To further probe the structural effects on the local environment of Trp 22 caused by inhibition of cleft formation, we report here the results of steady-state and time-resolved fluorescence quenching, differential phase/modulation fluorescence anisotropy, and 1H NMR studies. In Trp fluorescence experiments, the Stern-Volmer quenching constant increases in wild type versus the oxidized disulfide mutant with increasing temperature. At 50 degrees C, KSV is nearly 1.5-fold greater in wild type compared to the oxidized disulfide mutant. In the reduced disulfide mutant, KSV was the same as wild type. The bimolecular collisional quenching constant, kq, for acrylamide quenching of Trp 22 increases 2.7-fold for wild type and only 1.8-fold for S18C:R47C, upon increasing the temperature from 25 to 50 degrees C. The time-resolved anisotropy decay at 25 degrees C was fit to a double-exponential decay for both the wild type and S18C:R47C. Both proteins exhibited a minor contribution from a low-amplitude fast decay, consistent with local motion of Trp 22. This component was more prevalent in

  6. NMR of unfolded proteins

    Indian Academy of Sciences (India)

    Amarnath Chtterjee; Ashutosh Kumar; Jeetender Chugh; Sudha Srivastava; Neel S Bhavesh; Ramakrishna V Hosur

    2005-01-01

    In the post-genomic era, as more and more genome sequences are becoming known and hectic efforts are underway to decode the information content in them, it is becoming increasingly evident that flexibility in proteins plays a crucial role in many of the biological functions. Many proteins have intrinsic disorder either wholly or in specific regions. It appears that this disorder may be important for regulatory functions of the proteins, on the one hand, and may help in directing the folding process to reach the compact native state, on the other. Nuclear magnetic resonance (NMR) has over the last two decades emerged as the sole, most powerful technique to help characterize these disordered protein systems. In this review, we first discuss the significance of disorder in proteins and then describe the recent developments in NMR methods for their characterization. A brief description of the results obtained on several disordered proteins is presented at the end.

  7. 13C NMR Quantitative Study-Part 1: Relationships between the Conformation of Amino Acids, Peptide, Carboxylic Acids and Integration Intensity of 13C NMR

    Institute of Scientific and Technical Information of China (English)

    TIAN; JinPing

    2001-01-01

    In proton broad band decoupling 13C NMR, carbon atoms have different integration intensity because of NOE effects and their different relaxation time(T1), thus it makes a 13C NMR quantitative analyses very difficult. To acquire a 3C NMR quantitative analyses, a gated decoupling with suppressed NOE technology, i.e., an inversed gated decoupling pulse (IGDP), must be used. In IGDP relay time (tR) between two acquisition cycles must be more than 5T1, the time needed for a acquisition cycles is so long that makes the total 13C NMR quantitative analyses time much longer. For this reason, the 13C NMR quantitative analyses is paid less attention.  ……

  8. 13C NMR Quantitative Study-Part 1: Relationships between the Conformation of Amino Acids, Peptide, Carboxylic Acids and Integration Intensity of 13C NMR

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ In proton broad band decoupling 13C NMR, carbon atoms have different integration intensity because of NOE effects and their different relaxation time(T1), thus it makes a 13C NMR quantitative analyses very difficult. To acquire a 3C NMR quantitative analyses, a gated decoupling with suppressed NOE technology, i.e., an inversed gated decoupling pulse (IGDP), must be used. In IGDP relay time (tR) between two acquisition cycles must be more than 5T1, the time needed for a acquisition cycles is so long that makes the total 13C NMR quantitative analyses time much longer. For this reason, the 13C NMR quantitative analyses is paid less attention.

  9. NMR studies of metalloproteins

    OpenAIRE

    Li, H; H. Sun

    2011-01-01

    Metalloproteins represent a large share of the proteomes, with the intrinsic metal ions providing catalytic, regulatory, and structural roles critical to protein functions. Structural characterization of metalloproteins and identification of metal coordination features including numbers and types of ligands and metal-ligand geometry, and mapping the structural and dynamic changes upon metal binding are significant for understanding biological functions of metalloproteins. NMR spectroscopy has...

  10. NMR Hyperpolarization Techniques of Gases.

    Science.gov (United States)

    Barskiy, Danila A; Coffey, Aaron M; Nikolaou, Panayiotis; Mikhaylov, Dmitry M; Goodson, Boyd M; Branca, Rosa T; Lu, George J; Shapiro, Mikhail G; Telkki, Ville-Veikko; Zhivonitko, Vladimir V; Koptyug, Igor V; Salnikov, Oleg G; Kovtunov, Kirill V; Bukhtiyarov, Valerii I; Rosen, Matthew S; Barlow, Michael J; Safavi, Shahideh; Hall, Ian P; Schröder, Leif; Chekmenev, Eduard Y

    2017-01-18

    Nuclear spin polarization can be significantly increased through the process of hyperpolarization, leading to an increase in the sensitivity of nuclear magnetic resonance (NMR) experiments by 4-8 orders of magnitude. Hyperpolarized gases, unlike liquids and solids, can often be readily separated and purified from the compounds used to mediate the hyperpolarization processes. These pure hyperpolarized gases enabled many novel MRI applications including the visualization of void spaces, imaging of lung function, and remote detection. Additionally, hyperpolarized gases can be dissolved in liquids and can be used as sensitive molecular probes and reporters. This Minireview covers the fundamentals of the preparation of hyperpolarized gases and focuses on selected applications of interest to biomedicine and materials science. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Indirect spin-spin coupling constants in CH{sub 4}, SiH{sub 4} and GeH{sub 4} - Gas-phase NMR experiment and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Antusek, Andrej [Slovak University of Technology in Bratislava, Faculty of Materials Science and Technology in Trnava, Paulinska 16, 917 24 Trnava (Slovakia); Department of Chemistry, Nicolaus Copernicus University, Gagarina 7, PL 87-100 Torun (Poland); Kedziera, Dariusz [Department of Chemistry, Nicolaus Copernicus University, Gagarina 7, PL 87-100 Torun (Poland); Jackowski, Karol [Laboratory of NMR Spectroscopy, Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Jaszunski, Michal [Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01224 Warsaw (Poland)], E-mail: michaljz@icho.edu.pl; Makulski, Wlodzimierz [Laboratory of NMR Spectroscopy, Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)

    2008-09-03

    New values of the indirect spin-spin coupling constants in CH{sub 4}, SiH{sub 4} and GeH{sub 4}, derived from experiment and ab initio calculations, are reported. The new experimental values of {sup 1}J(CH), {sup 1}J(SiH) and {sup 1}J(GeH) are obtained from gas-phase NMR spectra. The dependence of the measured one-bond coupling constants on the density is analysed and the results are extrapolated to zero-density point to eliminate the effects due to intermolecular forces. In the calculation of the coupling constants, at the nonrelativistic level coupled cluster singles and doubles (CCSD) perturbation theory is used and the basis set convergence of the results is discussed. The relativistic corrections are estimated from Dirac-Hartree-Fock (DHF) calculations. The final theoretical values are obtained adding available estimates of the vibrational and temperature corrections. The agreement of the calculated and experimental {sup 1}J(XH), X = C, Si, Ge, constants is very satisfying, the differences are approximately 1-3%.

  12. Advanced solid-state NMR spectroscopy of natural organic matter.

    Science.gov (United States)

    Mao, Jingdong; Cao, Xiaoyan; Olk, Dan C; Chu, Wenying; Schmidt-Rohr, Klaus

    2017-05-01

    Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially a systematic approach to NOM characterization, and their applications to the study of NOM. We discuss some basics of how to acquire high-quality and quantitative solid-state (13)C NMR spectra, and address some common technical mistakes that lead to unreliable spectra of NOM. The identification of specific functional groups in NOM, primarily based on (13)C spectral-editing techniques, is described and the theoretical background of some recently-developed spectral-editing techniques is provided. Applications of solid-state NMR to investigating nitrogen (N) in NOM are described, focusing on limitations of the widely used (15)N CP/MAS experiment and the potential of improved advanced NMR techniques for characterizing N forms in NOM. Then techniques used for identifying proximities, heterogeneities and domains are reviewed, and some examples provided. In addition, NMR techniques for studying segmental dynamics in NOM are reviewed. We also briefly discuss applications of solid-state NMR to NOM from various sources, including soil organic matter, aquatic organic matter, organic matter in atmospheric particulate matter, carbonaceous meteoritic organic matter, and fossil fuels. Finally, examples of NMR-based structural models and an outlook are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2014-10-01

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

  14. NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR.

    Science.gov (United States)

    Schreckenbach, Georg

    2002-12-16

    In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-09-15

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

  16. Half of the world’s population experience robust changes in the water cycle for a 2 °C warmer world

    Science.gov (United States)

    Sedláček, Jan; Knutti, Reto

    2014-04-01

    Fresh water is a critical resource on Earth, yet projections of changes in the water cycle resulting from anthropogenic warming are challenging. It is important to not only know the best estimate of change, but also how robust these projections are, where changes occur, which variables will change, and how many people are affected by it. Here we synthesize the changes in the water cycle, based on results of the latest climate model intercomparison (CMIP5). Several variables of the water cycle, such as evaporation and relative humidity, show robust changes over more than 50% of the land area already with an anthropogenic global warming of 1 °C. A warming of 2 °C shows more than half of the world’s population to be directly affected by robust local changes in the water cycle, and everybody experiences a robust change in at least one variable of the water cycle. While the physical changes are widespread, the affected people are concentrated in a few hot-spots mainly in Asia and Central Africa. The occurrence of these hot-spots is driven by population density, as well as by the early emergence of the anthropogenic signal from variability in these areas. Large uncertainties remain in projections of soil moisture and runoff changes.

  17. Characteristics, cycling patterns, and crash and injury experiences at baseline of a cohort of transport and recreational cyclists in New South Wales, Australia.

    Science.gov (United States)

    Poulos, R G; Hatfield, J; Rissel, C; Flack, L K; Murphy, S; Grzebieta, R; McIntosh, A S

    2015-05-01

    This paper examines self-reported retrospective data for a 12 month period from 2038 adult cyclists from New South Wales (Australia), and compares cyclists according to whether they self-identify as riding mainly for transport or mainly for recreation. Statistically significant differences were found in the demographic characteristics, cycling patterns, and crash experiences between these two groups of cyclists. Transport cyclists tended to be younger, travel more days per week, and within morning and evening peak hours than recreational cyclists; recreational cyclists were more likely to identify fitness as a purpose for cycling. The proportion of cyclists experiencing a crash or crash-related injury in the previous 12 months was similar for transport and recreational cyclists, but there were differences in crash types and location which likely reflect different cycling environments. Heterogeneity within transport and recreational cyclists was also found, based on self-reported riding intensity. An understanding of the different cycling patterns and experiences of various types of cyclists is useful to inform road safety, transport and health promotion policy.

  18. Five years' experience of preimplantation genetic diagnosis in the Parisian Center: outcome of the first 441 started cycles.

    Science.gov (United States)

    Feyereisen, Estelle; Steffann, Julie; Romana, Serge; Lelorc'h, Marc; Ray, Pierre; Kerbrat, Violaine; Tachdjian, Gérard; Frydman, René; Frydman, Nelly

    2007-01-01

    To investigate the evolution of techniques and strategies and to evaluate the results of preimplantation genetic diagnosis (PGD) from January 2000 to December 2004 in chromosomal, monogenic and mitochondrial DNA disorders treated at our institution. Retrospective study. Single French Parisian PGD center. Patients at risk of transmitting a serious genetic disorder to their offspring. 171 couples enrolled in the program undergoing stimulated and frozen embryo replacement cycles with PGD. Results of the 441 first PGD cycles performed for various genetic conditions. During 5 years, 416 stimulation and 25 frozen embryo replacement cycles were started, among which 52 clinical and 47 ongoing pregnancies occurred. In stimulation cycles, the overall ongoing pregnancy rate was 24% per embryo transfer, 11% per started cycle, and 27% per couple. The implantation rate was 16%. These encouraging results demonstrate that PGD might be considered as a valid alternative to prenatal diagnosis. Nevertheless, couples referred for PGD must be selected and counseled appropriately, considering the complexity of the treatment and the relatively low take-home baby rate.

  19. NMR-Based Diffusion Lattice Imaging

    CERN Document Server

    Laun, Frederik Bernd

    2013-01-01

    Nuclear magnetic resonance (NMR) diffusion experiments are widely employed as they yield information about structures hindering the diffusion process, e.g. about cell membranes. While it has been shown in recent articles, that these experiments can be used to determine the exact shape of closed pores averaged over a volume of interest, it is still an open question how much information can be gained in open systems. In this theoretical work, we show that the full structure information of periodic open systems is accessible. To this end, the so-called 'SEquential Rephasing by Pulsed field-gradient Encoding N Time-intervals' (SERPENT) sequence is used, which employs several diffusion weighting gradient pulses with different amplitudes. The structural information is obtained by an iterative technique relying on a Gaussian envelope model of the diffusion propagator. Two solid matrices that are surrounded by an NMR-visible medium are considered: a hexagonal lattice of cylinders and a cubic lattice of triangles.

  20. Structural Studies of Biological Solids Using NMR

    Science.gov (United States)

    Ramamoorthy, Ayyalusamy

    2011-03-01

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

  1. Structural biology applications of solid state MAS DNP NMR

    Science.gov (United States)

    Akbey, Ümit; Oschkinat, Hartmut

    2016-08-01

    Dynamic Nuclear Polarization (DNP) has long been an aim for increasing sensitivity of nuclear magnetic resonance (NMR) spectroscopy, delivering spectra in shorter experiment times or of smaller sample amounts. In recent years, it has been applied in magic angle spinning (MAS) solid-state NMR to a large range of samples, including biological macromolecules and functional materials. New research directions in structural biology can be envisaged by DNP, facilitating investigations on very large complexes or very heterogeneous samples. Here we present a summary of state of the art DNP MAS NMR spectroscopy and its applications to structural biology, discussing the technical challenges and factors affecting DNP performance.

  2. Structure of high-resolution NMR spectra

    CERN Document Server

    Corio, PL

    2012-01-01

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

  3. 3D Reconstruction of NMR Images

    Directory of Open Access Journals (Sweden)

    Peter Izak

    2007-01-01

    Full Text Available This paper introduces experiment of 3D reconstruction NMR images scanned from magnetic resonance device. There are described methods which can be used for 3D reconstruction magnetic resonance images in biomedical application. The main idea is based on marching cubes algorithm. For this task was chosen sophistication method by program Vision Assistant, which is a part of program LabVIEW.

  4. Transformer-coupled NMR probe

    Science.gov (United States)

    Utsuzawa, Shin; Mandal, Soumyajit; Song, Yi-Qiao

    2012-03-01

    In this study, we propose an NMR probe circuit that uses a transformer with a ferromagnetic core for impedance matching. The ferromagnetic core provides a strong but confined coupling that result in efficient energy transfer between the sample coil and NMR spectrometer, while not disturbing the B1 field generated by the sample coil. We built a transformer-coupled NMR probe and found that it offers comparable performance (loss NQR.

  5. Solid-state NMR structures of integral membrane proteins.

    Science.gov (United States)

    Patching, Simon G

    2015-01-01

    Solid-state NMR is unique for its ability to obtain three-dimensional structures and to measure atomic-resolution structural and dynamic information for membrane proteins in native lipid bilayers. An increasing number and complexity of integral membrane protein structures have been determined by solid-state NMR using two main methods. Oriented sample solid-state NMR uses macroscopically aligned lipid bilayers to obtain orientational restraints that define secondary structure and global fold of embedded peptides and proteins and their orientation and topology in lipid bilayers. Magic angle spinning (MAS) solid-state NMR uses unoriented rapidly spinning samples to obtain distance and torsion angle restraints that define tertiary structure and helix packing arrangements. Details of all current protein structures are described, highlighting developments in experimental strategy and other technological advancements. Some structures originate from combining solid- and solution-state NMR information and some have used solid-state NMR to refine X-ray crystal structures. Solid-state NMR has also validated the structures of proteins determined in different membrane mimetics by solution-state NMR and X-ray crystallography and is therefore complementary to other structural biology techniques. By continuing efforts in identifying membrane protein targets and developing expression, isotope labelling and sample preparation strategies, probe technology, NMR experiments, calculation and modelling methods and combination with other techniques, it should be feasible to determine the structures of many more membrane proteins of biological and biomedical importance using solid-state NMR. This will provide three-dimensional structures and atomic-resolution structural information for characterising ligand and drug interactions, dynamics and molecular mechanisms of membrane proteins under physiological lipid bilayer conditions.

  6. Magic Angle Spinning NMR Metabolomics

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Jian Z.

    2016-05-31

    Nuclear Magnetic Resonance (NMR) spectroscopy is a non-destructive, quantitative, reproducible, untargeted and unbiased method that requires no or minimal sample preparation, and is one of the leading analytical tools for metabonomics research [1-3]. The easy quantification and the no need of prior knowledge about compounds present in a sample associated with NMR are advantageous over other techniques [1,4]. 1H NMR is especially attractive because protons are present in virtually all metabolites and its NMR sensitivity is high, enabling the simultaneous identification and monitoring of a wide range of low molecular weight metabolites.

  7. Development of a 1-week cycle menu for an Advanced Life Support System (ALSS) utilizing practical biomass production data from the Closed Ecology Experiment Facilities (CEEF).

    Science.gov (United States)

    Masuda, Tsuyoshi; Arai, Ryuuji; Komatsubara, Osamu; Tako, Yasuhiro; Harashima, Emiko; Nitta, Keiji

    2005-01-01

    Productivities of 29 crops in the Closed Ecology Experiment Facilities (CEEF) were measured. Rice and soybean showed higher productivities than these given by the Advanced Life Support System Modeling and Analysis Project Baseline Values and Assumption Document (BVAD), but productivities of some other crops, such as potato and sweet potato, were lower. The cultivation data were utilized to develop a 1-week cycle menu for Closed Habitation Experiment. The menu met most of the nutritional requirements. Necessary cultivation area per crew was estimated to be 255 m2. Results from this study can be used to help design the future Advanced Life Support System (ALSS) including the CEEF.

  8. The decrease of carbonation efficiency of CaO along calcination-carbonation cycles: Experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Bouquet, E.; Leyssens, G.; Schonnenbeck, C.; Gilot, P. [Laboratoire de Gestion des Risques et Environnement, Mulhouse (France)

    2009-05-15

    Successive calcination-carbonation cycles, using CaO as sorbent, have been performed either in a classical fixed bed reactor or using a thermogravimetric analyser. Significant differences in carbonation efficiencies were obtained, possibly due to different conditions prevailing for CaO sintering during the calcination stage. The effect of the presence of CO{sub 2} on sintering was confirmed. A simple model of the decay of the carbonation capacity along cycles based on the specific surface area of non-sintered micrograins of CaO is able to predict the decrease of the extent of conversion obtained after 40 carbonations along calcination-carbonation cycles. The asymptotic extent of conversion is obtained when all the micrograins present within a grain are sintered. A detailed model of the carbonation shows that the voids present between the micrograins are filled up by carbonate when a critical thickness of the carbonate layer around each micrograin reaches 43 nm. Then, carbonation becomes controlled by diffusion at the scale of the whole grain, with the CO{sub 2} diffusion coefficient decreasing (at 650 {sup o}C) from 2 x 10{sup -12} to 6.5 x 10{sup -14} m{sup 2}/s as carbonation proceeds from 50% conversion to 76% (first cycle). This scale change for diffusion is responsible for the drastic decrease of the carbonation rate after the voids between micrograins are filled up.

  9. Phytoplankton responses and associated carbon cycling during shipboard carbonate chemistry manipulation experiments conducted around Northwest European shelf seas

    OpenAIRE

    Richier, S.; Achterberg, E. P.; C. Dumousseaud; A. J. Poulton; Suggett, D.J.; T. Tyrrell; M. V. Zubkov; Moore, C.M.

    2014-01-01

    The ongoing oceanic uptake of anthropogenic carbon dioxide (CO2) is significantly altering the carbonate chemistry of seawater, a phenomenon referred to as ocean acidification. Experimental manipulations have been increasingly used to gauge how continued ocean acidification will potentially impact marine ecosystems and their associated biogeochemical cycles in the future; however, results amongst studies, particularly when performed on natural communities, are highly variabl...

  10. Carbon cycling and phytoplankton responses within highly-replicated shipboard carbonate chemistry manipulation experiments conducted around Northwest European Shelf Seas

    OpenAIRE

    Richier, S.; Achterberg, E. P.; C. Dumousseaud; A. J. Poulton; Suggett, D.J.; T. Tyrrell; M. V. Zubkov; Moore, C.M.

    2014-01-01

    The ongoing oceanic uptake of anthropogenic carbon dioxide (CO2) is significantly altering the carbonate chemistry of seawater, a phenomenon referred to as ocean acidification. Experimental manipulations have been increasingly used to gauge how continued ocean acidification will potentially impact marine ecosystems and their associated biogeochemical cycles in the future; however, results amongst studies, particularly when performed on natural communities, a...

  11. A Quick and Easy Simplification of Benzocaine's NMR Spectrum

    Science.gov (United States)

    Carpenter, Suzanne R.; Wallace, Richard H.

    2006-04-01

    The preparation of benzocaine is a common experiment used in sophomore-level organic chemistry. Its straightforward procedure and predictable good yields make it ideal for the beginning organic student. Analysis of the product via NMR spectroscopy, however, can be confusing to the novice interpreter. An inexpensive, quick, and effective method for simplifying the NMR spectrum is reported. The method results in a spectrum that is cleanly integrated and more easily interpreted.

  12. Analyzing protein-ligand interactions by dynamic NMR spectroscopy.

    Science.gov (United States)

    Mittermaier, Anthony; Meneses, Erick

    2013-01-01

    Nuclear magnetic resonance (NMR) spectroscopy can provide detailed information on protein-ligand interactions that is inaccessible using other biophysical techniques. This chapter focuses on NMR-based approaches for extracting affinity and rate constants for weakly binding transient protein complexes with lifetimes of less than about a second. Several pulse sequences and analytical techniques are discussed, including line-shape simulations, spin-echo relaxation dispersion methods (CPMG), and magnetization exchange (EXSY) experiments.

  13. Retracing trajectories : the embodied experience of cycling, urban sensescapes and the commute between 'neighbourhood' and 'city' in Utrecht, NL

    NARCIS (Netherlands)

    van Duppen, J.; Spierings, B.

    2013-01-01

    This paper looks into the experience of “passing through different territories of the city” (Sennett, 2006, p. 3). Despite their importance for making sense of the city as a whole, these experiences are often not acknowledged in urban planning. This paper compares the everyday, embodied experiences

  14. Assessing the fate and transformation of plant residues in the terrestrial environment using HR-MAS NMR spectroscopy

    Science.gov (United States)

    Kelleher, Brian P.; Simpson, Myrna J.; Simpson, Andre J.

    2006-08-01

    Plant litter decomposition plays a fundamental role in carbon and nitrogen cycles, provides key nutrients to the soil environment and represents a potentially large positive feedback to atmospheric CO 2. However, the full details of decomposition pathways and products are unknown. Here we present the first application of HR-MAS NMR spectroscopy on 13C and 15N labeled plant materials, and apply this approach in a preliminary study to monitor the environmental degradation of the pine and wheatgrass residues over time. In HR-MAS, is it possible to acquire very high resolution NMR data of plant biomass, and apply the vast array of multidimensional experiments available in conventional solution-state NMR. High levels of isotopic enrichment combined with HR-MAS significantly enhance the detection limits, and provide a wealth of information that is unattainable by any other method. Diffusion edited HR-MAS NMR data reveal the rapid loss of carbohydrate structures, while two-dimensional (2-D) HR-MAS NMR spectra demonstrate the relatively fast loss of both hydrolysable and condensed tannin structures from all plant tissues studied. Aromatic (partially lignin) and aliphatic components (waxes, cuticles) tend to persist, along with a small fraction of carbohydrate, and become highly functionalized over time. While one-dimensional (1-D) 13C HR-MAS NMR spectra of fresh plant tissue reflect compositional differences between pine and grass, these differences become negligible after decomposition suggesting that recalcitrant carbon may be similar despite the plant source. Two-dimensional 1H- 15N HR-MAS NMR analysis of the pine residue suggests that nitrogen from specific peptides is either selectively preserved or used for the synthesis of what appears to be novel structures. The amount of relevant data generated from plant components in situ using HR-MAS NMR is highly encouraging, and demonstrates that complete assignment will yield unprecedented structural knowledge of plant cell

  15. NMR data visualization, processing, and analysis on mobile devices.

    Science.gov (United States)

    Cobas, Carlos; Iglesias, Isaac; Seoane, Felipe

    2015-08-01

    Touch-screen computers are emerging as a popular platform for many applications, including those in chemistry and analytical sciences. In this work, we present our implementation of a new NMR 'app' designed for hand-held and portable touch-controlled devices, such as smartphones and tablets. It features a flexible architecture formed by a powerful NMR processing and analysis kernel and an intuitive user interface that makes full use of the smart devices haptic capabilities. Routine 1D and 2D NMR spectra acquired in most NMR instruments can be processed in a fully unattended way. More advanced experiments such as non-uniform sampled NMR spectra are also supported through a very efficient parallelized Modified Iterative Soft Thresholding algorithm. Specific technical development features as well as the overall feasibility of using NMR software apps will also be discussed. All aspects considered the functionalities of the app allowing it to work as a stand-alone tool or as a 'companion' to more advanced desktop applications such as Mnova NMR.

  16. NMR Studies of 3-Acylcamphor

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    NMR studies of some chiral 3-acyclcamphor were conducted.A complete assignment was given to 3-(4-pyridyl)carbonylcamphor by the 2D NMR technology.Assignments were also given to other b -diketones.The results showed that those 3-acylcamphors exist in the enol forms,while 2-benzoyl menthone exists in diketon form.

  17. Hydrological Cycle over South and Southeast Asian River Basins as Simulated by PCMDI/CMIP3 Experiments

    CERN Document Server

    Hasson, Shabeh ul; Pascale, Salvatore

    2013-01-01

    We investigate how CMIP3 climate models describe the hydrological cycle over four major South Asian river basins (Indus, Ganges, Brahmaputra and Mekong) for the XX, XXI, and XXII centuries. For the XX century, models simulated water balance and total runoff quantities are neither consistent with the observed mean river discharges nor among the models. Most of the models underestimate the water balance for the Ganges, Brahmaputra and Mekong basin and overestimate it for the Indus basin. The only modest inter-model agreement is found for the Indus basin in terms of precipitation, evaporation and the strength of the hydrological cycle and for the Brahmaputra basin in terms of evaporation. While some models show inconsistencies for the Indus and the Ganges basins, most of the models seem to conserve water at the river basin scale up to a good degree of approximation. Models agree on a negative change of the water balance for Indus and a positive change in the strength of the hydrological cycle, whereas for Brahma...

  18. Structural Biology: Practical NMR Applications

    CERN Document Server

    Teng, Quincy

    2005-01-01

    This textbook begins with an overview of NMR development and applications in biological systems. It describes recent developments in instrument hardware and methodology. Chapters highlight the scope and limitation of NMR methods. While detailed math and quantum mechanics dealing with NMR theory have been addressed in several well-known NMR volumes, chapter two of this volume illustrates the fundamental principles and concepts of NMR spectroscopy in a more descriptive manner. Topics such as instrument setup, data acquisition, and data processing using a variety of offline software are discussed. Chapters further discuss several routine stategies for preparing samples, especially for macromolecules and complexes. The target market for such a volume includes researchers in the field of biochemistry, chemistry, structural biology and biophysics.

  19. Dipeptide Structural Analysis Using Two-Dimensional NMR for the Undergraduate Advanced Laboratory

    Science.gov (United States)

    Gonzalez, Elizabeth; Dolino, Drew; Schwartzenburg, Danielle; Steiger, Michelle A.

    2015-01-01

    A laboratory experiment was developed to introduce students in either an organic chemistry or biochemistry lab course to two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy using simple biomolecules. The goal of this experiment is for students to understand and interpret the information provided by a 2D NMR spectrum. Students are…

  20. Dipeptide Structural Analysis Using Two-Dimensional NMR for the Undergraduate Advanced Laboratory

    Science.gov (United States)

    Gonzalez, Elizabeth; Dolino, Drew; Schwartzenburg, Danielle; Steiger, Michelle A.

    2015-01-01

    A laboratory experiment was developed to introduce students in either an organic chemistry or biochemistry lab course to two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy using simple biomolecules. The goal of this experiment is for students to understand and interpret the information provided by a 2D NMR spectrum. Students are…

  1. Experimental Determination of pK[subscript a] Values by Use of NMR Chemical Shifts, Revisited

    Science.gov (United States)

    Gift, Alan D.; Stewart, Sarah M.; Bokashanga, Patrick Kwete

    2012-01-01

    This laboratory experiment, using proton NMR spectroscopy to determine the dissociation constant for heterocyclic bases, has been modified from a previously described experiment. A solution of a substituted pyridine is prepared using deuterium oxide (D[subscript 2]O) as the solvent. The pH of the solution is adjusted and proton NMR spectra are…

  2. NMR molecular photography

    CERN Document Server

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

    2002-01-01

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

  3. Some nitrogen-14 NMR studies in solids

    Energy Technology Data Exchange (ETDEWEB)

    Pratum, T.K.

    1983-11-01

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

  4. Separation of components of a broad 1H-NMR composite signal by means of nutation experiments under low amplitude radiofrequency fields. Application to the water signal in synthetic clays; Developpement et mise en oeuvre d'une nouvelle methode fondee sur le phenomene de nutation pour la decomposition d'un signal composite de resonance magnetique nucleaire. Application au signal 1h de l'eau dans des argiles synthetiques

    Energy Technology Data Exchange (ETDEWEB)

    Trausch, G

    2006-11-15

    Nowadays, geologic nuclear waste storage is envisioned according to a multi-layer model which implies clays. The latter exhibit retention capacities and low permeability to water; that is why they are considered as a good candidate for engineered barriers to radioactive waste disposal. The present work here aims at studying transport phenomena which involve water molecules in three samples of synthetic clays (two of them exhibiting a Pake doublet) by means of Nuclear Magnetic Resonance (NMR). The first chapter describes structural properties of clays and presents the state-of-art of NMR and other experimental techniques used for such systems. The second chapter deals with the interpretation and the simulation of each conventional proton spectrum. These simulations allow us to evidence and to characterize a chemical exchange phenomenon. The third chapter is dedicated to original nutation experiments performed under low radiofrequency field in the case of broad NMR signal. It is shown that this type of NMR experiment can yield the number and the proportion of each species contributing to the whole signal. These results are exploited in the fourth chapter for processing relaxation and diffusion experiments. Finally, the diffusion coefficients obtained by NMR are divided by a factor 4 with respect to pure water while relaxation rates are two orders of magnitude greater. (author)

  5. Structural characterization of homogalacturonan by NMR spectroscopy - assignment of reference compounds

    DEFF Research Database (Denmark)

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

    2008-01-01

    Complete assignment of 1H and 13C NMR of six hexagalactopyranuronic acids with varying degree and pattern of methyl esterification is reported. The NMR experiments were run at room temperature using approximately 2 mg of sample making this method convenient for studying the structure of homogalac......Complete assignment of 1H and 13C NMR of six hexagalactopyranuronic acids with varying degree and pattern of methyl esterification is reported. The NMR experiments were run at room temperature using approximately 2 mg of sample making this method convenient for studying the structure...

  6. Study of molecular interactions with 13C DNP-NMR.

    Science.gov (United States)

    Lerche, Mathilde H; Meier, Sebastian; Jensen, Pernille R; Baumann, Herbert; Petersen, Bent O; Karlsson, Magnus; Duus, Jens Ø; Ardenkjaer-Larsen, Jan H

    2010-03-01

    NMR spectroscopy is an established, versatile technique for the detection of molecular interactions, even when these interactions are weak. Signal enhancement by several orders of magnitude through dynamic nuclear polarization alleviates several practical limitations of NMR-based interaction studies. This enhanced non-equilibrium polarization contributes sensitivity for the detection of molecular interactions in a single NMR transient. We show that direct (13)C NMR ligand binding studies at natural isotopic abundance of (13)C gets feasible in this way. Resultant screens are easy to interpret and can be performed at (13)C concentrations below muM. In addition to such ligand-detected studies of molecular interaction, ligand binding can be assessed and quantified with enzymatic assays that employ hyperpolarized substrates at varying enzyme inhibitor concentrations. The physical labeling of nuclear spins by hyperpolarization thus provides the opportunity to devise fast novel in vitro experiments with low material requirement and without the need for synthetic modifications of target or ligands.

  7. Observations of Quantum Dynamics by Solution-State NMR Spectroscopy

    CERN Document Server

    Pravia, M A; Weinstein, Yu S; Price, M D; Teklemariam, G; Nelson, R J; Sharf, Y; Somaroo, S S; Tseng, C H; Havel, T F; Cory, D G

    1999-01-01

    NMR is emerging as a valuable testbed for the investigation of foundational questions in quantum mechanics. The present paper outlines the preparation of a class of mixed states, called pseudo-pure states, that emulate pure quantum states in the highly mixed environment typically used to describe solution-state NMR samples. It also describes the NMR observation of spinor behavior in spin 1/2 nuclei, the simulation of wave function collapse using a magnetic field gradient, the creation of entangled (or Bell) pseudo-pure states, and a brief discussion of quantum computing logic gates, including the Quantum Fourier Transform. These experiments show that liquid-state NMR can be used to demonstrate quantum dynamics at a level suitable for laboratory exercises.

  8. Interfaces in polymer nanocomposites – An NMR study

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-03-09

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

  9. Long-term responses of snails exposed to cadmium-contaminated soils in a partial life-cycle experiment.

    Science.gov (United States)

    Gimbert, Frédéric; de Vaufleury, Annette; Douay, Francis; Coeurdassier, Michaël; Scheifler, Renaud; Badot, Pierre-Marie

    2008-05-01

    Juvenile snails were exposed during their growth period to Cd-contaminated field and artificial soils and then transferred to uncontaminated soil to assess the sequels of previous exposure on adult reproduction. Growth modelling highlighted growth inhibitions of 5% and 10% after 70 and 84 days of exposure to 20 and 100 mg Cd kg(-1) in artificial soils, respectively. Growth disruption was accompanied by a decrease in the clutch number and a 4-week delay in the egg-laying cycle. Although it was also contaminated at 20 mg Cd kg(-1), the contaminated field soil did not lead to detectable effects in snails, suggesting a lower Cd bioavailability confirmed by the bioaccumulation analysis. We demonstrated that the 28-day growth test, as advised by the ISO-guideline, may not be sufficient to assess sublethal toxic effects of realistically contaminated soils. For this purpose, a life cycle experimental set-up is proposed, allowing a thorough assessment of toxicity during successive life stages.

  10. nmr spectroscopic study and dft calculations of giao nmr shieldings ...

    African Journals Online (AJOL)

    Preferred Customer

    various fields of science and industry such as microelectronic and aerospace ... GIAO/DFT (Gauge Including Atomic Orbitals/Density Functional Theory) approach is .... successfully by using NMR and quantum chemical calculations.

  11. NMR spectrometers as "magnetic tongues"

    DEFF Research Database (Denmark)

    Malmendal, Anders; Amoresano, Claudia; Trotta, Roberta

    2011-01-01

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

  12. Annual reports on NMR spectroscopy

    CERN Document Server

    Webb, Graham A; McCarthy, M J

    1995-01-01

    Over recent years, no other technique has grown to such importance as that of NMR spectroscopy. It is used in all branches of science where precise structural determination is required and where the nature of interactions and reactions in solution is being studied. Annual Reports on NMR Spectroscopy has established itself as a means for the specialist and non-specialist alike to become familiar with new applications of the technique in all branches of chemistry, including biochemistry, and pharmaceutics. This volume focuses on theoretical aspects of NMR nuclear shielding and on applications of

  13. Richness, biomass, and nutrient content of a wetland macrophyte community affect soil nitrogen cycling in a diversity-ecosystem functioning experiment

    Science.gov (United States)

    Korol, Alicia R.; Ahn, Changwoo; Noe, Gregory

    2016-01-01

    The development of soil nitrogen (N) cycling in created wetlands promotes the maturation of multiple biogeochemical cycles necessary for ecosystem functioning. This development proceeds from gradual changes in soil physicochemical properties and influential characteristics of the plant community, such as competitive behavior, phenology, productivity, and nutrient composition. In the context of a 2-year diversity experiment in freshwater mesocosms (0, 1, 2, 3, or 4 richness levels), we assessed the direct and indirect impacts of three plant community characteristics – species richness, total biomass, and tissue N concentration – on three processes in the soil N cycle – soil net ammonification, net nitrification, and denitrification potentials. Species richness had a positive effect on net ammonification potential (NAP) through higher redox potentials and likely faster microbial respiration. All NAP rates were negative, however, due to immobilization and high rates of ammonium removal. Net nitrification was inhibited at higher species richness without mediation from the measured soil properties. Higher species richness also inhibited denitrification potential through increased redox potential and decreased nitrification. Both lower biomass and/or higher tissue ratios of carbon to nitrogen, characteristics indicative of the two annual plants, were shown to have stimulatory effects on all three soil N processes. The two mediating physicochemical links between the young macrophyte community and microbial N processes were soil redox potential and temperature. Our results suggest that early-successional annual plant communities play an important role in the development of ecosystem N multifunctionality in newly created wetland soils.

  14. Characterizations of Some N-Substituted-salicylhydrazide in Mixtures by NMR Diffusion Ordered Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    张芳; 于贤勇; 陈忠; 林深; 刘世雄

    2003-01-01

    Several novel N-substituted-salicylhydrazide ligands, most of which are difficult to be purified or recrystallized so that their chemical configurations can not be confirmed by conventional NMR and/or X-ray diffraction techniques, were synthesized in this experiment, and their chemical configurations in mixture were analyzed and characterized by 2D NMR diffusion ordered spectroscopy (DOSY), a labor-saving virtual separation based on diffusion properties,together with several routine NMR techniques.

  15. NMR methodologies for studying mitochondrial bioenergetics.

    Science.gov (United States)

    Alves, Tiago C; Jarak, Ivana; Carvalho, Rui A

    2012-01-01

    Nuclear magnetic resonance (NMR) spectroscopy is a technique with an increasing importance in the study of metabolic diseases. Its initial important role in the determination of chemical structures (1, 2) has been considerably overcome by its potential for the in vivo study of metabolism (3-5). The main characteristic that makes this technique so attractive is its noninvasiveness. Only nuclei capable of transitioning between energy states, in the presence of an intense and constant magnetic field, are studied. This includes abundant nuclei such as proton ((1)H) and phosphorous ((31)P), as well as stable isotopes such as deuterium ((2)H) and carbon 13 ((13)C). This allows a wide range of applications that vary from the determination of water distribution in tissues (as obtained in a magnetic resonance imaging scan) to the calculation of metabolic fluxes under ex vivo and in vivo conditions without the need to use radioactive tracers or tissue biopsies (as in a magnetic resonance spectroscopy (MRS) scan). In this chapter, some technical aspects of the methodology of an NMR/MRS experiment as well as how it can be used to study mitochondrial bioenergetics are overviewed. Advantages and disadvantages of in vivo MRS versus high-resolution NMR using proton high rotation magic angle spinning (HRMAS) of tissue biopsies and tissue extracts are also discussed.

  16. Earth's field NMR; a surface moisture detector?

    Science.gov (United States)

    Fukushima, Eiichi; Altobelli, Stephen; McDowell, Andrew; Zhang, Tongsheng

    2012-10-01

    Earth's field NMR (EFNMR), being free of magnets, would be an ideal teaching medium as well as a mobile NMR technique except for its weak S/N. The common EFNMR apparatus uses a powerful prepolarization field to enhance the spin magnetization before the experiment. We introduce a coil design geared to larger but manageable samples with sufficient sensitivity without prepolarization to move EFNMR closer to routine use and to provide an inexpensive teaching tool. Our coil consists of parallel wires spread out on a plywood to form a current sheet with the current return wires separated so they will not influence the main part of the coil assembly. The sensitive region is a relatively thin region parallel to the coil and close to it. A single turn of the coil is wound to be topologically equivalent to a figure-8. The two crossing segments in the center of a figure-8 form two of the parallel wires of the flat coil. Thus, a two-turn figure-8 has four crossing wires so its topologically equivalent coil will have four parallel wires with currents in phase. Together with the excellent sensitivity, this coil offers outstanding interference rejection because of the figure-8 geometry. An example of such a coil has 328 parallel wires covering a ˜1 meter square plywood which yields a good NMR signal from 26 liters of water spread out roughly over the area of the coil in less than one minute in a nearby park.

  17. Cutoff-Free Traveling Wave NMR

    CERN Document Server

    Tang, Joel A; Sodickson, Daniel K; Jerschow, Alexej

    2011-01-01

    Recently, the concept of traveling-wave NMR/MRI was introduced by Brunner et al. (Nature 457, 994-992 (2009)), who demonstrated MR images acquired using radio frequency (RF) waves propagating down the bore of an MR scanner. One of the significant limitations of this approach is that each bore has a specific cutoff frequency, which can be higher than most Larmor frequencies of at the magnetic field strengths commonly in use for MR imaging and spectroscopy today. We overcome this limitation by using a central conductor in the waveguide and thereby converting it to a transmission line (TL), which has no cutoff frequency. Broadband propagation of waves through the sample thus becomes possible. NMR spectra and images with such an arrangement are presented and genuine traveling wave behavior is demonstrated. In addition to facilitating NMR spectroscopy and imaging in smaller bores via traveling waves, this approach also allows one to perform multinuclear traveling wave experiments (an example of which is shown), an...

  18. Influence of roots and mycorrhiza on the internal nitrogen cycle in an organic forest soil ­revealed by a 15N tracing experiment

    Science.gov (United States)

    Holz, M.; Rutting, T.; Klemedtsson, L.; Kuzyakov, Y.

    2014-12-01

    The cycle of nitrogen in soil is complex, consisting of many simultaneous occurring transformation processes. So far, microorganisms have been thought to govern N cycling in soil. Nevertheless, plant roots and their associated mycorrhizal symbionts may exert control on N turnover for example by input of labile C to soil. However, studies investigating the effect of roots on gross N turnover rates are scarce. We conducted a 15N tracer study under field conditions to reveal the effect of plants on soil N cycle. The experiment includes three treatments: (a) control, (b) excluding roots and (c) excluding roots + mycorrhiza. On the study site, exclusion of roots + mycorrhiza has previously been shown to increase N2O emissions which indicate that plants affect internal N cycling. 15NH4NO3 and NH415NO3 were given to the soil and traced for a period of 10 days. Gross N turnover rates were determined applying a numerical 15N tracing model. Results on N turnover rates showed that roots and their fungal symbionts increased N cycling probably by input of labile C to soil which may results in an activation of the microbial biomass. While gross N mineralization increased by 270 and 313 % compared to the treatment excluding roots + mycorrhiza, NH4+ immobilization increased by 402 and 489 %. Differences in ammonium and nitrate immobilization further indicated that ammonium was the preferred N source for roots and microorganisms. While ammonium availability decreased with trenching (0.59 compared to -0.47 and -0.96 μg N g-1 d-1), the opposite was true for nitrate (0.50 compared to 2.08 and 2.18 μg N g-1 d-1), explaining the increased N2O emissions which were likely caused by denitrification. Further, plants increased dissimilarity nitrate reduction to ammonium (DNRA) and affected autotrophic nitrification probably by the release of nitrification inhibitors and by influencing ammonium availability. We conclude that plants and their mycorrhizal symbionts actively control N cycling

  19. Analysis of current research addressing complementary use of life-cycle assessment and risk assessment for engineered nanomaterials: have lessons been learned from previous experience with chemicals?

    DEFF Research Database (Denmark)

    Grieger, Khara Deanne; Laurent, Alexis; Miseljic, Mirko

    2012-01-01

    While it is generally agreed that successful strategies to address the health and environmental impacts of engineered nanomaterials (NM) should consider the well-established frameworks for conducting life-cycle assessment (LCA) and risk assessment (RA), scientific research, and specific guidance...... on how to practically apply these methods are still very much under development. This paper evaluates how research efforts have applied LCA and RA together for NM, particularly reflecting on previous experiences with applying these methods to chemicals. Through a literature review and a separate analysis...... of research focused on applying LCA and RA together for NM, it appears that current research efforts have taken into account some key ‘‘lessons learned’’ from previous experience with chemicals while many key challenges remain for practically applying these methods to NM. We identified two main approaches...

  20. β-NMR sample optimization

    CERN Document Server

    Zakoucka, Eva

    2013-01-01

    During my summer student programme I was working on sample optimization for a new β-NMR project at the ISOLDE facility. The β-NMR technique is well-established in solid-state physics and just recently it is being introduced for applications in biochemistry and life sciences. The β-NMR collaboration will be applying for beam time to the INTC committee in September for three nuclei: Cu, Zn and Mg. Sample optimization for Mg was already performed last year during the summer student programme. Therefore sample optimization for Cu and Zn had to be completed as well for the project proposal. My part in the project was to perform thorough literature research on techniques studying Cu and Zn complexes in native conditions, search for relevant binding candidates for Cu and Zn applicable for ß-NMR and eventually evaluate selected binding candidates using UV-VIS spectrometry.

  1. Integrative NMR for biomolecular research.

    Science.gov (United States)

    Lee, Woonghee; Cornilescu, Gabriel; Dashti, Hesam; Eghbalnia, Hamid R; Tonelli, Marco; Westler, William M; Butcher, Samuel E; Henzler-Wildman, Katherine A; Markley, John L

    2016-04-01

    NMR spectroscopy is a powerful technique for determining structural and functional features of biomolecules in physiological solution as well as for observing their intermolecular interactions in real-time. However, complex steps associated with its practice have made the approach daunting for non-specialists. We introduce an NMR platform that makes biomolecular NMR spectroscopy much more accessible by integrating tools, databases, web services, and video tutorials that can be launched by simple installation of NMRFAM software packages or using a cross-platform virtual machine that can be run on any standard laptop or desktop computer. The software package can be downloaded freely from the NMRFAM software download page ( http://pine.nmrfam.wisc.edu/download_packages.html ), and detailed instructions are available from the Integrative NMR Video Tutorial page ( http://pine.nmrfam.wisc.edu/integrative.html ).

  2. Compact orthogonal NMR field sensor

    Science.gov (United States)

    Gerald, II, Rex E.; Rathke, Jerome W [Homer Glen, IL

    2009-02-03

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

  3. Reactor physics studies for the Advanced Fuel Cycle Initiative (AFCI) Reactor-Accelerator Coupling Experiments (RACE) Project

    Science.gov (United States)

    Stankovskiy, Evgeny Yuryevich

    In the recently completed RACE Project of the AFCI, accelerator-driven subcritical systems (ADS) experiments were conducted to develop technology of coupling accelerators to nuclear reactors. In these experiments electron accelerators induced photon-neutron reactions in heavy-metal targets to initiate fission reactions in ADS. Although the Idaho State University (ISU) RACE ADS was constructed only to develop measurement techniques for advanced experiments, many reactor kinetics experiments were conducted there. In the research reported in this dissertation, a method was developed to calculate kinetics parameters for measurement and calculation of the reactivity of ADS, a safety parameter that is necessary for control and monitoring of power production. Reactivity is measured in units of fraction of delayed versus prompt neutron from fission, a quantity that cannot be directly measured in far-subcritical reactors such as the ISU RACE configuration. A new technique is reported herein to calculate it accurately and to predict kinetic behavior of a far-subcritical ADS. Experiments conducted at ISU are first described and experimental data are presented before development of the kinetic theory used in the new computational method. Because of the complexity of the ISU ADS, the Monte-Carlo method as applied in the MCNP code is most suitable for modeling reactor kinetics. However, the standard method of calculating the delayed neutron fraction produces inaccurate values. A new method was developed and used herein to evaluate actual experiments. An advantage of this method is that its efficiency is independent of the fission yield of delayed neutrons, which makes it suitable for fuel with a minor actinide component (e.g. transmutation fuels). The implementation of this method is based on a correlated sampling technique which allows the accurate evaluation of delayed and prompt neutrons. The validity of the obtained results is indicated by good agreement between experimental

  4. Nonuniform sampling and maximum entropy reconstruction in multidimensional NMR.

    Science.gov (United States)

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

    2014-02-18

    NMR spectroscopy is one of the most powerful and versatile analytic tools available to chemists. The discrete Fourier transform (DFT) played a seminal role in the development of modern NMR, including the multidimensional methods that are essential for characterizing complex biomolecules. However, it suffers from well-known limitations: chiefly the difficulty in obtaining high-resolution spectral estimates from short data records. Because the time required to perform an experiment is proportional to the number of data samples, this problem imposes a sampling burden for multidimensional NMR experiments. At high magnetic field, where spectral dispersion is greatest, the problem becomes particularly acute. Consequently multidimensional NMR experiments that rely on the DFT must either sacrifice resolution in order to be completed in reasonable time or use inordinate amounts of time to achieve the potential resolution afforded by high-field magnets. Maximum entropy (MaxEnt) reconstruction is a non-Fourier method of spectrum analysis that can provide high-resolution spectral estimates from short data records. It can also be used with nonuniformly sampled data sets. Since resolution is substantially determined by the largest evolution time sampled, nonuniform sampling enables high resolution while avoiding the need to uniformly sample at large numbers of evolution times. The Nyquist sampling theorem does not apply to nonuniformly sampled data, and artifacts that occur with the use of nonuniform sampling can be viewed as frequency-aliased signals. Strategies for suppressing nonuniform sampling artifacts include the careful design of the sampling scheme and special methods for computing the spectrum. Researchers now routinely report that they can complete an N-dimensional NMR experiment 3(N-1) times faster (a 3D experiment in one ninth of the time). As a result, high-resolution three- and four-dimensional experiments that were prohibitively time consuming are now practical

  5. NMR characterization of thin films

    Science.gov (United States)

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

    2008-11-25

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

  6. Analysis of current research addressing complementary use of life-cycle assessment and risk assessment for engineered nanomaterials: have lessons been learned from previous experience with chemicals?

    Energy Technology Data Exchange (ETDEWEB)

    Grieger, Khara D., E-mail: kgrieger@rti.org [RTI International (United States); Laurent, Alexis; Miseljic, Mirko [Technical University of Denmark, Department of Management Engineering (Denmark); Christensen, Frans [Sustainability and Risk Management, COWI A/S, Department for Pollution Prevention (Denmark); Baun, Anders [Technical University of Denmark, Department of Environmental Engineering (Denmark); Olsen, Stig I. [Technical University of Denmark, Department of Management Engineering (Denmark)

    2012-07-15

    While it is generally agreed that successful strategies to address the health and environmental impacts of engineered nanomaterials (NM) should consider the well-established frameworks for conducting life-cycle assessment (LCA) and risk assessment (RA), scientific research, and specific guidance on how to practically apply these methods are still very much under development. This paper evaluates how research efforts have applied LCA and RA together for NM, particularly reflecting on previous experiences with applying these methods to chemicals. Through a literature review and a separate analysis of research focused on applying LCA and RA together for NM, it appears that current research efforts have taken into account some key 'lessons learned' from previous experience with chemicals while many key challenges remain for practically applying these methods to NM. We identified two main approaches for using these methods together for NM: 'LC-based RA' (traditional RA applied in a life-cycle perspective) and 'RA-complemented LCA' (conventional LCA supplemented by RA in specific life-cycle steps). Hence, the latter is the only identified approach which genuinely combines LC- and RA-based methods for NM-risk research efforts to date as the former is rather a continuation of normal RA according to standard assessment procedures (e.g., REACH). Both these approaches along with recommendations for using LCA and RA together for NM are similar to those made previously for chemicals, and thus, there does not appear to be much progress made specific for NM. We have identified one issue in particular that may be specific for NM when applying LCA and RA at this time: the need to establish proper dose metrics within both methods.

  7. Space-based Observation System Simulation Experiments for the Global Water Cycle: Information Tradeoffs, Model Diagnostics, and Exascale Computing

    Science.gov (United States)

    Reed, P. M.

    2011-12-01

    Global scale issues such as population growth, changing land-use, and climate change place our natural resources at the center of focus for a broad range of interdependent science, engineering, and policy problems. Our ability to mitigate and adapt to the accelerating rate of environmental change is critically dependent on our ability to observe and predict the natural, built, and social systems that define sustainability at the global scale. Despite the risks and challenges posed by global change, we are faced with critical risks to our ability to maintain and improve long term space-based observations of these changes. Despite consensus agreement on the critical importance of space-based Earth science, the fundamental challenge remains: How should we manage the severe tradeoffs and design challenges posed by maximizing the value of existing and proposed spaced-based Earth observation systems? Addressing this question requires transformative innovations in the design and management of spaced-based Earth observation systems that effectively take advantage of massively parallel computing architectures to enable the discovery and exploitation of critical mission tradeoffs using high-resolution space-based observation system simulation events (OSSEs) that simulate the global water cycle data that would result from sensing innovations and evaluates their merit with carefully constructed prediction and management benchmarks.

  8. Drought effects on litterfall, wood production and belowground carbon cycling in an Amazon forest: results of a throughfall reduction experiment.

    Science.gov (United States)

    Brando, Paulo M; Nepstad, Daniel C; Davidson, Eric A; Trumbore, Susan E; Ray, David; Camargo, Plínio

    2008-05-27

    The Amazon Basin experiences severe droughts that may become more common in the future. Little is known of the effects of such droughts on Amazon forest productivity and carbon allocation. We tested the prediction that severe drought decreases litterfall and wood production but potentially has multiple cancelling effects on belowground production within a 7-year partial throughfall exclusion experiment. We simulated an approximately 35-41% reduction in effective rainfall from 2000 through 2004 in a 1ha plot and compared forest response with a similar control plot. Wood production was the most sensitive component of above-ground net primary productivity (ANPP) to drought, declining by 13% the first year and up to 62% thereafter. Litterfall declined only in the third year of drought, with a maximum difference of 23% below the control plot. Soil CO2 efflux and its 14C signature showed no significant treatment response, suggesting similar amounts and sources of belowground production. ANPP was similar between plots in 2000 and declined to a low of 41% below the control plot during the subsequent treatment years, rebounding to only a 10% difference during the first post-treatment year. Live aboveground carbon declined by 32.5Mgha-1 through the effects of drought on ANPP and tree mortality. Results of this unreplicated, long-term, large-scale ecosystem manipulation experiment demonstrate that multi-year severe drought can substantially reduce Amazon forest carbon stocks.

  9. Quenched Hydrogen Exchange NMR of Amyloid Fibrils.

    Science.gov (United States)

    Alexandrescu, Andrei T

    2016-01-01

    Amyloid fibrils are associated with a number of human diseases. These aggregatively misfolded intermolecular β-sheet assemblies constitute some of the most challenging targets in structural biology because to their complexity, size, and insolubility. Here, protocols and controls are described for experiments designed to study hydrogen-bonding in amyloid fibrils indirectly, by transferring information about amide proton occupancy in the fibrils to the dimethyl sulfoxide-denatured state. Since the denatured state is amenable to solution NMR spectroscopy, the method can provide residue-level-resolution data on hydrogen exchange for the monomers that make up the fibrils.

  10. Functional Analysis of the Nitrogen Metabolite Repression Regulator Gene nmrA in Aspergillus flavus

    Directory of Open Access Journals (Sweden)

    Xiaoyun Han

    2016-11-01

    Full Text Available In Aspergillus nidulans, the nitrogen metabolite repression regulator NmrA plays a major role in regulating the activity of the GATA transcription factor AreA during nitrogen metabolism. However, the function of nmrA in Aspergillus flavus has notbeen previously studied. Here, we report the identification and functional analysis of nmrA in A. flavus. Our work showed that the amino acid sequences of NmrA are highly conserved among Aspergillus species and that A. flavus NmrA protein contains a canonical Rossmann fold motif. Deletion of nmrA slowed the growth of A. flavus but significantly increased conidiation and sclerotia production. Moreover, seed infection experiments indicated that nmrA is required for the invasive virulence of A. flavus. In addition, the ΔnmrA mutant showed increased sensitivity to rapamycin and methyl methanesulfonate, suggesting that nmrA could be responsive to target of rapamycin signaling and DNA damage. Furthermore, quantitative real-time reverse transcription polymerase chain reaction analysis suggested that nmrA might interact with other nitrogen regulatory and catabolic genes. Our study provides a better understanding of nitrogen metabolite repression and the nitrogen metabolism network in fungi.

  11. Variable-temperature NMR and conformational analysis of Oenothein B

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Suzana C.; Carvalho, Ariadne G.; Fortes, Gilmara A.C.; Ferri, Pedro H.; Oliveira, Anselmo E. de, E-mail: suzana.quimica.ufg@hotmail.com [Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Instituto de Quimica

    2014-02-15

    Oenothein B is a dimeric hydrolyzable tannin with a wide range of biological activities, such as antitumour, anti-inflammatory and antiviral. Its nuclear magnetic resonance (NMR) at room temperature show duplications and broadening of signals. Experiments of 1D and 2D NMR at lower temperatures were useful for the complete NMR assignments of all hydrogens and carbons. The 3D structure of the most stable conformer was determined for the first time by nuclear Overhauser effect spectroscopy (NOESY) experiment (-20 deg C) and density functional theory (DFT)(B3LYP/6-31G)/ polarizable continuum model (PCM) quantum chemical calculations. The favoured conformation showed a highly compacted geometry and a lack of symmetry, in which the two valoneoyl groups showed distinct conformational parameters and stabilities. (author)

  12. Studies of metal-biomolecule systems in liquids with beta-detected NMR

    CERN Document Server

    Walczak, Michal

    2017-01-01

    My internship took place within a small research team funded via the European Research Council (ERC Starting Grant: Beta-Drop NMR) at ISOLDE. It was devoted to laser spin-polarization and beta-detected NMR techniques and their future applications in chemistry and biology. I was involved in the design and tests of the beta-NMR spectrometer which will be used in the upcoming experiments. In this way I have been exposed to many topics in physics (atomic and nuclear physics), experimental techniques (vacuum technology, lasers, beta detectors, electronics, DAQ software), as well as chemistry and biology (NMR on metal ions, metal ion binding to biomolecules, quantum chemistry calculations).

  13. "Afterlife experiment": use of MALDI-MS and SIMS imaging for the study of the nitrogen cycle within plants.

    Science.gov (United States)

    Seaman, Callie; Flinders, Bryn; Eijkel, Gert; Heeren, Ron M A; Bricklebank, Neil; Clench, Malcolm R

    2014-10-21

    As part of a project to demonstrate the science of decay, a series of mass spectrometry imaging experiments were performed. The aim was to demonstrate that decay and decomposition are only part of the story and to show pictorially that atoms and molecules from dead plants and animals are incorporated into new life. Radish plants (Raphanus sativus) were grown hydroponically using a nutrient system containing (15)N KNO3 (98% labeled) as the only source of nitrogen. Plants were cropped and left to ferment in water for 2 weeks to create a radish "tea", which was used as a source of nitrogen for radish grown in a second hydroponics experiment. After 5 weeks of growth, the radish plants were harvested and cryosectioned, and sections were imaged by positive-ion MALDI and SIMS mass spectrometry imaging. The presence of labeled species in the plants grown using (15)N KNO3 as nutrient and those grown from the radish "tea" was readily discernible. The uptake of (15)N into a number of identifiable metabolites has been studied by MALDI-MS and SIMS imaging.

  14. Method development in quantitative NMR towards metrologically traceable organic certified reference materials used as (31)P qNMR standards.

    Science.gov (United States)

    Weber, Michael; Hellriegel, Christine; Rueck, Alexander; Wuethrich, Juerg; Jenks, Peter; Obkircher, Markus

    2015-04-01

    Quantitative nuclear magnetic resonance (qNMR) spectroscopy is employed by an increasing number of analytical and industrial laboratories for the assignment of content and quantitative determination of impurities. Within the last few years, it was demonstrated that (1)H qNMR can be performed with high accuracy leading to measurement uncertainties below 1 % relative. It was even demonstrated that the combination of (1)H qNMR with metrological weighing can lead to measurement uncertainties below 0.1 % when highly pure substances are used. Although qNMR reference standards are already available as certified reference materials (CRM) providing traceability on the basis of (1)H qNMR experiments, there is an increasing demand for purity assays on phosphorylated organic compounds and metabolites requiring CRM for quantification by (31)P qNMR. Unfortunately, the number of available primary phosphorus standards is limited to a few inorganic CRM which only can be used for the analysis of water-soluble analytes but fail when organic solvents must be employed. This paper presents the concept of value assignment by (31)P qNMR measurements for the development of CRM and describes different approaches to establish traceability to primary Standard Reference Material from the National Institute of Standards and Technology (NIST SRM). Phosphonoacetic acid is analyzed as a water-soluble CRM candidate, whereas triphenyl phosphate is a good candidate for the use as qNMR reference material in organic solvents. These substances contain both nuclei, (1)H and (31)P, and the concept is to show that it is possible to indirectly quantify a potential phosphorus standard via its protons using (1)H qNMR. The same standard with its assigned purity can then be used for the quantification of an analyte via its phosphorus using (31)P qNMR. For the validation of the concept, triphenyl phosphate and phosphonoacetic acid have been used as (31)P qNMR standards to determine the purity of the analyte

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

    Energy Technology Data Exchange (ETDEWEB)

    Talnishnikh, E.

    2007-08-21

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

  16. Measurement of Solution Viscosity via Diffusion-Ordered NMR Spectroscopy (DOSY)

    Science.gov (United States)

    Li, Weibin; Kagan, Gerald; Hopson, Russell; Williard, Paul G.

    2011-01-01

    Increasingly, the undergraduate chemistry curriculum includes nuclear magnetic resonance (NMR) spectroscopy. Advanced NMR techniques are often taught including two-dimensional gradient-based experiments. An investigation of intermolecular forces including viscosity, by a variety of methods, is often integrated in the undergraduate physical and…

  17. Organic Spectroscopy Laboratory: Utilizing IR and NMR in the Identification of an Unknown Substance

    Science.gov (United States)

    Glagovich, Neil M.; Shine, Timothy D.

    2005-01-01

    A laboratory experiment that emphasizes the interpretation of both infrared (IR) and nuclear magnetic resonance (NMR) spectra in the elucidation of the structure of an unknown compound was developed. The method helps students determine [to the first power]H- and [to the thirteenth power]C-NMR spectra from the structures of compounds and to…

  18. An Oil Spill in a Tube: An Accessible Approach for Teaching Environmental NMR Spectroscopy

    Science.gov (United States)

    Simpson, Andre´ J.; Mitchell, Perry J.; Masoom, Hussain; Mobarhan, Yalda Liaghati; Adamo, Antonio; Dicks, Andrew P.

    2015-01-01

    NMR spectroscopy has great potential as an instrumental method for environmental chemistry research and monitoring but may be underused in teaching laboratories because of its complexity and the level of expertise required in operating the instrument and interpreting data. This laboratory experiment introduces environmental NMR spectroscopy to…

  19. Structural characterization of homogalacturonan by NMR spectroscopy-assignment of reference compounds.

    Science.gov (United States)

    Petersen, Bent O; Meier, Sebastian; Duus, Jens Ø; Clausen, Mads H

    2008-11-03

    Complete assignment of (1)H and (13)C NMR of six hexagalactopyranuronic acids with varying degree and pattern of methyl esterification is reported. The NMR experiments were run at room temperature using approximately 2mg of sample making this method convenient for studying the structure of homogalacturonan oligosaccharides.

  20. Adiabatic low-pass J filters for artifact suppression in heteronuclear NMR.

    Science.gov (United States)

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

    2009-04-14

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

  1. An Oil Spill in a Tube: An Accessible Approach for Teaching Environmental NMR Spectroscopy

    Science.gov (United States)

    Simpson, Andre´ J.; Mitchell, Perry J.; Masoom, Hussain; Mobarhan, Yalda Liaghati; Adamo, Antonio; Dicks, Andrew P.

    2015-01-01

    NMR spectroscopy has great potential as an instrumental method for environmental chemistry research and monitoring but may be underused in teaching laboratories because of its complexity and the level of expertise required in operating the instrument and interpreting data. This laboratory experiment introduces environmental NMR spectroscopy to…

  2. Measurement of Solution Viscosity via Diffusion-Ordered NMR Spectroscopy (DOSY)

    Science.gov (United States)

    Li, Weibin; Kagan, Gerald; Hopson, Russell; Williard, Paul G.

    2011-01-01

    Increasingly, the undergraduate chemistry curriculum includes nuclear magnetic resonance (NMR) spectroscopy. Advanced NMR techniques are often taught including two-dimensional gradient-based experiments. An investigation of intermolecular forces including viscosity, by a variety of methods, is often integrated in the undergraduate physical and…

  3. The NMR restraints grid at BMRB for 5,266 protein and nucleic acid PDB entries.

    NARCIS (Netherlands)

    Doreleijers, J.F.; Vranken, W.F.; Schulte, C.; Lin, J.; Wedell, J.R.; Penkett, C.J.; Vuister, G.W.; Vriend, G.; Markley, J.L.; Ulrich, E.L.

    2009-01-01

    Several pilot experiments have indicated that improvements in older NMR structures can be expected by applying modern software and new protocols (Nabuurs et al. in Proteins 55:483-186, 2004; Nederveen et al. in Proteins 59:662-672, 2005; Saccenti and Rosato in J Biomol NMR 40:251-261, 2008). A recen

  4. Permanent Magnet with Very Low Field Gradient (0.1G/mm) for NMR Spectroscopy

    Science.gov (United States)

    Ilic, Ognjen; Issadore, David; Hunt, Tom; Westervelt, Robert

    2007-03-01

    Nuclear Magnetic Resonance (NMR) is a powerful analytical tool for obtaining chemical, physical and structural information. To produce the uniform fields required, NMR experiments typically employ large, expensive electromagnets and shimming coils. We have developed a small permanent magnet with an iron yoke that produces a field of ˜10 kG with gradient CCNE.

  5. Menstrual Cycle

    Science.gov (United States)

    ... Luteal (after egg release) Changes During the Menstrual Cycle The menstrual cycle is regulated by the complex interaction of ... egg release) Luteal (after egg release) The menstrual cycle begins with menstrual bleeding (menstruation), which marks the first day of ...

  6. Two-Dimensional NMR Lineshape Analysis

    Science.gov (United States)

    Waudby, Christopher A.; Ramos, Andres; Cabrita, Lisa D.; Christodoulou, John

    2016-04-01

    NMR titration experiments are a rich source of structural, mechanistic, thermodynamic and kinetic information on biomolecular interactions, which can be extracted through the quantitative analysis of resonance lineshapes. However, applications of such analyses are frequently limited by peak overlap inherent to complex biomolecular systems. Moreover, systematic errors may arise due to the analysis of two-dimensional data using theoretical frameworks developed for one-dimensional experiments. Here we introduce a more accurate and convenient method for the analysis of such data, based on the direct quantum mechanical simulation and fitting of entire two-dimensional experiments, which we implement in a new software tool, TITAN (TITration ANalysis). We expect the approach, which we demonstrate for a variety of protein-protein and protein-ligand interactions, to be particularly useful in providing information on multi-step or multi-component interactions.

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

    Energy Technology Data Exchange (ETDEWEB)

    Matwiyoff, N.A.

    1983-01-01

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

  8. Large-eddy simulation of the diurnal cycle of the atmospheric boundary layer and influence of the radiative forcing during the Wangara experiment.

    Science.gov (United States)

    Dall'Ozzo, Cédric; Carissimo, Bertrand; Milliez, Maya; Musson-Genon, Luc; Dupont, Eric

    2013-04-01

    The ability to simulate the whole diurnal cycle of the atmospheric boundary layer in order to study the complex turbulent structures remains a difficult topic. Consequently large-eddy simulations (LES) are performed with the open source CFD code Code_Saturne [Archambeau et al., 2004]. First the code is validated on an atmospheric convective case [Schmidt and Schumann, 1989] where different subgrid-scale (SGS) models are compared: two non-dynamical SGS models [Smagorinsky, 1963] [Nicoud and Ducros, 1999] and two dynamical SGS models [Germano et al., 1991 ; Lilly, 1992] [Wong and Lilly, 1994]. Then LES are performed to simulate the whole diurnal cycle of the Wangara experiment (Day 33-34). The results are compared to measurements , RANS "k-ɛ" model and other LES performed by [Basu et al., 2008] using a locally averaged scale-dependent dynamic (LASDD) SGS model. Thereafter the influence of the radiative forcing on the atmosphere is studied testing several SGS models. The results are especially discussed on nocturnal low level jet and potential temperature gradient in the stable boundary layer. References: [Archambeau et al., 2004] Archambeau F., Mehitoua N., Sakiz M. (2004). Code_Saturne: a finite volume code for the computation of turbulent incompressible flows. International Journal on Finite Volumes 1(1). [Basu et al., 2008] Basu S., Vinuesa J. F., and Swift A. (2008). Dynamic LES modeling of a diurnal cycle. Journal of Applied Meteorology and Climatology, 47 :1156-1174. [Germano et al., 1991] Germano M., Piomelli U., Moin P., and Cabot W. H. (1991). A dynamic subgrid-scale eddy-viscosity model. Physics of Fluids, A3 :1760-1765. [Lilly, 1992] Lilly D. K. (1992). A proposed modification of the Germano subgrid-scale closure method. Physics of Fluids, A 4 :633-635. [Schmidt and Schumann, 1989] Schmidt H. and Schumann U. (1989). Coherent structure of the convective boundary layer derived from lage-eddy simulation. Journal of Fluid Mechanics, 200 :511-562. [Smagorinsky

  9. Time domain NMR evaluation of poly(vinyl alcohol) xerogels

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, Elton Jorge da Rocha; Cavalcante, Maxwell de Paula; Tavares, Maria Ines Bruno, E-mail: mibt@ima.ufrj.br [Universidade Federal do Rio de Janeiro (IMA/UFRJ), Rio de Janeiro, RJ (Brazil). Centro de Tecnologia. Instituto de Macromoleculas Professora Eloisa Mano

    2016-05-15

    Poly(vinyl alcohol) (PVA)-based chemically cross-linked xerogels, both neat and loaded with nanoparticulate hydrophilic silica (SiO{sub 2}), were obtained and characterized mainly through time domain NMR experiments (TD-NMR). Fourier-transform infrared (FT-IR) and wide angle X-ray diffraction (WAXD) analyses were employed as secondary methods. TD-NMR, through the interpretation of the spin-lattice relaxation constant values and related information, showed both cross-linking and nanoparticle influences on PVA matrix. SiO{sub 2} does not interact chemically with the PVA chains, but has effect on its molecular mobility, as investigated via TD-NMR. Apparent energy of activation, spin-lattice time constant and size of spin domains in the sample have almost linear dependence with the degree of cross-linking of the PVA and are affected by the addition of SiO{sub 2}. These three parameters were derived from a single set of TD-NMR experiments, which demonstrates the versatility of the technique for characterization of inorganic-organic hybrid xerogels, an important class of materials. (author)

  10. High resolution NMR study of T{sub 1} magnetic relaxation dispersion. IV. Proton relaxation in amino acids and Met-enkephalin pentapeptide

    Energy Technology Data Exchange (ETDEWEB)

    Pravdivtsev, Andrey N.; Yurkovskaya, Alexandra V.; Ivanov, Konstantin L., E-mail: ivanov@tomo.nsc.ru [International Tomography Center, Institutskaya 3a, Novosibirsk 630090 (Russian Federation); Department of Physics, Novosibirsk State University, Pirogova 2, Novosibirsk 630090 (Russian Federation); Vieth, Hans-Martin [Institut für Experimentalphysik, Freie Universität Berlin Arnimallee 14, 14195 Berlin (Germany)

    2014-10-21

    Nuclear Magnetic Relaxation Dispersion (NMRD) of protons was studied in the pentapeptide Met-enkephalin and the amino acids, which constitute it. Experiments were run by using high-resolution Nuclear Magnetic Resonance (NMR) in combination with fast field-cycling, thus enabling measuring NMRD curves for all individual protons. As in earlier works, Papers I–III, pronounced effects of intramolecular scalar spin-spin interactions, J-couplings, on spin relaxation were found. Notably, at low fields J-couplings tend to equalize the apparent relaxation rates within networks of coupled protons. In Met-enkephalin, in contrast to the free amino acids, there is a sharp increase in the proton T{sub 1}-relaxation times at high fields due to the changes in the regime of molecular motion. The experimental data are in good agreement with theory. From modelling the relaxation experiments we were able to determine motional correlation times of different residues in Met-enkephalin with atomic resolution. This allows us to draw conclusions about preferential conformation of the pentapeptide in solution, which is also in agreement with data from two-dimensional NMR experiments (rotating frame Overhauser effect spectroscopy). Altogether, our study demonstrates that high-resolution NMR studies of magnetic field-dependent relaxation allow one to probe molecular mobility in biomolecules with atomic resolution.

  11. NMR Dynamic Studies in Living Systems

    Institute of Scientific and Technical Information of China (English)

    闫永彬; 范明杰; 罗雪春; 张日清

    2002-01-01

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

  12. Translational diffusion in paramagnetic liquids by 1H NMR relaxometry: nitroxide radicals in solution.

    Science.gov (United States)

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

    2013-01-14

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

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

    Science.gov (United States)

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

    2013-01-01

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

  14. NMR studies of actinide dioxides

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-10-11

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

  15. DNTF的核磁表征及理论研究%NMR Characterization and Theoretical Investigation of DNTF

    Institute of Scientific and Technical Information of China (English)

    王民昌; 毕福强; 张皋; 栾洁玉; 徐敏; 宁艳利; 樊学忠

    2013-01-01

    为了完善3,4-双(4′-硝基呋咱-3′-基)氧化呋咱(DNTF)的核磁表征,采用 NMR 实验与 GIAO-NMR 理论计算相结合的方法区分并归属13 C 和15 N 的化学位移。采用二甲基亚砜( DMSO-d6)、丙酮( Acetone-d6)和氯仿( CDCl3)为溶剂,进行了 DNTF 的一维13 C NMR和15 N NMR实验,并在 DMSO-d6中获得 DNTF的所有核磁信号。采用二维 INADEQUATE实验完成了13 C NMR 的归属。采用高斯09程序,在 DFT-B3LYP/6-311+G(2d,p)水平上优化了 DNTF 结构,用 GIAO 方法在不同基组上计算了13C NMR和15N NMR的化学位移,计算结果与实验值一致性较好。结果表明,受氧化呋咱环上氧原子 O(22)吸电子作用的影响, C(9)与 C(13)的化学位移出现较大的差别,与 C(13)相比,C(9)出现在高场。%In order to optimize the NMR assignment of 3,4-dinitrofurazanfuroxan(DNTF),a combination of experimental NMR and computational GIAO-NMR techniques was utilized to distinguish the chemical shifts of 13C and 15N. One dimensional(1D) 13 C and 15 N NMR analyses were performed using DMSO-d6 ,acetone-d6 and CDCl3 as solvent. All signals of DNTF were found in DMSO-d6 . In the 13 C NMR,the chemical shifts were assigned by 2D INADEQUATE NMR experiment. Based on the geometry of DNTF optimized at the DFT-B3LYP/6-311 +G(2d,p)level by using Guassian 09 program,the 13C and 15N NMR chemical shifts were calculated by GIAO method at different level,which agree with experimental data. Results show that the electro-withdrawing effect of the O(22)in furoxan cycle leads to large 13C chemical shift changes of C(9)and C(13),and makes C(9)appear in higher field than C(13).

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

    Science.gov (United States)

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

    2007-07-12

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

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

    Directory of Open Access Journals (Sweden)

    Jaume Bastida

    2007-07-01

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

  18. Studies on supramolecular gel formation using DOSY NMR.

    Science.gov (United States)

    Nonappa; Šaman, David; Kolehmainen, Erkki

    2015-04-01

    Herein, we present the results obtained from our studies on supramolecular self-assembly and molecular mobility of low-molecular-weight gelators (LMWGs) in organic solvents using pulsed field gradient (PFG) diffusion ordered spectroscopy (DOSY) NMR. A series of concentration-dependent DOSY NMR experiments were performed on selected LMWGs to determine the critical gelation concentration (CGC) as well as to understand the behaviour of the gelator molecules in the gel state. In addition, variable-temperature DOSY NMR experiments were performed to determine the gel-to-sol transition. The PFG NMR experiments performed as a function of gradient strength were further analyzed using monoexponential DOSY processing, and the results were compared with the automated Bayesian DOSY transformation to obtain 2D plots. Our results provide useful information on the stepwise self-assembly of small molecules leading to gelation. We believe that the results obtained from these experiments are applicable in determining the CGC and gel melting temperatures of supramolecular gels.

  19. Non-uniform sampling of NMR relaxation data

    DEFF Research Database (Denmark)

    Schwarz-Linnet, Troels; Teilum, Kaare

    2016-01-01

    The use of non-uniform sampling of NMR spectra may give significant reductions in the data acquisition time. For quantitative experiments such as the measurement of spin relaxation rates, non-uniform sampling is however not widely used as inaccuracies in peak intensities may lead to errors...

  20. High-temperature MAS-NMR at high spinning speeds.

    Science.gov (United States)

    Kirchhain, Holger; Holzinger, Julian; Mainka, Adrian; Spörhase, Andreas; Venkatachalam, Sabarinathan; Wixforth, Achim; van Wüllen, Leo

    2016-09-01

    A low cost version to enable high temperature MAS NMR experiments at temperatures of up to 700°C and spinning speeds of up to 10kHz is presented. The method relies on inductive heating using a metal coated rotor insert. The metal coating is accomplished via a two step process involving physical vapor deposition and galvanization.

  1. Facing and Overcoming Sensitivity Challenges in Biomolecular NMR Spectroscopy

    DEFF Research Database (Denmark)

    Ardenkjær-Larsen, Jan Henrik; Boebinger, Gregory S.; Comment, Arnaud

    2015-01-01

    enhance the sensitivity of solid‐ and liquid‐state experiments. While substantial advances have been made in all these areas, numerous challenges remain in the quest of endowing NMR spectroscopy with the sensitivity that has characterized forms of spectroscopies based on electrical or optical measurements....... These challenges, and the ways by which scientists and engineers are striving to solve them, are also addressed....

  2. Numerical simulation of NQR/NMR: Applications in quantum computing.

    Science.gov (United States)

    Possa, Denimar; Gaudio, Anderson C; Freitas, Jair C C

    2011-04-01

    A numerical simulation program able to simulate nuclear quadrupole resonance (NQR) as well as nuclear magnetic resonance (NMR) experiments is presented, written using the Mathematica package, aiming especially applications in quantum computing. The program makes use of the interaction picture to compute the effect of the relevant nuclear spin interactions, without any assumption about the relative size of each interaction. This makes the program flexible and versatile, being useful in a wide range of experimental situations, going from NQR (at zero or under small applied magnetic field) to high-field NMR experiments. Some conditions specifically required for quantum computing applications are implemented in the program, such as the possibility of use of elliptically polarized radiofrequency and the inclusion of first- and second-order terms in the average Hamiltonian expansion. A number of examples dealing with simple NQR and quadrupole-perturbed NMR experiments are presented, along with the proposal of experiments to create quantum pseudopure states and logic gates using NQR. The program and the various application examples are freely available through the link http://www.profanderson.net/files/nmr_nqr.php.

  3. High-Resolution NMR of Quadrupolar Nuclei in the Solid State

    Energy Technology Data Exchange (ETDEWEB)

    Gann, Sheryl Lee

    1995-11-30

    This dissertation describes recent developments in solid state nuclear magnetic resonance (NMR), for the most part involving the use of dynamic-angle spinning (DAS) NMR to study quadrupolar nuclei. Chapter 1 introduces some of the basic concepts and theory that will be referred to in later chapters, such as the density operator, product operators, rotations, coherence transfer pathways, phase cycling, and the various nuclear spin interactions, including the quadrupolar interaction. Chapter 2 describes the theory behind motional averaging experiments, including DAS, which is a technique where a sample is spun sequentially about two axis oriented at different angles with respect to the external magnetic field such that the chemical shift and quadrupolar anisotropy are averaged to zero. Work done on various rubidium-87 salts is presented as a demonstration of DAS. Chapter 3 explains how to remove sidebands from DAS and magic-angle spinning (MAS) experiments, which result from the time-dependence of the Hamiltonian under sample spinning conditions, using rotor-synchronized {pi}-pulses. Data from these experiments, known as DAH-180 and MAH-180, respectively, are presented for both rubidium and lead salts. In addition, the applicability of this technique to double rotation (DOR) experiments is discussed. Chapter 4 concerns the addition of cross-polarization to DAS (CPDAS). The theory behind spin locking and cross polarizing quadrupolar nuclei is explained and a method of avoiding the resulting problems by performing cross polarization at 0{sup o} (parallel) with respect to the magnetic field is presented. Experimental results are shown for a sodium-23 compound, sodium pyruvate, and for oxygen-17 labeled L-akmine. In Chapter 5, a method for broadening the Hartmann-Hahn matching condition under MAS, called variable effective field cross-polarization (VEFCI?), is presented, along with experimental work on adamantane and polycarbonate.

  4. NMR and dynamics of biopolymers

    Energy Technology Data Exchange (ETDEWEB)

    Lian, L.Y.; Barsukov, I.L. [Leicester Univ. (United Kingdom)

    1994-12-31

    Several basic experimental analytical NMR techniques that are frequently used for the qualitative and quantitative analysis of dynamic and exchange processes, focusing on proteins systems, are described: chemical exchange (slow exchange, fast exchange, intermediate exchange), heteronuclear relaxation measurements (relaxation parameters, strategy of relaxation data analysis, experimental results and examples, motional model interpretation of relaxation data, homonuclear relaxation); slow large-scale exchange and hydrogen-deuterium exchange are also studied: mechanisms of hydrogen exchange in a native protein, methods for measuring amide exchange rates by NMR, interpretation of amide exchange rates. 9 fig., 3 tab., 56 ref.

  5. Spectral Estimation of NMR Relaxation

    Science.gov (United States)

    Naugler, David G.; Cushley, Robert J.

    2000-08-01

    In this paper, spectral estimation of NMR relaxation is constructed as an extension of Fourier Transform (FT) theory as it is practiced in NMR or MRI, where multidimensional FT theory is used. nD NMR strives to separate overlapping resonances, so the treatment given here deals primarily with monoexponential decay. In the domain of real error, it is shown how optimal estimation based on prior knowledge can be derived. Assuming small Gaussian error, the estimation variance and bias are derived. Minimum bias and minimum variance are shown to be contradictory experimental design objectives. The analytical continuation of spectral estimation is constructed in an optimal manner. An important property of spectral estimation is that it is phase invariant. Hence, hypercomplex data storage is unnecessary. It is shown that, under reasonable assumptions, spectral estimation is unbiased in the context of complex error and its variance is reduced because the modulus of the whole signal is used. Because of phase invariance, the labor of phasing and any error due to imperfect phase can be avoided. A comparison of spectral estimation with nonlinear least squares (NLS) estimation is made analytically and with numerical examples. Compared to conventional sampling for NLS estimation, spectral estimation would typically provide estimation values of comparable precision in one-quarter to one-tenth of the spectrometer time when S/N is high. When S/N is low, the time saved can be used for signal averaging at the sampled points to give better precision. NLS typically provides one estimate at a time, whereas spectral estimation is inherently parallel. The frequency dimensions of conventional nD FT NMR may be denoted D1, D2, etc. As an extension of nD FT NMR, one can view spectral estimation of NMR relaxation as an extension into the zeroth dimension. In nD NMR, the information content of a spectrum can be extracted as a set of n-tuples (ω1, … ωn), corresponding to the peak maxima

  6. Utilization of {sup 13}C-enriched substrates for the NMR study of the channelling of Krebs cycle intermediates in glioma C6; Utilisation de substrats enrichis en {sup 13}C pour l`etude par RMN de la canalisation des intermediaires du cycle de Krebs dans le gliome C6

    Energy Technology Data Exchange (ETDEWEB)

    Merle, M.; Peron, M.; Valeins, H.; Canioni, P. [Bordeaux-2 Univ., 33 (France)

    1994-12-31

    Unequal enrichments are observed for the C2 and C3 carbons of glutamate (C2>C3) and of aspartate (C3>C2) during incubation of C6 cells with (1-{sup 13} C) glucose. In order to study if this result is the result of an entry of {sup 13}C at the oxalo-acetate level or of another phenomenon, the enrichment distribution on asparte C1 and C4 carbons of C6 cells incubated with (1-{sup 13} C) glucose and the enrichment of C2 and C3 carbons of glutamate during cell incubation with (2-{sup 13} C) acetate, i.e. cases where the entry of {sup 13}C in the cycle, via the activity of the pyruvate carboxylase, is very unlikely, are examined. 4 figs., 1 tab., 1 ref.

  7. Leveraging 35 years of Pinus taeda research in the southeastern US to constrain forest carbon cycle predictions: regional data assimilation using ecosystem experiments

    Directory of Open Access Journals (Sweden)

    R. Q. Thomas

    2017-07-01

    Full Text Available Predicting how forest carbon cycling will change in response to climate change and management depends on the collective knowledge from measurements across environmental gradients, ecosystem manipulations of global change factors, and mathematical models. Formally integrating these sources of knowledge through data assimilation, or model–data fusion, allows the use of past observations to constrain model parameters and estimate prediction uncertainty. Data assimilation (DA focused on the regional scale has the opportunity to integrate data from both environmental gradients and experimental studies to constrain model parameters. Here, we introduce a hierarchical Bayesian DA approach (Data Assimilation to Predict Productivity for Ecosystems and Regions, DAPPER that uses observations of carbon stocks, carbon fluxes, water fluxes, and vegetation dynamics from loblolly pine plantation ecosystems across the southeastern US to constrain parameters in a modified version of the Physiological Principles Predicting Growth (3-PG forest growth model. The observations included major experiments that manipulated atmospheric carbon dioxide (CO2 concentration, water, and nutrients, along with nonexperimental surveys that spanned environmental gradients across an 8.6  ×  105 km2 region. We optimized regionally representative posterior distributions for model parameters, which dependably predicted data from plots withheld from the data assimilation. While the mean bias in predictions of nutrient fertilization experiments, irrigation experiments, and CO2 enrichment experiments was low, future work needs to focus modifications to model structures that decrease the bias in predictions of drought experiments. Predictions of how growth responded to elevated CO2 strongly depended on whether ecosystem experiments were assimilated and whether the assimilated field plots in the CO2 study were allowed to have different mortality parameters than the other field

  8. Leveraging 35 years of Pinus taeda research in the southeastern US to constrain forest carbon cycle predictions: regional data assimilation using ecosystem experiments

    Science.gov (United States)

    Quinn Thomas, R.; Brooks, Evan B.; Jersild, Annika L.; Ward, Eric J.; Wynne, Randolph H.; Albaugh, Timothy J.; Dinon-Aldridge, Heather; Burkhart, Harold E.; Domec, Jean-Christophe; Fox, Thomas R.; Gonzalez-Benecke, Carlos A.; Martin, Timothy A.; Noormets, Asko; Sampson, David A.; Teskey, Robert O.

    2017-07-01

    Predicting how forest carbon cycling will change in response to climate change and management depends on the collective knowledge from measurements across environmental gradients, ecosystem manipulations of global change factors, and mathematical models. Formally integrating these sources of knowledge through data assimilation, or model-data fusion, allows the use of past observations to constrain model parameters and estimate prediction uncertainty. Data assimilation (DA) focused on the regional scale has the opportunity to integrate data from both environmental gradients and experimental studies to constrain model parameters. Here, we introduce a hierarchical Bayesian DA approach (Data Assimilation to Predict Productivity for Ecosystems and Regions, DAPPER) that uses observations of carbon stocks, carbon fluxes, water fluxes, and vegetation dynamics from loblolly pine plantation ecosystems across the southeastern US to constrain parameters in a modified version of the Physiological Principles Predicting Growth (3-PG) forest growth model. The observations included major experiments that manipulated atmospheric carbon dioxide (CO2) concentration, water, and nutrients, along with nonexperimental surveys that spanned environmental gradients across an 8.6 × 105 km2 region. We optimized regionally representative posterior distributions for model parameters, which dependably predicted data from plots withheld from the data assimilation. While the mean bias in predictions of nutrient fertilization experiments, irrigation experiments, and CO2 enrichment experiments was low, future work needs to focus modifications to model structures that decrease the bias in predictions of drought experiments. Predictions of how growth responded to elevated CO2 strongly depended on whether ecosystem experiments were assimilated and whether the assimilated field plots in the CO2 study were allowed to have different mortality parameters than the other field plots in the region. We present

  9. MVAPACK: a complete data handling package for NMR metabolomics.

    Science.gov (United States)

    Worley, Bradley; Powers, Robert

    2014-05-16

    Data handling in the field of NMR metabolomics has historically been reliant on either in-house mathematical routines or long chains of expensive commercial software. Thus, while the relatively simple biochemical protocols of metabolomics maintain a low barrier to entry, new practitioners of metabolomics experiments are forced to either purchase expensive software packages or craft their own data handling solutions from scratch. This inevitably complicates the standardization and communication of data handling protocols in the field. We report a newly developed open-source platform for complete NMR metabolomics data handling, MVAPACK, and describe its application on an example metabolic fingerprinting data set.

  10. Results of molten salt panel and component experiments for solar central receivers: Cold fill, freeze/thaw, thermal cycling and shock, and instrumentation tests

    Energy Technology Data Exchange (ETDEWEB)

    Pacheco, J.E.; Ralph, M.E.; Chavez, J.M.; Dunkin, S.R.; Rush, E.E.; Ghanbari, C.M.; Matthews, M.W.

    1995-01-01

    Experiments have been conducted with a molten salt loop at Sandia National Laboratories in Albuquerque, NM to resolve issues associated with the operation of the 10MW{sub e} Solar Two Central Receiver Power Plant located near Barstow, CA. The salt loop contained two receiver panels, components such as flanges and a check valve, vortex shedding and ultrasonic flow meters, and an impedance pressure transducer. Tests were conducted on procedures for filling and thawing a panel, and assessing components and instrumentation in a molten salt environment. Four categories of experiments were conducted: (1) cold filling procedures, (2) freeze/thaw procedures, (3) component tests, and (4) instrumentation tests. Cold-panel and -piping fill experiments are described, in which the panels and piping were preheated to temperatures below the salt freezing point prior to initiating flow, to determine the feasibility of cold filling the receiver and piping. The transient thermal response was measured, and heat transfer coefficients and transient stresses were calculated from the data. Freeze/thaw experiments were conducted with the panels, in which the salt was intentionally allowed to freeze in the receiver tubes, then thawed with heliostat beams. Slow thermal cycling tests were conducted to measure both how well various designs of flanges (e.g., tapered flanges or clamp type flanges) hold a seal under thermal conditions typical of nightly shut down, and the practicality of using these flanges on high maintenance components. In addition, the flanges were thermally shocked to simulate cold starting the system. Instrumentation such as vortex shedding and ultrasonic flow meters were tested alongside each other, and compared with flow measurements from calibration tanks in the flow loop.

  11. Lithium Polymer Electrolytes and Solid State NMR

    Science.gov (United States)

    Berkeley, Emily R.

    2004-01-01

    Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for

  12. Micellar kinetics of a fluorosurfactant through stopped-flow NMR.

    Science.gov (United States)

    Yushmanov, Pavel V; Furó, István; Stilbs, Peter

    2006-02-28

    19F NMR chemical shifts and transverse relaxation times T2 were measured as a function of time after quick stopped-flow dilution of aqueous solutions of sodium perfluorooctanoate (NaPFO) with water. Different initial concentrations of micellar solution and different proportions of mixing were tested. Previous stopped-flow studies by time-resolved small-angle X-ray scattering (TR-SAXS) detection indicated a slow (approximately 10 s) micellar relaxation kinetics in NaPFO solutions. In contrast, no evidence of any comparable slow (>100 ms) relaxation process was found in our NMR studies. Possible artifacts of stopped-flow experiments are discussed as well as differences between NMR and SAXS detection methods. Upper bounds on the relative weight of a slow relaxation process are given within existing kinetic theories of micellar dissolution.

  13. NMRFx Processor: a cross-platform NMR data processing program.

    Science.gov (United States)

    Norris, Michael; Fetler, Bayard; Marchant, Jan; Johnson, Bruce A

    2016-08-01

    NMRFx Processor is a new program for the processing of NMR data. Written in the Java programming language, NMRFx Processor is a cross-platform application and runs on Linux, Mac OS X and Windows operating systems. The application can be run in both a graphical user interface (GUI) mode and from the command line. Processing scripts are written in the Python programming language and executed so that the low-level Java commands are automatically run in parallel on computers with multiple cores or CPUs. Processing scripts can be generated automatically from the parameters of NMR experiments or interactively constructed in the GUI. A wide variety of processing operations are provided, including methods for processing of non-uniformly sampled datasets using iterative soft thresholding. The interactive GUI also enables the use of the program as an educational tool for teaching basic and advanced techniques in NMR data analysis.

  14. Relaxation dispersion NMR spectroscopy for the study of protein allostery.

    Science.gov (United States)

    Farber, Patrick J; Mittermaier, Anthony

    2015-06-01

    Allosteric transmission of information between distant sites in biological macromolecules often involves collective transitions between active and inactive conformations. Nuclear magnetic resonance (NMR) spectroscopy can yield detailed information on these dynamics. In particular, relaxation dispersion techniques provide structural, dynamic, and mechanistic information on conformational transitions occurring on the millisecond to microsecond timescales. In this review, we provide an overview of the theory and analysis of Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion NMR experiments and briefly describe their application to the study of allosteric dynamics in the homeodomain from the PBX transcription factor (PBX-HD). CPMG NMR data show that local folding (helix/coil) transitions in one part of PBX-HD help to communicate information between two distant binding sites. Furthermore, the combination of CPMG and other spin relaxation data show that this region can also undergo local misfolding, reminiscent of conformational ensemble models of allostery.

  15. Ligand screening by saturation-transfer difference (STD) NMR spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan, V V

    2005-04-26

    NMR based methods to screen for high-affinity ligands have become an indispensable tool for designing rationalized drugs, as these offer a combination of good experimental design of the screening process and data interpretation methods, which together provide unprecedented information on the complex nature of protein-ligand interactions. These methods rely on measuring direct changes in the spectral parameters, that are often simpler than the complex experimental procedures used to study structure and dynamics of proteins. The goal of this review article is to provide the basic details of NMR based ligand-screening methods, with particular focus on the saturation transfer difference (STD) experiment. In addition, we provide an overview of other NMR experimental methods and a practical guide on how to go about designing and implementing them.

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

    Science.gov (United States)

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

    2006-01-01

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

  17. Theoretical Modeling of 99 Tc NMR Chemical Shifts

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-06

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

  18. Recovering Invisible Signals by Two-Field NMR Spectroscopy.

    Science.gov (United States)

    Cousin, Samuel F; Kadeřávek, Pavel; Haddou, Baptiste; Charlier, Cyril; Marquardsen, Thorsten; Tyburn, Jean-Max; Bovier, Pierre-Alain; Engelke, Frank; Maas, Werner; Bodenhausen, Geoffrey; Pelupessy, Philippe; Ferrage, Fabien

    2016-08-16

    Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two-field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low-field dimension. Two-field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields.

  19. Push-through Direction Injectin NMR Automation

    Science.gov (United States)

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

  20. Push-through Direction Injectin NMR Automation

    Science.gov (United States)

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

  1. A Modified Alderman-Grant Coil makes possible an efficient cross-coil probe for high field solid-state NMR of lossy biological samples

    Science.gov (United States)

    Grant, Christopher V.; Yang, Yuan; Glibowicka, Mira; Wu, Chin H.; Park, Sang Ho; Deber, Charles M.; Opella, Stanley J.

    2009-11-01

    The design, construction, and performance of a cross-coil double-resonance probe for solid-state NMR experiments on lossy biological samples at high magnetic fields are described. The outer coil is a Modified Alderman-Grant Coil (MAGC) tuned to the 1H frequency. The inner coil consists of a multi-turn solenoid coil that produces a B 1 field orthogonal to that of the outer coil. This results in a compact nested cross-coil pair with the inner solenoid coil tuned to the low frequency detection channel. This design has several advantages over multiple-tuned solenoid coil probes, since RF heating from the 1H channel is substantially reduced, it can be tuned for samples with a wide range of dielectric constants, and the simplified circuit design and high inductance inner coil provides excellent sensitivity. The utility of this probe is demonstrated on two electrically lossy samples of membrane proteins in phospholipid bilayers (bicelles) that are particularly difficult for conventional NMR probes. The 72-residue polypeptide embedding the transmembrane helices 3 and 4 of the Cystic Fibrosis Transmembrane Conductance Regulator (CFTR) (residues 194-241) requires a high salt concentration in order to be successfully reconstituted in phospholipid bicelles. A second application is to paramagnetic relaxation enhancement applied to the membrane-bound form of Pf1 coat protein in phospholipid bicelles where the resistance to sample heating enables high duty cycle solid-state NMR experiments to be performed.

  2. High resolution NMR theory and chemical applications

    CERN Document Server

    Becker, Edwin D

    1969-01-01

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

  3. Time domain NMR applied to food products

    NARCIS (Netherlands)

    Duynhoven, van J.P.M.; Voda, A.; Witek, M.M.; As, van H.

    2010-01-01

    Time-domain NMR is being used throughout all areas of food science and technology. A wide range of one- and two-dimensional relaxometric and diffusometric applications have been implemented on cost-effective, robust and easy-to-use benchtop NMR equipment. Time-domain NMR applications do not only

  4. NMR study of magnetism and superparamagnetism

    Science.gov (United States)

    Yuan, Shaojie

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

  5. NMR probe for dynamic-angle spinning

    Science.gov (United States)

    Mueller, K. T.; Chingas, G. C.; Pines, A.

    1991-06-01

    We describe the design of a probe for dynamic-angle spinning (DAS) NMR experiments, comprised of a spinning cylindrical sample holder whose axis may be reoriented rapidly between discrete directions within the bore of a superconducting magnet. This allows the refocusing of nuclear spin magnetization that evolves under anisotropic interactions such as chemical shift anisotropy and quadrupolar coupling, providing high resolution NMR spectra for quadrupolar nuclei in solid materials. The probe includes an axial air delivery system to bearing and drive jets which support and spin a rotor containing the sample. Axis reorientation is accomplished with a pulley attached to the probehead and coupled to a stepping motor outside of the magnet. The choice of motor and gear ratio is based on an analysis of the moments of inertia of the motor and load, the desired angular resolution, and simplicity of design. Control of angular accuracy and precision are discussed, as well as the efficiency of radiofrequency irradiation and detection. High resolution DAS spectra of oxygen-17 and aluminum-27 nuclei in polycrystalline minerals illustrate the experimental capabilities.

  6. Structure and Dynamics Studies of Cytolytic Peptides in Lipid Bilayers using NMR Spectroscopy

    DEFF Research Database (Denmark)

    Hansen, Sara Krogh

    2015-01-01

    different and cytolytic peptides were investigated in this work. The peptides were SPF-5506-A4 from Trichoderma sp, Conolysin-Mt1 from Conus mustelinus, and Alamethicin from Trichoderma viride. The studies employed solution and solid-state NMR spectroscopy in combination with different biophysical methods......- and 2H-labelled peptides. While the solution NMR experiments were performed to determine the structure of SPF-5506-A4 and Conolysin-Mt1, the oriented solid-state NMR experiments served to derive information about the orientation of the peptides with respect to the bilayer normal in order to understand...

  7. Study of a Conformational Equilibrium of Lisinopril by HPLC, NMR, and DFT

    Science.gov (United States)

    Bouabdallah, Sondes; Ben Dhia, Med Thaieb; Driss, Med Rida

    2014-01-01

    The isomerization of lisinopril has been investigated using chromatographic, NMR spectroscopic, and theoretical calculations. The NMR data, particularly the NOEDIFF experiments, show that the major species that was eluted first is the trans form. The proportion was 77% and 23% for the trans and cis, respectively. The thermodynamic parameters (ΔH, ΔS, and ΔG) were determined by varying the temperature in the NMR experiments. The interpretations of the experimental data were further supported by DFT/B3LYP calculations. PMID:24707291

  8. Study of a Conformational Equilibrium of Lisinopril by HPLC, NMR, and DFT

    Directory of Open Access Journals (Sweden)

    Sondes Bouabdallah

    2014-01-01

    Full Text Available The isomerization of lisinopril has been investigated using chromatographic, NMR spectroscopic, and theoretical calculations. The NMR data, particularly the NOEDIFF experiments, show that the major species that was eluted first is the trans form. The proportion was 77% and 23% for the trans and cis, respectively. The thermodynamic parameters (ΔH, ΔS, and ΔG were determined by varying the temperature in the NMR experiments. The interpretations of the experimental data were further supported by DFT/B3LYP calculations.

  9. Magic-angle spinning NMR of cold samples.

    Science.gov (United States)

    Concistrè, Maria; Johannessen, Ole G; Carignani, Elisa; Geppi, Marco; Levitt, Malcolm H

    2013-09-17

    Magic-angle-spinning solid-state NMR provides site-resolved structural and chemical information about molecules that complements many other physical techniques. Recent technical advances have made it possible to perform magic-angle-spinning NMR experiments at low temperatures, allowing researchers to trap reaction intermediates and to perform site-resolved studies of low-temperature physical phenomena such as quantum rotations, quantum tunneling, ortho-para conversion between spin isomers, and superconductivity. In examining biological molecules, the improved sensitivity provided by cryogenic NMR facilitates the study of protein assembly or membrane proteins. The combination of low-temperatures with dynamic nuclear polarization has the potential to boost sensitivity even further. Many research groups, including ours, have addressed the technical challenges and developed hardware for magic-angle-spinning of samples cooled down to a few tens of degrees Kelvin. In this Account, we briefly describe these hardware developments and review several recent activities of our group which involve low-temperature magic-angle-spinning NMR. Low-temperature operation allows us to trap intermediates that cannot be studied under ambient conditions by NMR because of their short lifetime. We have used low-temperature NMR to study the electronic structure of bathorhodopsin, the primary photoproduct of the light-sensitive membrane protein, rhodopsin. This project used a custom-built NMR probe that allows low-temperature NMR in the presence of illumination (the image shows the illuminated spinner module). We have also used this technique to study the behavior of molecules within a restricted environment. Small-molecule endofullerenes are interesting molecular systems in which molecular rotors are confined to a well-insulated, well-defined, and highly symmetric environment. We discuss how cryogenic solid state NMR can give information on the dynamics of ortho-water confined in a fullerene

  10. ELISE NMR: Experimental liquid sealing of NMR samples

    Science.gov (United States)

    Wieruszeski, Jean-Michel; Landrieu, Isabelle; Hanoulle, Xavier; Lippens, Guy

    2006-08-01

    We present a simple, generally applicable approach to prevent sample evaporation when working at elevated temperatures in high resolution NMR. It consists of experimentally sealing the NMR sample by a second liquid (Experimental Liquid Sealing, ELISE). For aqueous samples, we identified the mineral oil commonly used in PCR application as the best candidate, because it contains only a very limited amount of water-soluble contaminants, is stable over time and heat resistant. The procedure does not interfere with shim settings, and is compatible with a wide variety of samples, including oligosaccharides and proteins. For chloroform samples, a simple drop of water allows to efficiently seal the sample, avoiding solvent evaporation even over lengthy time periods.

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

    OpenAIRE

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

    2010-01-01

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

  12. Biogeochemical Cycling

    Science.gov (United States)

    Bebout, Brad; Fonda, Mark (Technical Monitor)

    2002-01-01

    This lecture will introduce the concept of biogeochemical cycling. The roles of microbes in the cycling of nutrients, production and consumption of trace gases, and mineralization will be briefly introduced.

  13. Profiling formulated monoclonal antibodies by (1)H NMR spectroscopy.

    Science.gov (United States)

    Poppe, Leszek; Jordan, John B; Lawson, Ken; Jerums, Matthew; Apostol, Izydor; Schnier, Paul D

    2013-10-15

    Nuclear magnetic resonance (NMR) is arguably the most direct methodology for characterizing the higher-order structure of proteins in solution. Structural characterization of proteins by NMR typically utilizes heteronuclear experiments. However, for formulated monoclonal antibody (mAb) therapeutics, the use of these approaches is not currently tenable due to the requirements of isotope labeling, the large size of the proteins, and the restraints imposed by various formulations. Here, we present a new strategy to characterize formulated mAbs using (1)H NMR. This method, based on the pulsed field gradient stimulated echo (PGSTE) experiment, facilitates the use of (1)H NMR to generate highly resolved spectra of intact mAbs in their formulation buffers. This method of data acquisition, along with postacquisition signal processing, allows the generation of structural and hydrodynamic profiles of antibodies. We demonstrate how variation of the PGSTE pulse sequence parameters allows proton relaxation rates and relative diffusion coefficients to be obtained in a simple fashion. This new methodology can be used as a robust way to compare and characterize mAb therapeutics.

  14. Ocean acidification and viral replication cycles: Frequency of lytically infected and lysogenic cells during a mesocosm experiment in the NW Mediterranean Sea

    Science.gov (United States)

    Tsiola, Anastasia; Pitta, Paraskevi; Giannakourou, Antonia; Bourdin, Guillaume; Marro, Sophie; Maugendre, Laure; Pedrotti, Maria Luiza; Gazeau, Frédéric

    2017-02-01

    The frequency of lytically infected and lysogenic cells (FLIC and FLC, respectively) was estimated during an in situ mesocosm experiment studying the impact of ocean acidification on the plankton community of a low nutrient low chlorophyll (LNLC) system in the north-western Mediterranean Sea (Bay of Villefranche, France) in February/March 2013. No direct effect of elevated partial pressure of CO2 (pCO2) on viral replication cycles could be detected. FLC variability was negatively correlated to heterotrophic bacterial and net community production as well as the ambient bacterial abundance, confirming that lysogeny is a prevailing life strategy under unfavourable-for-the-hosts conditions. Further, the phytoplankton community, assessed by chlorophyll a concentration and the release of >0.4 μm transparent exopolymeric particles, was correlated with the occurrence of lysogeny, indicating a possible link between photosynthetic processes and bacterial growth. Higher FLC was found occasionally at the highest pCO2-treated mesocosm in parallel to subtle differences in the phytoplankton community. This observation suggests that elevated pCO2 could lead to short-term alterations in lysogenic dynamics coupled to phytoplankton-derived processes. Correlation of FLIC with any environmental parameter could have been obscured by the sampling time or the synchronization of lysis to microbial processes not assessed in this experiment. Furthermore, alterations in microbial and viral assemblage composition and gene expression could be a confounding factor. Viral-induced modifications in organic matter flow affect bacterial growth and could interact with ocean acidification with unpredictable ecological consequences.

  15. An overview of the lightning and atmospheric electricity observations collected in Southern France during the HYdrological cycle in Mediterranean EXperiment (HyMeX, Special Observation Period 1

    Directory of Open Access Journals (Sweden)

    E. Defer

    2014-08-01

    Full Text Available The PEACH (Projet en Electricité Atmosphérique pour la Campagne HyMeX – the Atmospheric Electricity Project of HyMeX Program project is the Atmospheric Electricity component of the HyMeX (Hydrology cycle in the Mediterranean Experiment experiment and is dedicated to the observation of both lightning activity and electrical state of continental and maritime thunderstorms in the area of the Mediterranean Sea. During the HyMeX SOP1 (Special Observation Period; 5 September–6 November 2012, four European Operational Lightning Locating Systems (OLLSs (ATDNET, EUCLID, LINET, ZEUS and the HyMeX Lightning Mapping Array network (HyLMA were used to locate and characterize the lightning activity over the Southeastern Mediterranean at flash, storm and regional scales. Additional research instruments like slow antennas, video cameras, micro-barometer and microphone arrays were also operated. All these observations in conjunction with operational/research ground-based and airborne radars, rain gauges and in situ microphysical records aimed at characterizing and understanding electrically active and highly precipitating events over Southeastern France that often lead to severe flash floods. Simulations performed with Cloud Resolving Models like Meso-NH and WRF are used to interpret the results and to investigate further the links between dynamics, microphysics, electrification and lightning occurrence. A description of the different instruments deployed during the field campaign as well as the available datasets is given first. Examples of concurrent observations from radio frequency to acoustic for regular and atypical lightning flashes are then presented showing a rather comprehensive description of lightning flashes available from the SOP1 records. Then examples of storms recorded during HyMeX SOP1 over Southeastern France are briefly described to highlight the unique and rich dataset collected. Finally the next steps of the work required for the

  16. Complete {sup 1}H and {sup 13}C NMR structural assignments for a group of four goyazensolide-type furanoheliangolides

    Energy Technology Data Exchange (ETDEWEB)

    Soares, Ana Carolina Ferreira; Silva, Aline Nazare; Matos, Priscilla Mendonca; Silva, Eder Henrique da; Heleno, Vladimir Constantino Gomes [Universidade de Franca, Franca, SP (Brazil). Nucleo de Pesquisas em Ciencias Exatas e Tecnologicas; Lopes, Norberto Peporine; Lopes, Joao Luis Callegari [Universidade de Sao Paulo (FCFRP/USP), Ribeirao Preto, SP (Brazil). Fac. de Ciencias Farmaceuticas de Ribeirao Preto. Dept. de Quimica e Fisica; Sass, Daiane Cristina, E-mail: vheleno_05@yahoo.com.br [Universidade de Sao Paulo (FFCLRP/USP), Ribeirao Preto, SP (Brazil). Fac. de Filosofia, Ciencias e Letras de Ribeirao Preto. Dept. de Quimica

    2012-07-01

    Four goyazensolide-type sesquiterpene lactones - lychnofolide, centratherin, goyazensolide and goyazensolide acetate - were thoroughly studied by NMR experimental techniques. {sup 1}H NMR, {sup 13}C NMR {l_brace}{sup 1}H{r_brace}, COSY, HMQC, HMBC, J-res. and NOE experiments were performed to provide the needed structural information. Complete and unequivocal assignment, including the determination of all multiplicities, was obtained for each structure and the data collections are presented in tables (author)

  17. Rapid proton-detected NMR assignment for proteins with fast magic angle spinning.

    Science.gov (United States)

    Barbet-Massin, Emeline; Pell, Andrew J; Retel, Joren S; Andreas, Loren B; Jaudzems, Kristaps; Franks, W Trent; Nieuwkoop, Andrew J; Hiller, Matthias; Higman, Victoria; Guerry, Paul; Bertarello, Andrea; Knight, Michael J; Felletti, Michele; Le Marchand, Tanguy; Kotelovica, Svetlana; Akopjana, Inara; Tars, Kaspars; Stoppini, Monica; Bellotti, Vittorio; Bolognesi, Martino; Ricagno, Stefano; Chou, James J; Griffin, Robert G; Oschkinat, Hartmut; Lesage, Anne; Emsley, Lyndon; Herrmann, Torsten; Pintacuda, Guido

    2014-09-03

    Using a set of six (1)H-detected triple-resonance NMR experiments, we establish a method for sequence-specific backbone resonance assignment of magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of 5-30 kDa proteins. The approach relies on perdeuteration, amide (2)H/(1)H exchange, high magnetic fields, and high-spinning frequencies (ωr/2π ≥ 60 kHz) and yields high-quality NMR data, enabling the use of automated analysis. The method is validated with five examples of proteins in different condensed states, including two microcrystalline proteins, a sedimented virus capsid, and two membrane-embedded systems. In comparison to contemporary (13)C/(15)N-based methods, this approach facilitates and accelerates the MAS NMR assignment process, shortening the spectral acquisition times and enabling the use of unsupervised state-of-the-art computational data analysis protocols originally developed for solution NMR.

  18. Structural properties of carbon nanotubes derived from 13C NMR

    KAUST Repository

    Abou-Hamad, E.

    2011-10-10

    We present a detailed experimental and theoretical study on how structural properties of carbon nanotubes can be derived from 13C NMR investigations. Magic angle spinning solid state NMR experiments have been performed on single- and multiwalled carbon nanotubes with diameters in the range from 0.7 to 100 nm and with number of walls from 1 to 90. We provide models on how diameter and the number of nanotube walls influence NMR linewidth and line position. Both models are supported by theoretical calculations. Increasing the diameter D, from the smallest investigated nanotube, which in our study corresponds to the inner nanotube of a double-walled tube to the largest studied diameter, corresponding to large multiwalled nanotubes, leads to a 23.5 ppm diamagnetic shift of the isotropic NMR line position δ. We show that the isotropic line follows the relation δ = 18.3/D + 102.5 ppm, where D is the diameter of the tube and NMR line position δ is relative to tetramethylsilane. The relation asymptotically tends to approach the line position expected in graphene. A characteristic broadening of the line shape is observed with the increasing number of walls. This feature can be rationalized by an isotropic shift distribution originating from different diamagnetic shielding of the encapsulated nanotubes together with a heterogeneity of the samples. Based on our results, NMR is shown to be a nondestructive spectroscopic method that can be used as a complementary method to, for example, transmission electron microscopy to obtain structural information for carbon nanotubes, especially bulk samples.

  19. RECENT PROGRESS IN BIOMOLECULAR NMR

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    @@ Structural genomics and proteomics were born from the understanding that functions of a protein are dictated by its 3D structure and dynamics. To understand protein functions on a genomic scale, we must know protein structures on a genomic scale. High resolution NMR can be used for this purpose. Traditional multidimensional NMR structure determination protocols become ineffective for structural genomics since to obtain a structure of a small protein of 15kD requires many months of painstaking spectral analysis and modeling. Recent advances in magnet and probe technology and in experimental methods have expanded the range of proteins amenable to structure determination and make the large scale structure determination possible. These advances are (1) effective expression systems for protein production, (2) introduction of cryoprobe, (3) structure determination with the use of the minimal amount of structural restraints obtained from the chemical shifts, residual dipolar couplings, NOEs, and computer modeling. In this talk,Iwill briefly outline these developments and related works done in our NMR lab.

  20. NMR-Based Milk Metabolomics

    Directory of Open Access Journals (Sweden)

    Hanne C. Bertram

    2013-04-01

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

  1. Hyperpolarized 131Xe NMR spectroscopy

    Science.gov (United States)

    Stupic, Karl F.; Cleveland, Zackary I.; Pavlovskaya, Galina E.; Meersmann, Thomas

    2011-01-01

    Hyperpolarized (hp) 131Xe with up to 2.2% spin polarization (i.e., 5000-fold signal enhancement at 9.4 T) was obtained after separation from the rubidium vapor of the spin-exchange optical pumping (SEOP) process. The SEOP was applied for several minutes in a stopped-flow mode, and the fast, quadrupolar-driven T1 relaxation of this spin I = 3/2 noble gas isotope required a rapid subsequent rubidium removal and swift transfer into the high magnetic field region for NMR detection. Because of the xenon density dependent 131Xe quadrupolar relaxation in the gas phase, the SEOP polarization build-up exhibits an even more pronounced dependence on xenon partial pressure than that observed in 129Xe SEOP. 131Xe is the only stable noble gas isotope with a positive gyromagnetic ratio and shows therefore a different relative phase between hp signal and thermal signal compared to all other noble gases. The gas phase 131Xe NMR spectrum displays a surface and magnetic field dependent quadrupolar splitting that was found to have additional gas pressure and gas composition dependence. The splitting was reduced by the presence of water vapor that presumably influences xenon-surface interactions. The hp 131Xe spectrum shows differential line broadening, suggesting the presence of strong adsorption sites. Beyond hp 131Xe NMR spectroscopy studies, a general equation for the high temperature, thermal spin polarization, P, for spin I⩾1/2 nuclei is presented.

  2. Experimental implementation of a NMR entanglement witness

    CERN Document Server

    Filgueiras, J G; Auccaise, R E; Vianna, R O; Sarthour, R S; Oliveira, I S

    2012-01-01

    Entanglement witnesses (EW) allow the detection of entanglement in a quantum system, from the measurement of some few observables. They do not require the complete determination of the quantum state, which is regarded as a main advantage. On this paper it is experimentally analyzed an entanglement witness recently proposed in the context of Nuclear Magnetic Resonance (NMR) experiments to test it in some Bell-diagonal states. We also propose some optimal entanglement witness for Bell-diagonal states. The efficiency of the two types of EW's are compared to a measure of entanglement with tomographic cost, the generalized robustness of entanglement. It is used a GRAPE algorithm to produce an entangled state which is out of the detection region of the EW for Bell-diagonal states. Upon relaxation, the results show that there is a region in which both EW fails, whereas the generalized robustness still shows entanglement, but with the entanglement witness proposed here with a better performance.

  3. Solid state NMR of sulfa-drugs

    CERN Document Server

    Portieri, A

    2001-01-01

    deducted. Exact positions of the hydrogen has proved to be essential as well in order to improve the calculations. Finally a case study for the REDOR pulse sequence has been carried out. Different attempts to understand the effects influencing this particular experiment have been carried out on 20% and 99% doubly enriched glycine, as well as on a particular sample, doubly enriched BRL55834, but the internuclear distances measured with this technique still displayed some uncertainties that made results not thoroughly reliable. This work has been a study of systems, mostly of sulfa-drugs, showing polymorphic behaviour. Using different means as solid state NMR, X-ray analysis, * and theoretical calculations, we have seen how it is possible to understand results obtained from the different techniques, proving how the study of polymorphic systems needs cooperative advice from the different techniques that are able to detect polymorphic differences. Within the sulfa-drugs I have been mostly concentrating on sulfani...

  4. Establishing resolution-improved NMR spectroscopy in high magnetic fields with unknown spatiotemporal variations

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhiyong; Cai, Shuhui; Zheng, Zhenyao; Lin, Yulan, E-mail: chenz@xmu.edu.cn, E-mail: lylfj2005@xmu.edu.cn; Chen, Zhong, E-mail: chenz@xmu.edu.cn, E-mail: lylfj2005@xmu.edu.cn [Department of Electronic Science, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen (China); Smith, Pieter E. S. [Chemical Physics Department, Weizmann Institute of Science, Rehovot (Israel)

    2015-12-28

    A half-century quest for higher magnetic fields has been an integral part of the progress undergone in the Nuclear Magnetic Resonance (NMR) study of materials’ structure and dynamics. Because 2D NMR relies on systematic changes in coherences’ phases as a function of an encoding time varied over a series of independent experiments, it generally cannot be applied in temporally unstable fields. This precludes most NMR methods from being used to characterize samples situated in hybrid or resistive magnets that are capable of achieving extremely high magnetic field strength. Recently, “ultrafast” NMR has been developed into an effective and widely applicable methodology enabling the acquisition of a multidimensional NMR spectrum in a single scan; it can therefore be used to partially mitigate the effects of temporally varying magnetic fields. Nevertheless, the strong interference of fluctuating fields with the spatial encoding of ultrafast NMR still severely restricts measurement sensitivity and resolution. Here, we introduce a strategy for obtaining high resolution NMR spectra that exploits the immunity of intermolecular zero-quantum coherences (iZQCs) to field instabilities and inhomogeneities. The spatial encoding of iZQCs is combined with a J-modulated detection scheme that removes the influence of arbitrary field inhomogeneities during acquisition. This new method can acquire high-resolution one-dimensional NMR spectra in large inhomogeneous and fluctuating fields, and it is tested with fields experimentally modeled to mimic those of resistive and resistive-superconducting hybrid magnets.

  5. FES cycling.

    Science.gov (United States)

    Newham, D J; Donaldson, N de N

    2007-01-01

    Spinal cord injury (SCI) leads to a partial or complete disruption of motor, sensory, and autonomic nerve pathways below the level of the lesion. In paraplegic patients, functional electrical stimulation (FES) was originally widely considered as a means to restore walking function but this was proved technically very difficult because of the numerous degrees of freedom involved in walking. FES cycling was developed for people with SCI and has the advantages that cycling can be maintained for reasonably long periods in trained muscles and the risk of falls is low. In the article, we review research findings relevant to the successful application of FES cycling including the effects on muscle size, strength and function, and the cardiovascular and bone changes. We also describe important practical considerations in FES cycling regarding the application of surface electrodes, training and setting up the stimulator limitations, implanted stimulators and FES cycling including FES cycling in groups and other FES exercises such as FES rowing.

  6. Structural analysis of N,N-diacyl-1,4-dihydropyrazine by variable-temperature NMR and DFT calculation

    Science.gov (United States)

    Song, Xiu-qing; Tan, Hong-bo; Yan, Hong; Chang, Yu

    2017-04-01

    N,N-diacyl-1,4-dihydropyrazine derivatives (1) were prepared via an efficient microwave-assisted synthesis. 1 was isolated and unambiguously confirmed by NMR spectra and high-resolution mass spectrometry. The NMR spectra of 1 showed complicated rather than conventional spectroscopy. Variable-temperature experiments and DFT calculation (PES) were used to investigate this phenomenon. DFT calculations confirmed that the structures of the two rotamers of 1 correspond to those determined by NMR in solution, and gave the syn-anti interconversion barriers of rotamers. The results showed that two isomers exist in solution (deuterated solvent) at room temperature, resulting in complicated NMR spectra.

  7. $^{31}$Mg $\\beta$-NMR applied in chemistry and biochemistry

    CERN Multimedia

    Magnesium ions, Mg$^{2+}$, are essential in biological systems, taking part in practically all phosphate chemistry, in photosynthesis as an integral component of chlorophyll, and they are regulated via transport through selective membrane proteins. Nonetheless, the function of magnesium ions in biochemistry is difficult to characterize, as it is practically invisible to current experimental techniques. With this proposal we aim to advance the use of $^{31}$Mg $\\beta$-NMR to liquid samples, building on the experience from the successful Letter of Intent INTC-I-088 “$\\beta$-NMR as a novel technique for biological applications”. Initially a series of experiments will be conducted aiming to characterize the coordination chemistry of Mg$^{2+}$ in ionic liquids (ILs), demonstrating that it is possible within the lifetime of the radioisotope to achieve binding of Mg$^{2+}$ to a molecule dissolved in the IL. ILs are chosen as they display a very low vapor pressure, and are thus straightforwardly compatible with t...

  8. Dynamic pulsed-field-gradient NMR

    CERN Document Server

    Sørland, Geir Humborstad

    2014-01-01

    Dealing with the basics, theory and applications of dynamic pulsed-field-gradient NMR NMR (PFG NMR), this book describes the essential theory behind diffusion in heterogeneous media that can be combined with NMR measurements to extract important information of the system being investigated. This information could be the surface to volume ratio, droplet size distribution in emulsions, brine profiles, fat content in food stuff, permeability/connectivity in porous materials and medical applications currently being developed. Besides theory and applications it will provide the readers with background knowledge on the experimental set-ups, and most important, deal with the pitfalls that are numerously present in work with PFG-NMR. How to analyze the NMR data and some important basic knowledge on the hardware will be explained, too.

  9. Desktop NMR for structure elucidation and identification of strychnine adulteration.

    Science.gov (United States)

    Singh, Kawarpal; Blümich, Bernhard

    2017-05-02

    Elucidating the structure of complex molecules is difficult at low magnetic fields due to the overlap of different peak multiplets and second-order coupling effects. This is even more challenging for rigid molecules with small chemical shift differences and with prochiral centers. Since low-field NMR spectroscopy is sometimes presumed as restricted to the analysis of only small and simple molecules, this paper aims at countering this misconception: it demonstrates the use of low-field NMR spectroscopy in chemical forensics for identifying strychnine and its counterions by exploring the chemical shift as a signature in different 1D (1)H and (13)C experiments. Hereby the applied methodologies combine various 1D and 2D experiments such as 1D (1)H, (13)C, DEPT, and 2D COSY, HETCOR, HSQC, HMBC and J-resolved spectroscopy to elucidate the molecular structure and skeleton of strychnine at 1 Tesla. Strychnine is exemplified here, because it is a basic precursor in the chemistry of natural products and is employed as a chemical weapon and as a doping agent in sports including the Olympics. In our study, the molecular structure of the compound could be identified either with a 1D experiment at high magnetic field or with HMBC and HSQC experiments at 1 T. In conclusion, low-field NMR spectroscopy enables the chemical elucidation of the strychnine structure through a simple click with a computer mouse. In situations where a high-field NMR spectrometer is unavailable, compact NMR spectrometers can nevertheless generate knowledge of the structure, important for identifying the different chemical reaction mechanisms associated with the molecule. Desktop NMR is a cost-effective viable option in chemical forensics. It can prove adulteration and identify the origin of different strychnine salts, in particular, the strychnine free base, strychnine hemisulphate and strychnine hydrochloride. The chemical shift signatures report the chemical structure of the molecules due to the impact

  10. Ultra-low-field NMR relaxation and diffusion measurements using an optical magnetometer.

    Science.gov (United States)

    Ganssle, Paul J; Shin, Hyun D; Seltzer, Scott J; Bajaj, Vikram S; Ledbetter, Micah P; Budker, Dmitry; Knappe, Svenja; Kitching, John; Pines, Alexander

    2014-09-08

    Nuclear magnetic resonance (NMR) relaxometry and diffusometry are important tools for the characterization of heterogeneous materials and porous media, with applications including medical imaging, food characterization and oil-well logging. These methods can be extremely effective in applications where high-resolution NMR is either unnecessary, impractical, or both, as is the case in the emerging field of portable chemical characterization. Here, we present a proof-of-concept experiment demonstrating the use of high-sensitivity optical magnetometers as detectors for ultra-low-field NMR relaxation and diffusion measurements.

  11. Solution conformation of carbohydrates: a view by using NMR assisted by modeling.

    Science.gov (United States)

    Díaz, Dolores; Canales-Mayordomo, Angeles; Cañada, F Javier; Jiménez-Barbero, Jesús

    2015-01-01

    Structural elucidation of complex carbohydrates in solution is not a trivial task. From the NMR view point, the limited chemical shift dispersion of sugar NMR spectra demands the combination of a variety of NMR techniques as well as the employment of molecular modeling methods. Herein, a general protocol for assignment of resonances and determination of inter-proton distances within the saccharides by homonuclear and heteronuclear experiments (i.e., (1)H and (13)C) is described. In addition, several computational tools and procedures for getting a final ensemble of geometries that represent the structure in solution are presented.

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

    Science.gov (United States)

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

    2016-09-01

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

  13. In situ High-pressure NMR Observations on the Formation and Dissociation of Methane Hydrate

    Institute of Scientific and Technical Information of China (English)

    Ai Bing CHEN; Wei Ping ZHANG; Xi Jie LAN; Heng ZHENG; Xiu Mei LIU; Xiu Wen HAN; Xin He BAO

    2006-01-01

    A home-made static NMR cell with pressure up to 10 MPa was employed to observe the formation and dissociation processes of methane hydrate by in situ 1H and 13C NMR spectroscopies. Methane hydrate can be formed or decomposed in the temperature range of -5 to-13℃ at pressures between 4.0 and 7.0 MPa. The higher methane pressure, the formation or dissociation temperature of methane hydrate was higher. In situ 1H NMR experiments indicated that the critical size of the hydrate clusters is crucial for the formation of methane hydrate.

  14. Size-exclusion chromatographic NMR under HR-MAS

    OpenAIRE

    Lucena Alcalde, Guillermo; Anderson, Natalie; Day, Iain J.

    2016-01-01

    The addition of stationary phases or sample modifiers can be used to modify the separation achievable in the diffusion domain of diffusion NMR experiments or provide information on the nature of the analyte–sample modifier interaction. Unfortunately, the addition of insoluble chromatographic stationary phases can lead to line broadening and degradation in spectral resolution, largely because of differences in magnetic susceptibility between the sample and the stationary phase. High-resolution...

  15. 3D Reconstruction of NMR Images by LabVIEW

    Directory of Open Access Journals (Sweden)

    Peter IZAK

    2007-01-01

    Full Text Available This paper introduces the experiment of 3D reconstruction NMR images via virtual instrumentation - LabVIEW. The main idea is based on marching cubes algorithm and image processing implemented by module of Vision assistant. The two dimensional images shot by the magnetic resonance device provide information about the surface properties of human body. There is implemented algorithm which can be used for 3D reconstruction of magnetic resonance images in biomedical application.

  16. NMR experimental implementation of three-parties quantum superdense coding

    Institute of Scientific and Technical Information of China (English)

    WEI Daxiu; YANG Xiaodong; LUO Jun; SUN Xianping; ZENG Xizhi; LIU Maili

    2004-01-01

    In this study, we report an experiment realization of quantum superdense coding (QSDC) between three parties using nuclear magnetic resonance (NMR). The experimental results have shown that in terms of the QSDC schemes between multiparties proposed by Liu et al. and Crudka et al., three-qubit QSDC can transmit three bits of classical information by sending two qubits only. Our results experimentally show that quantum superdense coding, as one of the quantum information processing protocols, is superior to classical ones.

  17. Applications of NMR in Dairy Research

    Directory of Open Access Journals (Sweden)

    Anthony D. Maher

    2014-03-01

    Full Text Available NMR is a robust analytical technique that has been employed to investigate the properties of many substances of agricultural relevance. NMR was first used to investigate the properties of milk in the 1950s and has since been employed in a wide range of studies; including properties analysis of specific milk proteins to metabolomics techniques used to monitor the health of dairy cows. In this brief review, we highlight the different uses of NMR in the dairy industry.

  18. NMR spectroscopy using liquid crystal solvents

    CERN Document Server

    Emsley, JW

    2013-01-01

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

  19. NMR studies of isotopically labeled RNA

    Energy Technology Data Exchange (ETDEWEB)

    Pardi, A. [Univ. of Colorado, Boulder, CO (United States)

    1994-12-01

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

  20. NMR exposure sensitizes tumor cells to apoptosis.

    Science.gov (United States)

    Ghibelli, L; Cerella, C; Cordisco, S; Clavarino, G; Marazzi, S; De Nicola, M; Nuccitelli, S; D'Alessio, M; Magrini, A; Bergamaschi, A; Guerrisi, V; Porfiri, L M

    2006-03-01

    NMR technology has dramatically contributed to the revolution of image diagnostic. NMR apparatuses use combinations of microwaves over a homogeneous strong (1 Tesla) static magnetic field. We had previously shown that low intensity (0.3-66 mT) static magnetic fields deeply affect apoptosis in a Ca2+ dependent fashion (Fanelli et al., 1999 FASEBJ., 13;95-102). The rationale of the present study is to examine whether exposure to the static magnetic fields of NMR can affect apoptosis induced on reporter tumor cells of haematopoietic origin. The impressive result was the strong increase (1.8-2.5 fold) of damage-induced apoptosis by NMR. This potentiation is due to cytosolic Ca2+ overload consequent to NMR-promoted Ca2+ influx, since it is prevented by intracellular (BAPTA-AM) and extracellular (EGTA) Ca2+ chelation or by inhibition of plasma membrane L-type Ca2+ channels. Three-days follow up of treated cultures shows that NMR decrease long term cell survival, thus increasing the efficiency of cytocidal treatments. Importantly, mononuclear white blood cells are not sensitised to apoptosis by NMR, showing that NMR may increase the differential cytotoxicity of antitumor drugs on tumor vs normal cells. This strong, differential potentiating effect of NMR on tumor cell apoptosis may have important implications, being in fact a possible adjuvant for antitumor therapies.

  1. Spin-Exchange Pumped NMR Gyros

    CERN Document Server

    Walker, Thad G

    2016-01-01

    We present the basic theory governing spin-exchange pumped NMR gyros. We review the basic physics of spin-exchange collisions and relaxation as they pertain to precision NMR. We present a simple model of operation as an NMR oscillator and use it to analyze the dynamic response and noise properties of the oscillator. We discuss the primary systematic errors (differential alkali fields, quadrupole shifts, and offset drifts) that limit the bias stability, and discuss methods to minimize them. We give with a brief overview of a practical implementation and performance of an NMR gyro built by Northrop-Grumman Corporation, and conclude with some comments about future prospects.

  2. Solid-state NMR and Membrane Proteins

    Science.gov (United States)

    Opella, Stanley J.

    2015-01-01

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

  3. NMR studies of field induced magnetism in CeCoIn5

    Energy Technology Data Exchange (ETDEWEB)

    Graf, Matthias [Los Alamos National Laboratory; Curro, Nicholas J [UC/DAVIS; Young, Ben - Li [NATIONAL CHIAO TUNG UNIV; Urbano, Ricardo R [FLORIDA STATE UNIV

    2009-01-01

    Recent Nuclear Magnetic Resonance and elastic neutron scattering experiments have revealed conclusively the presence of static incommensurate magnetism in the field-induced B phase of CeCoIns, We analyze the NMR data assuming the hyperfine coupling to the 1n(2) nuclei is anisotropic and simulate the spectra for several different magnetic structures, The NMR data are consistent with ordered Ce moments along the [001] direction, but are relatively insensitive to the direction of the incommensurate wavevector.

  4. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    KAUST Repository

    Falivene, Laura

    2016-12-26

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise surprising experimental results. In this review, the main conclusions from recent literature are discussed, with the aim to offer a vision of the potential of theoretical analyses of NMR properties.

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

    Science.gov (United States)

    Mills, Nancy S.; Shanklin, Michael

    2011-01-01

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

  6. Enzyme dynamics from NMR spectroscopy.

    Science.gov (United States)

    Palmer, Arthur G

    2015-02-17

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

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

    Science.gov (United States)

    Jankuru Hennadige, Sohan Roshel De Silva

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

  8. UTOPIA NMR: activating unexploited magnetization using interleaved low-gamma detection

    Energy Technology Data Exchange (ETDEWEB)

    Viegas, Aldino; Viennet, Thibault [Heinrich-Heine-University, Institute of Physical Biology (Germany); Yu, Tsyr-Yan [Academia Sinica, Institute of Atomic and Molecular Sciences (China); Schumann, Frank [Bruker BioSpin GmbH (Switzerland); Bermel, Wolfgang [Bruker BioSpin GmbH (Germany); Wagner, Gerhard [Harvard Medical School, Department of Biological Chemistry and Molecular Pharmacology (United States); Etzkorn, Manuel, E-mail: manuel.etzkorn@hhu.de [Heinrich-Heine-University, Institute of Physical Biology (Germany)

    2016-01-15

    A growing number of nuclear magnetic resonance (NMR) spectroscopic studies are impaired by the limited information content provided by the standard set of experiments conventionally recorded. This is particularly true for studies of challenging biological systems including large, unstructured, membrane-embedded and/or paramagnetic proteins. Here we introduce the concept of unified time-optimized interleaved acquisition NMR (UTOPIA-NMR) for the unified acquisition of standard high-γ (e.g. {sup 1}H) and low-γ (e.g. {sup 13}C) detected experiments using a single receiver. Our aim is to activate the high level of polarization and information content distributed on low-γ nuclei without disturbing conventional magnetization transfer pathways. We show that using UTOPIA-NMR we are able to recover nearly all of the normally non-used magnetization without disturbing the standard experiments. In other words, additional spectra, that can significantly increase the NMR insights, are obtained for free. While we anticipate a broad range of possible applications we demonstrate for the soluble protein Bcl-x{sub L} (ca. 21 kDa) and for OmpX in nanodiscs (ca. 160 kDa) that UTOPIA-NMR is particularly useful for challenging protein systems including perdeuterated (membrane) proteins.

  9. UTOPIA NMR: activating unexploited magnetization using interleaved low-gamma detection.

    Science.gov (United States)

    Viegas, Aldino; Viennet, Thibault; Yu, Tsyr-Yan; Schumann, Frank; Bermel, Wolfgang; Wagner, Gerhard; Etzkorn, Manuel

    2016-01-01

    A growing number of nuclear magnetic resonance (NMR) spectroscopic studies are impaired by the limited information content provided by the standard set of experiments conventionally recorded. This is particularly true for studies of challenging biological systems including large, unstructured, membrane-embedded and/or paramagnetic proteins. Here we introduce the concept of unified time-optimized interleaved acquisition NMR (UTOPIA-NMR) for the unified acquisition of standard high-γ (e.g. (1)H) and low-γ (e.g. (13)C) detected experiments using a single receiver. Our aim is to activate the high level of polarization and information content distributed on low-γ nuclei without disturbing conventional magnetization transfer pathways. We show that using UTOPIA-NMR we are able to recover nearly all of the normally non-used magnetization without disturbing the standard experiments. In other words, additional spectra, that can significantly increase the NMR insights, are obtained for free. While we anticipate a broad range of possible applications we demonstrate for the soluble protein Bcl-xL (ca. 21 kDa) and for OmpX in nanodiscs (ca. 160 kDa) that UTOPIA-NMR is particularly useful for challenging protein systems including perdeuterated (membrane) proteins.

  10. Comparison of "sandwich chemo-radiotherapy" and six cycles of chemotherapy followed by adjuvant radiotherapy in patients with stage IIIC endometrial cancer: a single center experience.

    Science.gov (United States)

    Dogan, Nasuh Utku; Yavas, Guler; Yavas, Cagdas; Ata, Ozlem; Yılmaz, Setenay Arzu; Celik, Cetin

    2013-10-01

    To compare "sandwich chemo-radiotherapy" with six cycles of chemotherapy followed by adjuvant radiotherapy with respect to tolerability and acute toxicity. Twenty-five women with surgically staged IIIC endometrial cancer were included. Treatment consisted of either three cycles of paclitaxel (175 mg/m²) and carboplatin (AUC 6) on a q21-day schedule followed by irradiation (45-50.4 Gy) or six cycles of the same chemotherapy followed by radiotherapy. Acute toxicity related to either chemotherapy or radiotherapy was evaluated. Median age was 61.5 years (range 36-83 years). Eleven patients had sandwich chemo-radiotherapy, and the other 14 patients had 6 cycles of chemotherapy followed by radiotherapy. Three out of the five patients who could not complete all the cycles in the sandwich chemo-radiotherapy group had pelvic and para-aortic radiotherapy. Acute radiotherapy related grade 1-2 gastrointestinal system (GIS) and genitourinary system (GUS) toxicities were observed in 72.8 and 63.6 % of patients, respectively, for sandwich group. Undesired treatment breaks in the course of radiotherapy were observed in six patients for sandwich chemo-radiotherapy and in one patient receiving six cycles of chemotherapy followed by radiotherapy. All the patients who had undesired treatment breaks in the sandwich chemo-radiotherapy group had pelvic and para-aortic radiotherapy. Sandwich chemo-radiotherapy seems to be more toxic particularly for patients who had pelvic and para-aortic irradiation. Therefore, it might be more convenient to delay radiotherapy after six cycles of chemotherapy for patients with the indication of pelvic para-aortic radiotherapy.

  11. The characterization of NMR signal for blood pressure monitoring system and its testing

    Directory of Open Access Journals (Sweden)

    Bambang Murdaka Eka Jati

    2016-02-01

    Full Text Available ABSTRACT A blood monitoring system based on NMR method has been designed on constructed. This set-up of equipment used magnetic permanent, radio frequency (RF, receiver coil (RC, function generator (FG, amplifier which included the filter, as well as the oscilloscope digital storage. The background of this research was based on the sensitivity of NMR signal. The signal must be separated from signals background. This method was done by adjusting the frequency on FG, which was connected to radio frequency (RF coil, on empty sample. Subsequently, NMR signal was received by RC, and that signal could be shown on oscilloscope at resonance condition. The true frequency on NMR signal was Larmor frequency, and the other was background. The two variables of this experiment were the position of RF coil and the location temperature (20 up to 30oC. In conclusion, the resonance frequency of NMR signal (as Larmor frequency was 4.7 MHz (at static magnetic field of 1,600 gauss and it could be separated from background signals (3.4 and 6.2 MHz, and that signal was almost constant to room temperature. The equipment was used for sample testing. It gave systole/diastole data of 110/70 mmHg (on sphygmomanometer that was similar to 17/9 mV (on NMR signal. ABSTRAK Telah dikembangkan alat pemantauan tekanan darah berdasar prinsip NMR.

  12. Cryogenic sample exchange NMR probe for magic angle spinning dynamic nuclear polarization

    Science.gov (United States)

    Barnes, Alexander B.; Mak-Jurkauskas, Melody L.; Matsuki, Yoh; Bajaj, Vikram S.; van der Wel, Patrick C. A.; DeRocher, Ronald; Bryant, Jeffrey; Sirigiri, Jagadishwar R.; Temkin, Richard J.; Lugtenburg, Johan; Herzfeld, Judith; Griffin, Robert G.

    2009-01-01

    We describe a cryogenic sample exchange system that dramatically improves the efficiency of magic angle spinning (MAS) dynamic nuclear polarization (DNP) experiments by reducing the time required to change samples and by improving long-term instrument stability. Changing samples in conventional cryogenic MAS DNP/NMR experiments involves warming the probe to room temperature, detaching all cryogenic, RF, and microwave connections, removing the probe from the magnet, replacing the sample, and reversing all the previous steps, with the entire cycle requiring a few hours. The sample exchange system described here — which relies on an eject pipe attached to the front of the MAS stator and a vacuum jacketed dewar with a bellowed hole — circumvents these procedures. To demonstrate the excellent sensitivity, resolution, and stability achieved with this quadruple resonance sample exchange probe, we have performed high precision distance measurements on the active site of the membrane protein bacteriorhodopsin. We also include a spectrum of the tripeptide N-f-MLF-OH at 100 K which shows 30 Hz linewidths. PMID:19356957

  13. NMR Spectroscopy and Its Value: A Primer

    Science.gov (United States)

    Veeraraghavan, Sudha

    2008-01-01

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

  14. Using Cloud Storage for NMR Data Distribution

    Science.gov (United States)

    Soulsby, David

    2012-01-01

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

  15. Planar microcoil-based microfluidic NMR probes.

    NARCIS (Netherlands)

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

    2003-01-01

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

  16. Using Cloud Storage for NMR Data Distribution

    Science.gov (United States)

    Soulsby, David

    2012-01-01

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

  17. NMR Spectroscopy and Its Value: A Primer

    Science.gov (United States)

    Veeraraghavan, Sudha

    2008-01-01

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

  18. Planar microcoil-based microfluidic NMR probes.

    NARCIS (Netherlands)

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

    2003-01-01

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

  19. Fes cycling

    Directory of Open Access Journals (Sweden)

    Berkelmans Rik

    2008-01-01

    Full Text Available Many research with functional electrical stimulation (FES has been done to regain mobility and for health benefits. Better results have been reported for FES-cycling than for FES-walking. The majority of the subjects during such research are people with a spinal cord injury (SCI, cause they often lost skin sensation. Besides using surface stimulation also implanted stimulators can be used. This solves the skin sensation problem, but needs a surgery. Many physiological effects of FES-cycling has been reported, e.g., increase of muscles, better blood flow, reduction of pressure ulcers, improved self-image and some reduction of bone mineral density (BMD loss. Also people with an incomplete SCI benefit by FES-cycling, e.g. cycling time without FES, muscle strength and also the walking abilities increased. Hybrid exercise gives an even better cardiovascular training. Presently 4 companies are involved in FES-cycling. They all have a stationary mobility trainer. Two of them also use an outdoor tricycle. One combined with voluntary arm cranking. By optimizing the stimulation parameters the power output and fatigue resistance will increase, but will still be less compared to voluntary cycling.

  20. Rheo-NMR Measurements of Cocoa Butter Crystallized Under

    Energy Technology Data Exchange (ETDEWEB)

    Mudge, E.; Mazzanti, G

    2009-01-01

    Modifications of a benchtop NMR instrument were made to apply temperature control to a shearing NMR cell. This has enabled the determination in situ of the solid fat content (SFC) of cocoa butter under shearing conditions. The cocoa butter was cooled at 3 C/min to three final temperatures of 17.5, 20.0, and 22.5 C with applied shear rates between 45 and 720 s-1. Polymorphic transitions of the cocoa butter were determined using synchrotron X-ray diffraction with an identical shearing system constructed of Lexan. Sheared samples were shown to have accelerated phase transitions compared to static experiments. In experiments where form V was confirmed to be the dominant polymorph, the final SFC averaged around 50%. However, when other polymorphic forms were formed, a lower SFC was measured because the final temperature was within the melting range of that polymorph and only partial crystallization happened. A shear rate of 720 s-1 delayed phase transitions, likely due to viscous heating of the sample. Pulsed NMR is an invaluable tool for determining the crystalline fraction in hydrogen containing materials, yet its use for fundamental and industrial research on fat or alkanes crystallization under shear has only recently been developed.

  1. Tight-binding theory of NMR shifts in topological insulators

    Science.gov (United States)

    Garate, Ion; Boutin, Samuel; Ramirez Ruiz, Jorge

    To date, most experiments in topological insulators have focused on probing the surface states of these materials and suppressing the often inevitable contribution from bulk states. However, the latter are of interest on their own and contain useful information that can be extracted with a local probe like nuclear magnetic resonance (NMR). Recently, 77Se NMR experiments on Bi2Se3 single crystals have reported unusual field-independent linewidths and short spin-echo decays. It is likely that an unexpectedly strong indirect internuclear coupling, characteristic of some inverted band structures, is the cause of these peculiar results. Motivated by this hypothesis, we report on a microscopic theory of NMR shifts and linewidths in Bi2Se3 and Bi2Te3. Our theory provides quantitative estimates for the Knight shift, the orbital shift, the Ruderman-Kittel-Kasuya-Yoshida coupling and the Bloembergen-Rowland coupling. We will compare our findings with the available experimental data Funded by the National Science and Engineering Research Council of Canada, Fonds de Recherche Québécois Nature et Technologies, and Mitacs-Globalink.

  2. Challenges and perspectives in quantitative NMR.

    Science.gov (United States)

    Giraudeau, Patrick

    2017-01-01

    This perspective article summarizes, from the author's point of view at the beginning of 2016, the major challenges and perspectives in the field of quantitative NMR. The key concepts in quantitative NMR are first summarized; then, the most recent evolutions in terms of resolution and sensitivity are discussed, as well as some potential future research directions in this field. A particular focus is made on methodologies capable of boosting the resolution and sensitivity of quantitative NMR, which could open application perspectives in fields where the sample complexity and the analyte concentrations are particularly challenging. These include multi-dimensional quantitative NMR and hyperpolarization techniques such as para-hydrogen-induced polarization or dynamic nuclear polarization. Because quantitative NMR cannot be dissociated from the key concepts of analytical chemistry, i.e. trueness and precision, the methodological developments are systematically described together with their level of analytical performance. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  3. NMR and MRI apparatus and method

    Science.gov (United States)

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

    2007-03-06

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

  4. Carbon-13 NMR spectroscopy of biological systems

    CERN Document Server

    Beckmann, Nicolau

    1995-01-01

    This book is intended to provide an in-depth understanding of 13C NMR as a tool in biological research. 13C NMR has provided unique information concerning complex biological systems, from proteins and nucleic acids to animals and humans. The subjects addressed include multidimensional heteronuclear techniques for structural studies of molecules in the liquid and solid states, the investigation of interactions in model membranes, the elucidation of metabolic pathwaysin vitro and in vivo on animals, and noninvasive metabolic studies performed on humans. The book is a unique mix of NMR methods and biological applications which makes it a convenient reference for those interested in research in this interdisciplinary area of physics, chemistry, biology, and medicine.Key Features* An interdisciplinary text with emphasis on both 13C NMR methodology and the relevant biological and biomedical issues* State-of-the-art 13C NMR techniques are described; Whenever possible, their advantages over other approaches are empha...

  5. NMR-based milk metabolomics

    DEFF Research Database (Denmark)

    Sundekilde, Ulrik; Larsen, Lotte Bach; Bertram, Hanne Christine S.

    2013-01-01

    Milk is a key component in infant nutrition worldwide and, in the Western parts of the world, also in adult nutrition. Milk of bovine origin is both consumed fresh and processed into a variety of dairy products including cheese, fermented milk products, and infant formula. The nutritional quality...... and processing capabilities of bovine milk is closely associated to milk composition. Metabolomics is ideal in the study of the low-molecular-weight compounds in milk, and this review focuses on the recent nuclear magnetic resonance (NMR)-based metabolomics trends in milk research, including applications linking...... the milk metabolite profiling with nutritional aspects, and applications which aim to link the milk metabolite profile to various technological qualities of milk. The metabolite profiling studies encompass the identification of novel metabolites, which potentially can be used as biomarkers or as bioactive...

  6. Preprocessing of NMR metabolomics data.

    Science.gov (United States)

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

    2015-05-01

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

  7. Study of β-NMR for Liquid Biological Samples

    CERN Document Server

    Beattie, Caitlin

    2017-01-01

    β-NMR is an exotic form of NMR spectroscopy that allows for the characterization of matter based on the anisotropic β-decay of radioactive probe nuclei. This has been shown to be an effective spectroscopic technique for many different compounds, but its use for liquid biological samples is relatively unexplored. The work at the VITO line of ISOLDE seeks to employ this technique to study such samples. Currently, preparations are being made for an experiment to characterize DNA G-quadruplexes and their interactions with stabilizing cations. More specifically, the work in which I engaged as a summer student focused on the experiment’s liquid handling system and the stability of the relevant biological samples under vacuum.

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

    CERN Document Server

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

    2001-01-01

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

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

    Science.gov (United States)

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

    2010-12-16

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

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

    Science.gov (United States)

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

    2017-06-01

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

  11. Transabdominal follicular aspiration in an in vitro fertilization cycle: experiences with an unusual but necessary intervention in a resource-limited setting.

    Science.gov (United States)

    Osemwenkha, Abieyuwa; Osaikhuwuomwan, James

    2016-03-01

    Controlled ovarian hyperstimulation is one of the major steps of in vitro fertilization. The inaccessibility or non-visualization of developing follicles on transvaginal sonography (the preferred imaging method) may be misjudged as a poor response, resulting in cycle cancellation. It is necessary to scrupulously appraise proxy indicators for ovarian response, such as estradiol levels, endometrial thickness, and other individual clinical characteristics. This can prompt meticulous transabdominal ultrasound follicular monitoring and oocyte retrieval with the goal of averting cycle cancellation and improving treatment outcomes.

  12. Solid state NMR and pair distribution function studies of silicon electrodes for lithium-ion batteries

    Science.gov (United States)

    Key, Baris

    The universally used negative electrode material in a LIB is carbon, because of its moderate capacity (372 mAhg-1 for graphite), cyclability and high rate capability. However, new, low cost, safe electrode materials with higher capacities are still urgently required for both portable and transportation applications. Silicon anodes are particularly attractive alternatives to carbon with extremely high gravimetric energy densities (3572 mAhg-1). Compared to graphite, silicon has a massive volumetric capacity of 8322 mAhcm-3 (calculated based on the original volume of silicon) which is approximately ten times that graphite. At room temperature, upon electrochemical lithiation, silicon undergoes a crystalline to amorphous phase transition forming a lithiated amorphous silicide phase. Unfortunately, due to the amorphous nature of the lithiated silicides, it is not possible to monitor all the structural changes that occur during lithium insertion/removal with conventional methods such as diffraction. The short range order of the amorphous materials remains unknown, preventing attempts to optimize performance based on electrochemical-structure correlations. In this work, a combination of local structure probes, ex-situ 7Li nuclear magnetic resonance (NMR) studies and pair distribution function (PDF) analysis of X-ray data was applied to investigate the changes in short range order that occur during the initial charge and discharge cycles. The distinct electrochemical profiles observed subsequent to the 1 st discharge have been shown to be associated with the formation of distinct amorphous lithiated silicide structures. A (de)lithiation model consisting of four different mechanisms, each being valid for regions of the charge or discharge process is proposed to explain the hysteresis and the steps in the electrochemical profile observed during lithiation and delithiation of Si. A spontaneous reaction of the fully lithiated lithium silicide with the electrolyte is directly

  13. Single NMR image super-resolution based on extreme learning machine.

    Science.gov (United States)

    Wang, Zhiqiong; Xin, Junchang; Wang, Zhongyang; Tian, Shuo; Qiu, Xuejun

    2016-10-01

    The performance limitation of MRI equipment and higher resolution demand of NMR images from radiologists have formed a strong contrast. Therefore, it is important to study the super resolution algorithm suitable for NMR images, using low costs software to replace the expensive equipment-updating. Firstly, a series of NMR images are obtained from original NMR images with original noise to the lowest resolution images with the highest noise. Then, based on extreme learning machine, the mapping relation model is constructed from lower resolution NMR images with higher noise to higher resolution NMR images with lower noise in each pair of adjacent images in the obtained image sequence. Finally, the optimal mapping model is established by the ensemble way to reconstruct the higher resolution NMR images with lower noise on the basis of original resolution NMR images with original noise. Experiments are carried out by 990111 NMR brain images in datasets NITRC, REMBRANDT, RIDER NEURO MRI, TCGA-GBM and TCGA-LGG. The performance of proposed method is compared with three approaches through 7 indexes, and the experimental results show that our proposed method has a significant improvement. Since our method considers the influence of the noise, it has 20% higher in Peak-Signal-to-Noise-Ratio comparison. As our method is sensitive to details, and has a better characteristic retention, it has higher image quality upgrade of 15% in the additional evaluation. Finally, since extreme learning machine has a celerity learning speed, our method is 46.1% faster. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2016-09-21

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

  15. Automated Fragmentation Polarizable Embedding Density Functional Theory (PE-DFT) Calculations of Nuclear Magnetic Resonance (NMR) Shielding Constants of Proteins with Application to Chemical Shift Predictions

    DEFF Research Database (Denmark)

    Svendsen, Casper Steinmann; Bratholm, L.A.; Olsen, Jógvan Magnus Haugaard

    2017-01-01

    Full-protein nuclear magnetic resonance (NMR) shielding constants based on ab initio calculations are desirable, because they can assist in elucidating protein structures from NMR experiments. In this work, we present NMR shielding constants computed using a new automated fragmentation (J. Phys. ...... can obtain a representative subset of snapshots that gives the smallest predicted error, compared to experiment. Finally, we use this subset of snapshots to calculate the NMR shielding constants at the PE-KT3/pcSseg-2 level of theory for all atoms in the protein GB3....

  16. 31P NMR for the study of P metabolism and translocation in arbuscular mycorrhizal fungi

    DEFF Research Database (Denmark)

    Rasmussen, N.; Lloyd, D.C.; Ratcliffe, R.G.

    2000-01-01

    P-31 nuclear magnetic resonance (NMR) spectroscopy was used to study phosphate (P) metabolism in mycorrhizal and nonmycorrhizal roots of cucumber (Cucumis sativus L) and in external mycelium of the arbuscular mycorrhizal (AM) fungus Glomus intraradices Schenck & Smith. The in vivo NMR method allows...... biological systems to be studied non-invasively and non-destructively. (3)1P NMR experiments provide information about cytoplasmic and vacuolar pH, based on the pH-dependent chemical shifts of the signals arising from the inorganic P (P-i) located in the two compartments. Similarly, the resonances arising...... from alpha, beta and gamma phosphates of nucleoside triphosphates (NTP) and nucleoside diphosphates (NDP) supply knowledge about the metabolic activity and the energetic status of the tissue. In addition, the kinetic behaviour of P uptake and storage can be determined with this method. The (3)1P NMR...

  17. Ultralow field NMR spectrometer with an atomic magnetometer near room temperature.

    Science.gov (United States)

    Liu, Guobin; Li, Xiaofeng; Sun, Xianping; Feng, Jiwen; Ye, Chaohui; Zhou, Xin

    2013-12-01

    We present a Cs atomic magnetometer with a sensitivity of 150fT/Hz(1/2) operating near room temperature. The nuclear magnetic resonance (NMR) signal of 125μL tap water was detected at an ultralow magnetic field down to 47nT, with the signal-to-noise ratio (SNR) of the NMR signal approaching 50 after eight averages. Relaxivity experiments with a Gd(DTPA) contrast agent in zero field were performed, in order to show the magnetometer's ability to measure spin-lattice relaxation time with high accuracy. This demonstrates the feasibility of an ultralow field NMR spectrometer based on a Cs atomic magnetometer, which has a low working temperature, short data acquisition time and high sensitivity. This kind of NMR spectrometer has great potential in applications such as chemical analysis and magnetic relaxometry detection in ultralow or zero fields.

  18. Efficient cellular solid-state NMR of membrane proteins by targeted protein labeling

    Energy Technology Data Exchange (ETDEWEB)

    Baker, Lindsay A. [University of Oxford, Oxford Particle Imaging Centre, The Wellcome Trust Centre for Human Genetics, Division of Structural Biology, Nuffield Department of Medicine (United Kingdom); Daniëls, Mark; Cruijsen, Elwin A. W. van der; Folkers, Gert E.; Baldus, Marc, E-mail: m.baldus@uu.nl [Utrecht University, NMR Spectroscopy, Department of Chemistry, Faculty of Science, Bijvoet Center for Biomolecular Research (Netherlands)

    2015-06-15

    Solid-state NMR spectroscopy (ssNMR) has made significant progress towards the study of membrane proteins in their native cellular membranes. However, reduced spectroscopic sensitivity and high background signal levels can complicate these experiments. Here, we describe a method for ssNMR to specifically label a single protein by repressing endogenous protein expression with rifampicin. Our results demonstrate that treatment of E. coli with rifampicin during induction of recombinant membrane protein expression reduces background signals for different expression levels and improves sensitivity in cellular membrane samples. Further, the method reduces the amount of time and resources needed to produce membrane protein samples, enabling new strategies for studying challenging membrane proteins by ssNMR.

  19. Cycling was never so easy!” : An analysis of e-bike commuters’ motives, travel behaviour and experiences using GPS-tracking and interviews

    NARCIS (Netherlands)

    Plazier, Paul

    2017-01-01

    Introduction A major development in transportation in the past years has been the growth of electrically assisted cycling or e-biking. E-bikes (pedal-assisted or bicycle-style electric bicycles) make it possible to cover longer distances at higher speeds against reduced physical effort. Coupled with

  20. Complete (1)H and (13)C NMR chemical shift assignments of mono-, di-, and trisaccharides as basis for NMR chemical shift predictions of polysaccharides using the computer program casper.

    Science.gov (United States)

    Roslund, Mattias U; Säwén, Elin; Landström, Jens; Rönnols, Jerk; Jonsson, K Hanna M; Lundborg, Magnus; Svensson, Mona V; Widmalm, Göran

    2011-08-16

    The computer program casper uses (1)H and (13)C NMR chemical shift data of mono- to trisaccharides for the prediction of chemical shifts of oligo- and polysaccharides. In order to improve the quality of these predictions the (1)H and (13)C, as well as (31)P when applicable, NMR chemical shifts of 30 mono-, di-, and trisaccharides were assigned. The reducing sugars gave two distinct sets of NMR resonances due to the α- and β-anomeric forms. In total 35 (1)H and (13)C NMR chemical shift data sets were obtained from the oligosaccharides. One- and two-dimensional NMR experiments were used for the chemical shift assignments and special techniques were employed in some cases such as 2D (1)H,(13)C-HSQC Hadamard Transform methodology which was acquired approximately 45 times faster than a regular t(1) incremented (1)H,(13)C-HSQC experiment and a 1D (1)H,(1)H-CSSF-TOCSY experiment which was able to distinguish spin-systems in which the target protons were only 3.3Hz apart. The (1)H NMR chemical shifts were subsequently refined using total line-shape analysis with the PERCH NMR software. The acquired NMR data were then utilized in the casper program (http://www.casper.organ.su.se/casper/) for NMR chemical shift predictions of the O-antigen polysaccharides from Klebsiella O5, Shigella flexneri serotype X, and Salmonella arizonae O62. The data were compared to experimental data of the polysaccharides from the two former strains and the lipopolysaccharide of the latter strain showing excellent agreement between predicted and experimental (1)H and (13)C NMR chemical shifts.

  1. Realizing the quantum baker's map on a 3-qubit NMR quantum computer

    CERN Document Server

    Brun, T A; Brun, Todd A.; Schack, Ruediger

    1999-01-01

    By numerically simulating an implementation of the quantum baker's map on a 3-qubit NMR quantum computer based on the molecule trichloroethylene, we demonstrate the feasibility of quantum chaos experiments on present-day quantum computers. We give detailed descriptions of proposed experiments that investigate (a) the rate of entropy increase due to decoherence and (b) the phenomenon of hypersensitivity to perturbation.

  2. A solid-state NMR and DFT study of compositional modulations in AlxGa1-xAs

    NARCIS (Netherlands)

    Knijn, Paulus J.; Bentum, P. Jan M. van; Eck, Ernst R.H. van; Fang, Changming; Grimminck, Dennis L.A.G.; Groot, Robert A. de; Havenith, Remco W.A.; Marsman, Martijn; Meerts, W. Leo; Wijs, Gilles A. de; Kentgens, Arno P.M.

    2010-01-01

    We have conducted 75As and 69Ga Nuclear Magnetic Resonance (NMR) experiments to investigate order/disorder in AlxGa1-xAs lift-off films with x ~ 0.297 and 0.489. We were able to identify all possible As(AlnGa4-n) sites with n = 0–4 coordinations in 75As NMR spectra using spin-echo experiments at 18.

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

    Science.gov (United States)

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

    2011-08-01

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

  4. Glacial cycles

    DEFF Research Database (Denmark)

    Kaufmann, R. K.; Juselius, Katarina

    We use a statistical model, the cointegrated vector autoregressive model, to assess the degree to which variations in Earth's orbit and endogenous climate dynamics can be used to simulate glacial cycles during the late Quaternary (390 kyr-present). To do so, we estimate models of varying complexity...... and compare the accuracy of their in-sample simulations. Results indicate that strong statistical associations between endogenous climate variables are not enough for statistical models to reproduce glacial cycles. Rather, changes in solar insolation associated with changes in Earth's orbit are needed...

  5. An introduction to biological NMR spectroscopy.

    Science.gov (United States)

    Marion, Dominique

    2013-11-01

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

  6. Insights into the metabolic response to traumatic brain injury as revealed by 13C NMR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Brenda eBartnik-Olson

    2013-10-01

    Full Text Available The present review highlights critical issues related to cerebral metabolism following traumatic brain injury (TBI and the use of 13C labeled substrates and nuclear magnetic resonance (NMR spectroscopy to study these changes. First we address some pathophysiologic factors contributing to metabolic dysfunction following TBI. We then examine how 13C NMR spectroscopy strategies have been used to investigate energy metabolism, neurotransmission, the intracellular redox state, and neuroglial compartmentation following injury. 13C NMR spectroscopy studies of brain extracts from animal models of TBI have revealed enhanced glycolytic production of lactate, evidence of pentose phosphate pathway (PPP activation, and alterations in neuronal and astrocyte oxidative metabolism that are dependent on injury severity. Differential incorporation of label into glutamate and glutamine from 13C labeled glucose or acetate also suggest TBI-induced adaptations to the glutamate-glutamine cycle.

  7. Effect of fertilizers on galanthamine and metabolite profiles in Narcissus bulbs by 1H NMR.

    Science.gov (United States)

    Lubbe, Andrea; Choi, Young Hae; Vreeburg, Peter; Verpoorte, Robert

    2011-04-13

    Narcissus bulbs contain the biologically active alkaloid galanthamine, and Narcissus is being developed as a natural source of the molecule for the pharmaceutical industry. The effect of fertilizer on galanthamine production was investigated in a field study using a (1)H nuclear magnetic resonance (NMR) metabolite profiling approach. Galanthamine was quantitated and major metabolites in the bulbs were identified. The application of standard fertilization levels of nitrogen and potassium caused a significant increase in galanthamine as compared to a control. Multivariate data analysis of the (1)H NMR data revealed that applying double the standard level of nitrogen fertilizer resulted in production of more amino acids and citric acid cycle intermediates, but not more galanthamine. The results indicated that standard levels of fertilizer currently applied in The Netherlands are sufficient for optimal galanthamine accumulation in the bulbs. This study shows how (1)H NMR-based metabolic profiling can provide insight into the response of plant metabolism to agricultural practices.

  8. SQUID detected NMR and NQR. Superconducting Quantum Interference Device.

    Science.gov (United States)

    Augustine, M P; TonThat, D M; Clarke, J

    1998-03-01

    The dc Superconducting QUantum Interference Device (SQUID) is a sensitive detector of magnetic flux, with a typical flux noise of the order 1 muphi0 Hz(-1/2) at liquid helium temperatures. Here phi0 = h/2e is the flux quantum. In our NMR or NQR spectrometer, a niobium wire coil wrapped around the sample is coupled to a thin film superconducting coil deposited on the SQUID to form a flux transformer. With this untuned input circuit the SQUID measures the flux, rather than the rate of change of flux, and thus retains its high sensitivity down to arbitrarily low frequencies. This feature is exploited in a cw spectrometer that monitors the change in the static magnetization of a sample induced by radio frequency irradiation. Examples of this technique are the detection of NQR in 27Al in sapphire and 11B in boron nitride, and a level crossing technique to enhance the signal of 14N in peptides. Research is now focused on a SQUID-based spectrometer for pulsed NQR and NMR, which has a bandwidth of 0-5 MHz. This spectrometer is used with spin-echo techniques to measure the NQR longitudinal and transverse relaxation times of 14N in NH4ClO4, 63+/-6 ms and 22+/-2 ms, respectively. With the aid of two-frequency pulses to excite the 359 kHz and 714 kHz resonances in ruby simultaneously, it is possible to obtain a two-dimensional NQR spectrum. As a third example, the pulsed spectrometer is used to study NMR spectrum of 129Xe after polariza-tion with optically pumped Rb. The NMR line can be detected at frequencies as low as 200 Hz. At fields below about 2 mT the longitudinal relaxation time saturates at about 2000 s. Two recent experiments in other laboratories have extended these pulsed NMR techniques to higher temperatures and smaller samples. In the first, images were obtained of mineral oil floating on water at room temperature. In the second, a SQUID configured as a thin film gradiometer was used to detect NMR in a 50 microm particle of 195Pt at 6 mT and 4.2 K.

  9. MAS NMR of HIV-1 protein assemblies

    Science.gov (United States)

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

    2015-04-01

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

  10. Scalar operators in solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Boqin

    1991-11-01

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

  11. Oriented solid-state NMR spectrosocpy

    DEFF Research Database (Denmark)

    Bertelsen, Kresten

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

  12. NMR studies on UPt 3

    Science.gov (United States)

    Kitaoka, Y.; Tou, H.; Ishida, K.; Kimura, N.; Ōnuki, Y.; Yamamoto, E.; Haga, Y.; Maezawa, K.

    2000-06-01

    A complete set of the 195Pt Knight-shift (KS) data on the superconducting (SC) state in UPt 3 identified the spin structure of the Cooper pair corresponding to the multiple SC phases. UPt 3 was acclaimed as the first odd-parity superconductor including a non-unitary pairing state characterized by the two-component d vector like db+ idc at low T and low H [H. Tou et al., Phys. Rev. Lett. 77 (1996) 1374; 80 (1998) 3129]. We have shed further light on these novel results through a comparison with the singlet even-parity anisotropic superconductors CeCu 2Si 2 and UPd 2Al 3. In the singlet pairing state, the fractional decrease in KS below T c, δK obs is independent of the crystal direction. We have found that δ χobs=( NAμ B/ Ahf)δ Kobs where Ahf is the hyperfine coupling constant, is in good agreement with spin susceptibilities χγel calculated from an enhanced electronic specific heat γel and χnmr from the quasiparticle Korringa relation T1TKs2=const. This gives direct evidence that the χs of heavy quasiparticles in CeCu 2Si 2 and UPd 2Al 3 is rather isotropic and decreases to zero as T→0 due to the Cooper-pair formation. On the other hand in UPt 3, the δ χobsb, cs along the b- and c-axis in the non-unitary-pairing state (B phase) are two orders of magnitude smaller than χγel and χnmr. These anomalously small values for δ χobsb, cs may suggest either that the spin degree of freedom in the B phase is not perfectly locked to the a-axis or that χs is not enhanced although γel is. The latter is theoretically pointed out by Ikeda and Miyake [J. Phys. Soc. Japan 66 (1997) 3714] to be possible if 5f electrons in the non-Kramerse singlet ground state for 5f 2 are hybridized with conduction electrons. We need further effort towards coherent understanding of a microscopic mechanism leading to the occurrence of the odd-parity superconductivity in UPt 3.

  13. Happy Cycling

    DEFF Research Database (Denmark)

    Geert Jensen, Birgitte; Nielsen, Tom

    2013-01-01

    og Interaktions Design, Aarhus Universitet under opgave teamet: ”Happy Cycling City – Aarhus”. Udfordringen i studieopgaven var at vise nye attraktive løsningsmuligheder i forhold til cyklens og cyklismens integration i byrum samt at påpege relationen mellem design og overordnede diskussioner af...

  14. Glacial cycles

    DEFF Research Database (Denmark)

    Kaufmann, R. K.; Juselius, Katarina

    and compare the accuracy of their in-sample simulations. Results indicate that strong statistical associations between endogenous climate variables are not enough for statistical models to reproduce glacial cycles. Rather, changes in solar insolation associated with changes in Earth's orbit are needed...

  15. Koszul cycles

    CERN Document Server

    Bruns, Winfreid; Römer, Tim

    2010-01-01

    We prove regularity bounds for Koszul cycles holding for every ideal of dimension at most 1 in a polynomial ring. We generalize the lower bound for the Green-Lazarsfeld index of Veronese rings we proved in arXiv:0902.2431 to the multihomogeneous setting.

  16. Measuring the expected increase in cycling in the city of Milan and evaluating the positive effects on the population's health status: a Community-Based Urban Planning experience.

    Science.gov (United States)

    Rebecchi, A; Boati, L; Oppio, A; Buffoli, M; Capolongo, S

    2016-01-01

    It's scientifically known that inactivity is one of the major risk factors for Non-Communicable Diseases. One of the elements affecting the choice of transport mode, regarding circulation in the city, is the cities' urban morphology, i.e. the infrastructural facilities for the slow mobility service. Cyclability, in fact, can help to increase daily physical activity level, therefore becoming a protective factor for individual health. After a literature review about the state of the art regarding the correlation between built environment, active transport and quantification of the physical activity level, we have developed a specific questionnaire to collect information about current and forecast use of bicycle, in case of improvement and implementation of the cycling network. The questionnaire also investigated social and health aspects concerning the anamnesis of the interviewees (age, gender, health status, sport activity performed, etc) and users' opinions about existing infrastructure and planned interventions, designed to promote cycling mobility. Aim of the research was to quantify the increase of physical activity people would have realized in front of an improvement of the specific infrastructures, and the expected positive effects in terms of health. The collected data (343 interviewed in a district of Milan, named "Zona 7") demonstrate that through the implementation of the cycle network, there would be more cyclists to practice the 150 minutes weekly of physical activity recommended by WHO: time spent in cycling, indeed, would increases by 34.4% compared to the current level of cyclability, as detected by our survey. The investigation confirmed that urban interventions, especially those in small-scale, could play a key role in the promotion of healthy lifestyles, inducing therefore important positive effects on the population health. It was also carried out an application of the WHO "Health Economic Assessment Tool" to evaluate the benefits in terms of

  17. Perspectives in enzymology of membrane proteins by solid-state NMR.

    Science.gov (United States)

    Ullrich, Sandra J; Glaubitz, Clemens

    2013-09-17

    Membrane proteins catalyze reactions at the cell membrane and facilitate thetransport of molecules or signals across the membrane. Recently researchers have made great progress in understanding the structural biology of membrane proteins, mainly based on X-ray crystallography. In addition, the application of complementary spectroscopic techniques has allowed researchers to develop a functional understanding of these proteins. Solid-state NMR has become an indispensable tool for the structure-function analysis of insoluble proteins and protein complexes. It offers the possibility of investigating membrane proteins directly in their environment, which provides essential information about the intrinsic coupling of protein structure and functional dynamics within the lipid bilayer. However, to date, researchers have hardly explored the enzymology of mem-brane proteins. In this Account, we review the perspectives for investigating membrane-bound enzymes by solid-state NMR. Understanding enzyme mechanisms requires access to kinetic parameters, structural analysis of the catalytic center, knowledge of the 3D structure and methods to follow the structural dynamics of the enzyme during the catalytic cycle. In principle, solid-state NMR can address all of these issues. Researchers can characterize the enzyme kinetics by observing substrate turnover within the membrane or at the membrane interphase in a time-resolved fashion as shown for diacylglycerol kinase. Solid-state NMR has also provided a mechanistic understanding of soluble enzymes including triosephosphate isomerase (TIM) and different metal-binding proteins, which demonstrates a promising perspective also for membrane proteins. The increasing availability of high magnetic fields and the development of new experimental schemes and computational protocols have made it easier to determine 3D structure using solid-state NMR. Dynamic nuclear polarization, a key technique to boost sensitivity of solid-state NMR at low

  18. A study of sup 3 He films using SQUID NMR

    CERN Document Server

    Dyball, H C J

    2001-01-01

    Confinement of superfluid sup 3 He to a geometry of order the coherence length is predicted to produce interesting size effects and modify the superfluid phase diagram. This thesis describes the development of an experiment to measure these effects using NMR as a probe of the spin dynamics. A pulsed NMR spectrometer was developed with a low T sub c SQUID as the first stage amplifier. The sample was located in a receiver coil that formed part of a tuned circuit with the SQUID input coil. The first spectrometer was operated in an open-loop configuration but was later converted to use feedback to stabilize the SQUID gain. This later version used a DC SQUID with APF operating in flux-locked loop using the Direct Offset Integration Technique. The noise was limited by the Johnson noise in the tuned circuit in tests down to 1.5 K and the estimated noise temperature was approx 100 mK. NMR signals were observed at approx 1 MHz from low-density sup 3 He samples adsorbed on a Mylar substrate which were in reasonable agr...

  19. Human in vivo phosphate metabolite imaging with 31P NMR.

    Science.gov (United States)

    Bottomley, P A; Charles, H C; Roemer, P B; Flamig, D; Engeseth, H; Edelstein, W A; Mueller, O M

    1988-07-01

    Phosphorus (31P) spectroscopic images showing the distribution of high-energy phosphate metabolites in the human brain have been obtained at 1.5 T in scan times of 8.5 to 34 min at 27 and 64 cm3 spatial resolution using pulsed phase-encoding gradient magnetic fields and three-dimensional Fourier transform (3DFT) techniques. Data were acquired as free induction decays with a quadrature volume NMR detection coil of a truncated geometry designed to optimize the signal-to-noise ratio on the coil axis on the assumption that the sample noise represents the dominant noise source, and self-shielded magnetic field gradient coils to minimize eddy-current effects. The images permit comparison of metabolic data acquired simultaneously from different locations in the brain, as well as metabolite quantification by inclusion of a vial containing a standard of known 31P concentration in the image array. Values for the NMR visible adenosine triphosphate in three individuals were about 3 mM of tissue. The ratio of NMR detectable phosphocreatine to ATP in brain was 1.15 +/- 0.17 SD in these experiments. Potential sources of random and systematic error in these and other 31P measurements are identified.

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

    Science.gov (United States)

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

    2007-06-01

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

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

    Science.gov (United States)

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

    2000-06-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-15

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

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

    Science.gov (United States)

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

    2007-01-01

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

  4. NMR Analysis of Unknowns: An Introduction to 2D NMR Spectroscopy

    Science.gov (United States)

    Alonso, David E.; Warren, Steven E.

    2005-01-01

    A study combined 1D (one-dimensional) and 2D (two-dimensional) NMR spectroscopy to solve structural organic problems of three unknowns, which include 2-, 3-, and 4-heptanone. Results showed [to the first power]H NMR and [to the thirteenth power]C NMR signal assignments for 2- and 3-heptanone were more challenging than for 4-heptanone owing to the…

  5. NMR Analysis of Unknowns: An Introduction to 2D NMR Spectroscopy

    Science.gov (United States)

    Alonso, David E.; Warren, Steven E.

    2005-01-01

    A study combined 1D (one-dimensional) and 2D (two-dimensional) NMR spectroscopy to solve structural organic problems of three unknowns, which include 2-, 3-, and 4-heptanone. Results showed [to the first power]H NMR and [to the thirteenth power]C NMR signal assignments for 2- and 3-heptanone were more challenging than for 4-heptanone owing to the…

  6. Automated Pre-processing for NMR Assignments with Reduced Tedium

    Energy Technology Data Exchange (ETDEWEB)

    2004-05-11

    An important rate-limiting step in the reasonance asignment process is accurate identification of resonance peaks in MNR spectra. NMR spectra are noisy. Hence, automatic peak-picking programs must navigate between the Scylla of reliable but incomplete picking, and the Charybdis of noisy but complete picking. Each of these extremes complicates the assignment process: incomplete peak-picking results in the loss of essential connectivities, while noisy picking conceals the true connectivities under a combinatiorial explosion of false positives. Intermediate processing can simplify the assignment process by preferentially removing false peaks from noisy peak lists. This is accomplished by requiring consensus between multiple NMR experiments, exploiting a priori information about NMR spectra, and drawing on empirical statistical distributions of chemical shift extracted from the BioMagResBank. Experienced NMR practitioners currently apply many of these techniques "by hand", which is tedious, and may appear arbitrary to the novice. To increase efficiency, we have created a systematic and automated approach to this process, known as APART. Automated pre-processing has three main advantages: reduced tedium, standardization, and pedagogy. In the hands of experienced spectroscopists, the main advantage is reduced tedium (a rapid increase in the ratio of true peaks to false peaks with minimal effort). When a project is passed from hand to hand, the main advantage is standardization. APART automatically documents the peak filtering process by archiving its original recommendations, the accompanying justifications, and whether a user accepted or overrode a given filtering recommendation. In the hands of a novice, this tool can reduce the stumbling block of learning to differentiate between real peaks and noise, by providing real-time examples of how such decisions are made.

  7. Inverse problem for in vivo NMR spatial localization

    Energy Technology Data Exchange (ETDEWEB)

    Hasenfeld, A.C.

    1985-11-01

    The basic physical problem of NMR spatial localization is considered. To study diseased sites, one must solve the problem of adequately localizing the NMR signal. We formulate this as an inverse problem. As the NMR Bloch equations determine the motion of nuclear spins in applied magnetic fields, a theoretical study is undertaken to answer the question of how to design magnetic field configurations to achieve these localized excited spin populations. Because of physical constraints in the production of the relevant radiofrequency fields, the problem factors into a temporal one and a spatial one. We formulate the temporal problem as a nonlinear transformation, called the Bloch Transform, from the rf input to the magnetization response. In trying to invert this transformation, both linear (for the Fourier Transform) and nonlinear (for the Bloch Transform) modes of radiofrequency excitation are constructed. The spatial problem is essentially a statics problem for the Maxwell equations of electromagnetism, as the wavelengths of the radiation considered are on the order of ten meters, and so propagation effects are negligible. In the general case, analytic solutions are unavailable, and so the methods of computer simulation are used to map the rf field spatial profiles. Numerical experiments are also performed to verify the theoretical analysis, and experimental confirmation of the theory is carried out on the 0.5 Tesla IBM/Oxford Imaging Spectrometer at the LBL NMR Medical Imaging Facility. While no explicit inverse is constructed to ''solve'' this problem, the combined theoretical/numerical analysis is validated experimentally, justifying the approximations made. 56 refs., 31 figs.

  8. Bayesian peak picking for NMR spectra.

    Science.gov (United States)

    Cheng, Yichen; Gao, Xin; Liang, Faming

    2014-02-01

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

  9. Bayesian Peak Picking for NMR Spectra

    KAUST Repository

    Cheng, Yichen

    2014-02-01

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

  10. Relaxation time estimation in surface NMR

    Science.gov (United States)

    Grunewald, Elliot D.; Walsh, David O.

    2017-03-21

    NMR relaxation time estimation methods and corresponding apparatus generate two or more alternating current transmit pulses with arbitrary amplitudes, time delays, and relative phases; apply a surface NMR acquisition scheme in which initial preparatory pulses, the properties of which may be fixed across a set of multiple acquisition sequence, are transmitted at the start of each acquisition sequence and are followed by one or more depth sensitive pulses, the pulse moments of which are varied across the set of multiple acquisition sequences; and apply processing techniques in which recorded NMR response data are used to estimate NMR properties and the relaxation times T.sub.1 and T.sub.2* as a function of position as well as one-dimensional and two-dimension distributions of T.sub.1 versus T.sub.2* as a function of subsurface position.

  11. NMR analysis of compositional heterogeneity in polysaccharides

    Science.gov (United States)

    Many copolysaccharides are compositionally heterogeneous, and the composition determined by the usual analytical or spectroscopic methods provides only an average value. For some polysaccharides, the NMR data contain copolymer sequence information, such as diad, triad, and tetrad sequence intensiti...

  12. Relaxation time estimation in surface NMR

    Energy Technology Data Exchange (ETDEWEB)

    Grunewald, Elliot D.; Walsh, David O.

    2017-03-21

    NMR relaxation time estimation methods and corresponding apparatus generate two or more alternating current transmit pulses with arbitrary amplitudes, time delays, and relative phases; apply a surface NMR acquisition scheme in which initial preparatory pulses, the properties of which may be fixed across a set of multiple acquisition sequence, are transmitted at the start of each acquisition sequence and are followed by one or more depth sensitive pulses, the pulse moments of which are varied across the set of multiple acquisition sequences; and apply processing techniques in which recorded NMR response data are used to estimate NMR properties and the relaxation times T.sub.1 and T.sub.2* as a function of position as well as one-dimensional and two-dimension distributions of T.sub.1 versus T.sub.2* as a function of subsurface position.

  13. Frontiers of NMR in Molecular Biology

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-08-25

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

  14. NMR studies of multiphase flows II

    Energy Technology Data Exchange (ETDEWEB)

    Altobelli, S.A.; Caprihan, A.; Fukushima, E. [Lovelace Institutes, Albuquerque, NM (United States)] [and others

    1995-12-31

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

  15. Molecular mobility in Medicago truncatula seed during early stage of germination: Neutron scattering and NMR investigations

    Energy Technology Data Exchange (ETDEWEB)

    Falourd, Xavier [UR1268 Biopolymères Interactions Assemblages, INRA, F-44316 Nantes (France); Natali, Francesca [CNR-IOM-OGG, c/o Institut Laue-Langevin, 6 rue Jules Horowitz, BP 156, 38042 Grenoble Cedex 9 (France); Institut Laue-Langevin, 6 rue Jules Horowitz, BP 156, 38042 Grenoble Cedex 9 (France); Peters, Judith [Institut Laue-Langevin, 6 rue Jules Horowitz, BP 156, 38042 Grenoble Cedex 9 (France); Université Joseph Fourier UFR PhITEM, BP 53, 38041 Grenoble Cedex 9 (France); Institut de Biologie Structurale, 41 rue Jules Horowitz, 38027 Grenoble Cedex 1 (France); Foucat, Loïc, E-mail: Loic.Foucat@nantes.inra.fr [UR1268 Biopolymères Interactions Assemblages, INRA, F-44316 Nantes (France)

    2014-01-15

    Highlights: • Neutron scattering and NMR approaches were used to characterize seed germination. • A parallel between macromolecular motions and water dynamics was established. • Freezing/thawing cycle revealed a hysteresis connected to the seed hydration level. - Abstract: First hours of Medicago truncatula (MT) seeds germination were investigated using elastic incoherent neutron scattering (EINS) and nuclear magnetic resonance (NMR), to follow respectively how macromolecular motions and water mobility evolve when water permeates into the seed. From EINS results, it was shown that there is an increase in macromolecular mobility with the water uptake. Changes in NMR relaxation parameters reflected microstructural changes associated with the recovery of the metabolic processes. The EINS investigation of the effect of temperature on macromolecular motions showed that there is a relationship between the amount of water in the seeds and the effect of freezing–thawing cycle. The NMR relaxometry results obtained at 253 K allowed establishing possible link between the freezing of water molecules tightly bound to macromolecules and their drastic motion restriction around 250 K, as observed with EINS at the highest water content.

  16. Application Of Density Matrix Methods To Quadrupolar Spins In Solid State Nmr And Nqr

    CERN Document Server

    Ageev, S Z

    1997-01-01

    Spin dynamics in solid state NMR and NQR are studied using spin density matrix theory. First, the response of spin 7/2 subject to the first order quadrupolar interaction, excited by one and two pulse sequences is examined. Specific pulse sequences with appropriate phase cycling designed for detection of MQ coherences developed during the first pulse are calculated analytically. The results are applied to the determination of quadrupolar parameters and true chemical shifts utilizing a 1D nutation experiment. Solomon echoes under soft pulse excitation are also considered for spin 7/2. Second, analytical solutions of off-resonance nutation line intensities for spin 3/2 are presented. The first order quadrupolar interaction is retained during the pulse. The third case puts forward a new theory of composite pulses in NQR. Shaped pulses are also considered. The calculation is valid for a non-zero asymmetry parameter and arbitrary orientation of the rf field. The results are generalized for half integer spins of mag...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-21

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

  18. Thermostatted micro-reactor NMR probe head for monitoring fast reactions

    Science.gov (United States)

    Brächer, A.; Hoch, S.; Albert, K.; Kost, H. J.; Werner, B.; von Harbou, E.; Hasse, H.

    2014-05-01

    A novel nuclear magnetic resonance (NMR) probe head for monitoring fast chemical reactions is described. It combines micro-reaction technology with capillary flow NMR spectroscopy. Two reactants are fed separately into the probe head where they are effectively mixed in a micro-mixer. The mixed reactants then pass through a capillary NMR flow cell that is equipped with a solenoidal radiofrequency coil where the NMR signal is acquired. The whole flow path of the reactants is thermostatted using the liquid FC-43 (perfluorotributylamine) so that exothermic and endothermic reactions can be studied under almost isothermal conditions. The set-up enables kinetic investigation of reactions with time constants of only a few seconds. Non-reactive mixing experiments carried out with the new probe head demonstrate that it facilitates the acquisition of constant highly resolved NMR signals suitable for quantification of different species in technical mixtures. Reaction kinetic measurements on a test system are presented that prove the applicability of the novel NMR probe head for monitoring fast reactions.

  19. Interactions of protein side chains with RNA defined with REDOR solid state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Huang Wei; Varani, Gabriele; Drobny, Gary P., E-mail: drobny@chem.washington.edu [University of Washington, Department of Chemistry (United States)

    2011-11-15

    Formation of the complex between human immunodeficiency virus type-1 Tat protein and the transactivation response region (TAR) RNA is vital for transcriptional elongation, yet the structure of the Tat-TAR complex remains to be established. The NMR structures of free TAR, and TAR bound to Tat-derived peptides have been obtained by solution NMR, but only a small number of intermolecular NOEs could be identified unambiguously, preventing the determination of a complete structure. Here we show that a combination of multiple solid state NMR REDOR experiments can be used to obtain multiple distance constraints from {sup 15}N to {sup 13}C spins within the backbone and side chain guanidinium groups of arginine in a Tat-derived peptide, using {sup 19}F spins incorporated into the base of U23 in TAR and {sup 31}P spins in the P22 and P23 phosphate groups. Distances between the side chain of Arg52 and the base and phosphodiester backbone near U23 measured by REDOR NMR are comparable to distances observed in solution NMR-derived structural models, indicating that interactions of TAR RNA with key amino acid side chains in Tat are the same in the amorphous solid state as in solution. This method is generally applicable to other protein-RNA complexes where crystallization or solution NMR has failed to provide high resolution structural information.

  20. Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

    Directory of Open Access Journals (Sweden)

    Márcio S. Silva

    2017-02-01

    Full Text Available Nuclear magnetic resonance (NMR is a powerful tool for the elucidation of chemical structure and chiral recognition. In the last decade, the number of probes, media, and experiments to analyze chiral environments has rapidly increased. The evaluation of chiral molecules and systems has become a routine task in almost all NMR laboratories, allowing for the determination of molecular connectivities and the construction of spatial relationships. Among the features that improve the chiral recognition abilities by NMR is the application of different nuclei. The simplicity of the multinuclear NMR spectra relative to 1H, the minimal influence of the experimental conditions, and the larger shift dispersion make these nuclei especially suitable for NMR analysis. Herein, the recent advances in multinuclear (19F, 31P, 13C, and 77Se NMR spectroscopy for chiral recognition of organic compounds are presented. The review describes new chiral derivatizing agents and chiral solvating agents used for stereodiscrimination and the assignment of the absolute configuration of small organic compounds.