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Sample records for spin nmr spectroscopy

  1. Probing Spin Crossover in a Solution by Paramagnetic NMR Spectroscopy.

    Science.gov (United States)

    Pavlov, Alexander A; Denisov, Gleb L; Kiskin, Mikhail A; Nelyubina, Yulia V; Novikov, Valentin V

    2017-12-18

    Spin transitions in spin-crossover compounds are now routinely studied in the solid state by magnetometry; however, only a few methods exist for studies in solution. The currently used Evans method, which relies on NMR spectroscopy to measure the magnetic susceptibility, requires the availability of a very pure sample of the paramagnetic compound and its exact concentration. To overcome these limitations, we propose an alternative NMR-based technique for evaluating spin-state populations by only using the chemical shifts of a spin-crossover compound; those can be routinely obtained for a solution that contains unknown impurities and paramagnetic admixtures or is contaminated otherwise.

  2. Recent advances in solid-state NMR spectroscopy of spin I=1/2 nuclei.

    Science.gov (United States)

    Lesage, Anne

    2009-08-28

    This perspective contains a brief review of some of the most recent developments in solid-state NMR spectroscopy of spin I = 1/2 nuclei. Over the last few years, methodological advances have concerned both (1)H and lower gamma spin I = 1/2 nuclei (i.e. (13)C) and have led to the introduction of sophisticated high-resolution techniques that allow the structural investigation at an atomic level of wider and wider classes of materials. Significant developments have thus been reported in the characterisation of crystalline organic molecules, notably with the de novo structure determination of powders at natural isotopic abundance essentially by NMR alone. Key advances have been made in parallel in the structural characterisation of inorganic or hybrid frameworks, often in combination with first principle calculation of the NMR observed. Finally, progress has been reported in the structural investigation of proteins, which are not amenable to solution NMR or X-ray crystallography.

  3. EPR and NMR spectroscopy on spin-labeled proteins

    NARCIS (Netherlands)

    Finiguerra, Michelina Giuseppina

    2011-01-01

    Spin labeling and electron paramagnetic resonance (EPR) have been employed to study structure and dynamics of proteins. The surface polarity of four single cysteine mutants of the Zn-azurin in frozen solution were studied using 275 GHz EPR (J-band), with the advantage compared to 9 GHz (X-band) and

  4. Microfabricated inserts for magic angle coil spinning (MACS wireless NMR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Vlad Badilita

    Full Text Available This article describes the development and testing of the first automatically microfabricated probes to be used in conjunction with the magic angle coil spinning (MACS NMR technique. NMR spectroscopy is a versatile technique for a large range of applications, but its intrinsically low sensitivity poses significant difficulties in analyzing mass- and volume-limited samples. The combination of microfabrication technology and MACS addresses several well-known NMR issues in a concerted manner for the first time: (i reproducible wafer-scale fabrication of the first-in-kind on-chip LC microresonator for inductive coupling of the NMR signal and reliable exploitation of MACS capabilities; (ii improving the sensitivity and the spectral resolution by simultaneous spinning the detection microcoil together with the sample at the "magic angle" of 54.74° with respect to the direction of the magnetic field (magic angle spinning - MAS, accompanied by the wireless signal transmission between the microcoil and the primary circuit of the NMR spectrometer; (iii given the high spinning rates (tens of kHz involved in the MAS methodology, the microfabricated inserts exhibit a clear kinematic advantage over their previously demonstrated counterparts due to the inherent capability to produce small radius cylindrical geometries, thus tremendously reducing the mechanical stress and tearing forces on the sample. In order to demonstrate the versatility of the microfabrication technology, we have designed MACS probes for various Larmor frequencies (194, 500 and 700 MHz testing several samples such as water, Drosophila pupae, adamantane solid and LiCl at different magic angle spinning speeds.

  5. Solid-state 13C magic angle spinning NMR spectroscopy characterization of particle size structural variations in synthetic nanodiamonds

    International Nuclear Information System (INIS)

    Alam, Todd M.

    2004-01-01

    Solid-state 13 C magic angle spinning (MAS) NMR spectroscopy has been used to quantify the different carbon species observed in synthetically produced nanodiamonds. Two different diamond-like carbon species were observed using 13 C MAS NMR, which have been attributed to a highly ordered crystalline diamond phase and a disordered crystalline diamond phase. The relative ratio of these different diamond phases was found to vary with the particle size of the nanodiamond materials

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-01-01

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

  7. Discrimination of Basal Cell Carcinoma from Normal Skin Tissue Using High-Resolution Magic Angle Spinning 1H NMR Spectroscopy.

    Science.gov (United States)

    Mun, Je-Ho; Lee, Heonho; Yoon, Dahye; Kim, Byung-Soo; Kim, Moon-Bum; Kim, Shukmann

    2016-01-01

    High-resolution magic angle spinning nuclear magnetic resonance (HR-MAS NMR) spectroscopy is a useful tool for investigating the metabolism of various cancers. Basal cell carcinoma (BCC) is the most common skin cancer. However, to our knowledge, data on metabolic profiling of BCC have not been reported in the literature. The objective of the present study was to investigate the metabolic profiling of cutaneous BCC using HR-MAS (1)H NMR spectroscopy. HR-MAS (1)H NMR spectroscopy was used to analyze the metabolite profile and metabolite intensity of histopathologically confirmed BCC tissues and normal skin tissue (NST) samples. The metabolic intensity normalized to the total spectral intensities in BCC and NST was compared, and multivariate analysis was performed with orthogonal partial least-squares discriminant analysis (OPLS-DA). P values analysis revealed 9 metabolites that showed statistically significant difference between BCC and NST. In multivariate analysis, the OPLS-DA models built with the HR-MAS NMR metabolic profiles revealed a clear separation of BCC from NST. The receiver operating characteristic curve generated from the results revealed an excellent discrimination of BCC from NST with an area under the curve (AUC) value of 0.961. The present study demonstrated that the metabolite profile and metabolite intensity differ between BCC and NST, and that HR-MAS (1)H NMR spectroscopy can be a valuable tool in the diagnosis of BCC.

  8. High-resolution NMR spectroscopy of biological tissues usingprojected Magic Angle Spinning

    Energy Technology Data Exchange (ETDEWEB)

    Martin, Rachel W.; Jachmann, Rebecca C.; Sakellariou, Dimitris; Nielsen, Ulla Gro; Pines, Alexander

    2005-01-27

    High-resolution NMR spectra of materials subject toanisotropic broadening are usually obtained by rotating the sample aboutthe magic angle, which is 54.7 degrees to the static magnetic field. Inprojected Magic Angle Spinning (p-MAS), the sample is spun about twoangles, neither of which is the magic angle. This provides a method ofobtaining isotropic spectra while spinning at shallow angles. The p-MASexperiment may be used in situations where spinning the sample at themagic angle is not possible due to geometric or other constraints,allowing the choice of spinning angle to be determined by factors such asthe shape of the sample, rather than by the spin physics. The applicationof this technique to bovine tissue samples is demonstrated as a proof ofprinciple for future biological or medical applications.

  9. Nuclear spin singlet states as a contrast mechanism for NMR spectroscopy.

    Science.gov (United States)

    Devience, Stephen J; Walsworth, Ronald L; Rosen, Matthew S

    2013-10-01

    Nuclear magnetic resonance (NMR) spectra of complex chemical mixtures often contain unresolved or hidden spectral components, especially when strong background signals overlap weaker peaks. In this article we demonstrate a quantum filter utilizing nuclear spin singlet states, which allows undesired NMR spectral background to be removed and target spectral peaks to be uncovered. The quantum filter is implemented by creating a nuclear spin singlet state with spin quantum numbers j = 0, mz  = 0 in a target molecule, applying a continuous RF field to both preserve the singlet state and saturate the magnetization of undesired molecules and then mapping the target molecule singlet state back into an NMR observable state so that its spectrum can be read out unambiguously. The preparation of the target singlet state can be carefully controlled with pulse sequence parameters, so that spectral contrast can be achieved between molecules with very similar structures. We name this NMR contrast mechanism 'Suppression of Undesired Chemicals using Contrast-Enhancing Singlet States' (SUCCESS) and we demonstrate it in vitro for three target molecules relevant to neuroscience: aspartate, threonine and glutamine. Copyright © 2013 John Wiley & Sons, Ltd.

  10. Degree of Biomimicry of Artificial Spider Silk Spinning Assessed by NMR Spectroscopy.

    Science.gov (United States)

    Otikovs, Martins; Andersson, Marlene; Jia, Qiupin; Nordling, Kerstin; Meng, Qing; Andreas, Loren B; Pintacuda, Guido; Johansson, Jan; Rising, Anna; Jaudzems, Kristaps

    2017-10-02

    Biomimetic spinning of artificial spider silk requires that the terminal domains of designed minispidroins undergo specific structural changes in concert with the β-sheet conversion of the repetitive region. Herein, we combine solution and solid-state NMR methods to probe domain-specific structural changes in the NT2RepCT minispidroin, which allows us to assess the degree of biomimicry of artificial silk spinning. In addition, we show that the structural effects of post-spinning procedures can be examined. By studying the impact of NT2RepCT fiber drying, we observed a reversible beta-to-alpha conversion. We think that this approach will be useful for guiding the optimization of artificial spider silk fibers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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

  12. NMR-spectroscopy

    International Nuclear Information System (INIS)

    Lundin, A.G.; Fedin, Eh.I.

    1986-01-01

    Physical foundations are given and the most important areas of nuclear magnetic resonance (NMR) application in physics, chemistry, biology are described. A detailed review of the investigations conducted and the NMR applications in different science and technology fields is presented. The method basic experimental variants, including such new ones as high resolution in a solid body; rare isotope resonance; two-dimensional and multi-quantum fourier-spectroscopy; large molecule NMR; NMR tomography and NMR intrascopy etc. are considered. The instruments are briefly described. NMR is characterized as one of the most important investigation methods of the material composition, its molecular and crystal structure, visualization of the living organism and nonmetallic object inner structure

  13. A Coin-Flipping Analogy and Web App for Teaching Spin-Spin Splitting in [superscript 1]H NMR Spectroscopy

    Science.gov (United States)

    Azman, Adam M.; Esteb, John J.

    2016-01-01

    A coin-flipping analogy and free corresponding web app have been developed to facilitate student understanding of the origins of spin-spin splitting. First-order splitting patterns can easily be derived and understood. "Complex" splitting patterns (e.g., doublet of quartets), are easily incorporated into the analogy. A study of the…

  14. International symposium on NMR spectroscopy

    International Nuclear Information System (INIS)

    The publication consists of 32 papers and presentations from the field of NMR spectroscopy applications submitted to the International Symposium on NMR Spectroscopy held at Smolenice between 29 Sep and 3 Oct, 1980. (B.S.)

  15. Sub-minute kinetics of human red cell fumarase: 1 H spin-echo NMR spectroscopy and 13 C rapid-dissolution dynamic nuclear polarization.

    Science.gov (United States)

    Shishmarev, Dmitry; Wright, Alan J; Rodrigues, Tiago B; Pileio, Giuseppe; Stevanato, Gabriele; Brindle, Kevin M; Kuchel, Philip W

    2018-03-01

    Fumarate is an important probe of metabolism in hyperpolarized magnetic resonance imaging and spectroscopy. It is used to detect the release of fumarase in cancer tissues, which is associated with necrosis and drug treatment. Nevertheless, there are limited reports describing the detailed kinetic studies of this enzyme in various cells and tissues. Thus, we aimed to evaluate the sub-minute kinetics of human red blood cell fumarase using nuclear magnetic resonance (NMR) spectroscopy, and to provide a quantitative description of the enzyme that is relevant to the use of fumarate as a probe of cell rupture. The fumarase reaction was studied using time courses of 1 H spin-echo and 13 C-NMR spectra. 1 H-NMR experiments showed that the fumarase reaction in hemolysates is sufficiently rapid to make its kinetics amenable to study in a period of approximately 3 min, a timescale characteristic of hyperpolarized 13 C-NMR spectroscopy. The rapid-dissolution dynamic nuclear polarization (RD-DNP) technique was used to hyperpolarize [1,4- 13 C]fumarate, which was injected into concentrated hemolysates. The kinetic data were analyzed using recently developed FmR α analysis and modeling of the enzymatic reaction using Michaelis-Menten equations. In RD-DNP experiments, the decline in the 13 C-NMR signal from fumarate, and the concurrent rise and fall of that from malate, were captured with high spectral resolution and signal-to-noise ratio, which allowed the robust quantification of fumarase kinetics. The kinetic parameters obtained indicate the potential contribution of hemolysis to the overall rate of the fumarase reaction when 13 C-NMR RD-DNP is used to detect necrosis in animal models of implanted tumors. The analytical procedures developed will be applicable to studies of other rapid enzymatic reactions using conventional and hyperpolarized substrate NMR spectroscopy. Copyright © 2018 John Wiley & Sons, Ltd.

  16. Concentration profiling in rat tissue by high-resolution magic-angle spinning NMR spectroscopy: investigation of a model drug.

    Science.gov (United States)

    Lucas, Laura H; Wilson, Sarah F; Lunte, Craig E; Larive, Cynthia K

    2005-05-01

    The utility of high-resolution magic-angle spinning (HR-MAS) NMR for studying drug delivery in whole tissues was explored by dosing female Sprague-Dawley rats with topical or injectable benzoic acid (BA). In principle, HR-MAS NMR permits the detection of both intra- and extracellular compounds. This is an advantage over the previous detection of topically applied BA using microdialysis coupled to HPLC/UV as microdialysis samples only the extracellular space. Skin and muscle samples were analyzed by (1)H HR-MAS NMR, and BA levels were determined using an external standard solution added to the sample rotor. One to two percent of the BA topical dose was detected in the muscle, showing that BA penetrated through the dermal and subcutaneous layers. Since BA was not detected in the muscle in the microdialysis studies, the NMR spectra revealed the intracellular localization of BA. The amount of BA detected in muscle after subcutaneous injection correlated with the distance from the dosing site. Overall, the results suggest that HR-MAS NMR can distinguish differences in the local concentration of BA varying with tissue type, dosage method, and tissue proximity to the dosing site. The results illustrate the potential of this technique for quantitative analysis of drug delivery and distribution and the challenges to be addressed as the method is refined.

  17. 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

  18. 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...

  19. Broadband homonuclear correlation spectroscopy driven by combined R2nv sequences under fast magic angle spinning for NMR structural analysis of organic and biological solids

    Science.gov (United States)

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

    2013-07-01

    We recently described a family of experiments for R2nv Driven Spin Diffusion (RDSD) spectroscopy suitable for homonuclear correlation experiments under fast MAS conditions [G. Hou, S. Yan, S.J. Sun, Y. Han, I.J. Byeon, J. Ahn, J. Concel, A. Samoson, A.M. Gronenborn, T. Polenova, Spin diffusion drive by R-symmetry sequencs: applications to homonuclear correlation spectroscopy in MAS NMR of biological and organic solids, J. Am. Chem. Soc. 133 (2011) 3943-3953]. In these RDSD experiments, since the broadened second-order rotational resonance conditions are dominated by the radio frequency field strength and the phase shifts, as well as the size of reintroduced dipolar couplings, the different R2nv sequences display unique polarization transfer behaviors and different recoupling frequency bandwidths. Herein, we present a series of modified R2nv sequences, dubbed COmbined R2nv-Driven (CORD), that yield broadband homonuclear dipolar recoupling and give rise to uniform distribution of cross peak intensities across the entire correlation spectrum. We report NMR experiments and numerical simulations demonstrating that these CORD spin diffusion sequences are suitable for broadband recoupling at a wide range of magnetic fields and MAS frequencies, including fast-MAS conditions (νr = 40 kHz and above). Since these CORD sequences are largely insensitive to dipolar truncation, they are well suited for the determination of long-range distance constraints, which are indispensable for the structural characterization of a broad range of systems. Using U-13C,15N-alanine and U-13C,15N-histidine, we show that under fast-MAS conditions, the CORD sequences display polarization transfer efficiencies within broadband frequency regions that are generally higher than those offered by other existing spin diffusion pulse schemes. A 89-residue U-13C,15N-dynein light chain (LC8) protein has also been used to demonstrate that the CORD sequences exhibit uniformly high cross peak intensities

  20. The local physical structure of amorphous hydrogenated boron carbide: insights from magic angle spinning solid-state NMR spectroscopy.

    Science.gov (United States)

    Paquette, Michelle M; Li, Wenjing; Sky Driver, M; Karki, Sudarshan; Caruso, A N; Oyler, Nathan A

    2011-11-02

    Magic angle spinning solid-state nuclear magnetic resonance spectroscopy techniques are applied to the elucidation of the local physical structure of an intermediate product in the plasma-enhanced chemical vapour deposition of thin-film amorphous hydrogenated boron carbide (B(x)C:H(y)) from an orthocarborane precursor. Experimental chemical shifts are compared with theoretical shift predictions from ab initio calculations of model molecular compounds to assign atomic chemical environments, while Lee-Goldburg cross-polarization and heteronuclear recoupling experiments are used to confirm atomic connectivities. A model for the B(x)C:H(y) intermediate is proposed wherein the solid is dominated by predominantly hydrogenated carborane icosahedra that are lightly cross-linked via nonhydrogenated intraicosahedral B atoms, either directly through B-B bonds or through extraicosahedral hydrocarbon chains. While there is no clear evidence for extraicosahedral B aside from boron oxides, ∼40% of the C is found to exist as extraicosahedral hydrocarbon species that are intimately bound within the icosahedral network rather than in segregated phases.

  1. Integrating High-Resolution and Solid-State Magic Angle Spinning NMR Spectroscopy and a Transcriptomic Analysis of Soybean Tissues in Response to Water Deficiency.

    Science.gov (United States)

    Coutinho, Isabel D; Moraes, Tiago Bueno; Mertz-Henning, Liliane Marcia; Nepomuceno, Alexandre Lima; Giordani, Willian; Marcolino-Gomes, Juliana; Santagneli, Silvia; Colnago, Luiz Alberto

    2017-11-01

    Solid-state NMR (SSNMR) spectroscopy methods provide chemical environment and ultrastructural details that are not easily accessible by other non-destructive, high-resolution spectral techniques. High-resolution magic angle spinning (HR-MAS) has been widely used to obtain the metabolic profile of a heterogeneous sample, combining the resolution enhancement provided by MAS in SSNMR with the shimming and locking procedures in liquid-state NMR. In this work, we explored the feasibility of using the HR-MAS and SSNMR techniques to identify metabolic changes in soybean leaves subjected to water-deficient conditions. Control and water-deficient soybean leaves were analysed using one-dimensional (1D) HR-MAS and SSNMR. Total RNA was extracted from the leaves for the transcriptomic analysis. The 1 H HR-MAS and CP-MAS 13 C{ 1 H} spectra of soybean leaves grown with and without water deficiency stress revealed striking differences in metabolites. A total of 30 metabolites were identified, and the impact of water deficiency on the metabolite profile of soybean leaves was to induce amino acid synthesis. High expression levels of genes required for amino acid biosynthesis were highly correlated with the compounds identified by 1 H HR-MAS. The integration of the 1 H HR-MAS and SSNMR spectra with the transcriptomic data provided a complete picture of the major changes in the metabolic profile of soybeans in response to water deficiency. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  2. Atomic-resolution structure of the CAP-Gly domain of dynactin on polymeric microtubules determined by magic angle spinning NMR spectroscopy.

    Science.gov (United States)

    Yan, Si; Guo, Changmiao; Hou, Guangjin; Zhang, Huilan; Lu, Xingyu; Williams, John Charles; Polenova, Tatyana

    2015-11-24

    Microtubules and their associated proteins perform a broad array of essential physiological functions, including mitosis, polarization and differentiation, cell migration, and vesicle and organelle transport. As such, they have been extensively studied at multiple levels of resolution (e.g., from structural biology to cell biology). Despite these efforts, there remain significant gaps in our knowledge concerning how microtubule-binding proteins bind to microtubules, how dynamics connect different conformational states, and how these interactions and dynamics affect cellular processes. Structures of microtubule-associated proteins assembled on polymeric microtubules are not known at atomic resolution. Here, we report a structure of the cytoskeleton-associated protein glycine-rich (CAP-Gly) domain of dynactin motor on polymeric microtubules, solved by magic angle spinning NMR spectroscopy. We present the intermolecular interface of CAP-Gly with microtubules, derived by recording direct dipolar contacts between CAP-Gly and tubulin using double rotational echo double resonance (dREDOR)-filtered experiments. Our results indicate that the structure adopted by CAP-Gly varies, particularly around its loop regions, permitting its interaction with multiple binding partners and with the microtubules. To our knowledge, this study reports the first atomic-resolution structure of a microtubule-associated protein on polymeric microtubules. Our approach lays the foundation for atomic-resolution structural analysis of other microtubule-associated motors.

  3. Nuclear Magnetic Resonance spectroscopy of marine microalgae: Metabolic profiling and species discrimination from High-Resolution Magic Angle Spinning NMR analysis of whole-cell samples

    OpenAIRE

    Chauton, Matilde Skogen

    2005-01-01

    Based on what is said about the background and structure, this thesis presents a discussion of the use of NMR spectroscopy as a tool for species discrimination and metabolic profiling of microalgae. The results of various analyses including NMR and statistics are evaluated from what is known from already established identification methods such as pigment chromatography and chemotaxonomy, and the chemical composition of microalgal cells. The main focus is on the application of HR MAS on whole ...

  4. Molecular interactions in the ionic liquid emim acetate and water binary mixtures probed via NMR spin relaxation and exchange spectroscopy.

    Science.gov (United States)

    Allen, Jesse J; Bowser, Sage R; Damodaran, Krishnan

    2014-05-07

    Interactions of ionic liquids (ILs) with water are of great interest for many potential IL applications. 1-Ethyl-3-methylimidazolium (emim) acetate, in particular, has shown interesting interactions with water including hydrogen bonding and even chemical exchange. Previous studies have shown the unusual behavior of emim acetate when in the presence of 0.43 mole fraction of water, and a combination of NMR techniques is used herein to investigate the emim acetate-water system and the unusual behavior at 0.43 mole fraction of water. NMR relaxometry techniques are used to describe the effects of water on the molecular motion and interactions of emim acetate with water. A discontinuity is seen in nuclear relaxation behavior at the concentration of 0.43 mole fraction of water, and this is attributed to the formation of a hydrogen bonded network. EXSY measurements are used to determine the exchange rates between the H2 emim proton and water, which show a complex dependence on the concentration of the mixture. The findings support and expand our previous results, which suggested the presence of an extended hydrogen bonding network in the emim acetate-water system at concentrations close to 0.50 mole fraction of H2O.

  5. Structures of Biomolecules by NMR Spectroscopy

    Indian Academy of Sciences (India)

    IAS Admin

    solution makes NMR more suitable for studying the dynamic behavior of macromolecules. The first high resolution protein structure by NMR spectroscopy was carried out in mid-1980s [3]. Before the beginning of this millennium, NMR spectroscopy was limited to solving 3D struc- tures of proteins with molecular masses less ...

  6. Magic angle spinning 31P NMR spectroscopy reveals two essentially identical ionization states for the cardiolipin phosphates in phospholipid liposomes.

    Science.gov (United States)

    Kooijman, E E; Swim, L A; Graber, Z T; Tyurina, Y Y; Bayır, H; Kagan, V E

    2017-01-01

    Specific membrane lipid composition is crucial for optimized structural and functional organization of biological membranes. Cardiolipin is a unique phospholipid and important component of the inner mitochondrial membrane. It is involved in energy metabolism, inner mitochondrial membrane transport, regulation of multiple metabolic reactions and apoptotic cell death. The physico-chemical properties of cardiolipin have been studied extensively but despite all these efforts there is still lingering controversy regarding the ionization of the two phosphate groups of cardiolipin. Results obtained in the 1990s and early 2000s suggested that cardiolipin has two disparate pKa values where one of the protons was proposed to be stabilized by an intramolecular hydrogen bond. This has led to extensive speculations on the roles of these two putative ionization states of cardiolipin in mitochondria. More recently the notion of two pKa values has been challenged and rejected by several groups. These studies relied on external measurements of proton adsorption or electrophoretic mobility of membranes but did not take into account the low pH phase behavior and chemical stability of cardiolipin. Here we used 31 P NMR to show that in the physiologically relevant membrane phospholipid environment, cardiolipin carries two negative charges at physiological pH. We additionally demonstrate the pH dependent phase behavior and chemical stability of cardiolipin containing membranes. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. New techniques in NMR spectroscopy

    International Nuclear Information System (INIS)

    Hughes, C.E.

    1998-10-01

    In 1989, Soerensen introduced a method, the unitary bound, for calculating the maximum efficiencies of coherence transfer processes in NMR. This thesis applies this method to quadrupolar nuclei, an area not investigated by Soerensen. In doing so, several questions are raised, and answered, as to the implications of the unitary bound for coherence transfer processes in all areas of NMR. These include discussions of when such processes can be reversed without loss of signal and when sequential coherence transfer steps can be carried out with both steps having the maximum efficiency. One area of NMR of quadrupolar nuclei which has attracted some interest over the past few years has been the selective excitation of 23 Na nuclei in ordered environments. This was hinted at by Jaccard et al. in 1986 and demonstrated in biological systems by Eliav et al. in 1992, who achieved the selective excitation using a double-quantum filtration (DQF) experiment. The following year, Kemp-Harper and Wimperis demonstrated that the Jeener-Broekaert experiment could be used to achieve the same selectivity through excitation of quadrupolar order. The unitary bound shows that neither of these experiments achieve the maximum coherence transfer efficiency. This thesis sets out to improve upon the efficiency of these two experiments. Two multiple-pulse experiments are investigated. One seeks to improve upon the efficiency of the Jeener-Broekaert experiment for spin I = 3/2 nuclei by 33% to achieve the unitary bound efficiency. The other seeks to improve the efficiency of the selective DQF experiment by 41% to achieve the bound for spin I= 3/2 nuclei. 23 Na NMR spectra of cartilage and a lyotropic liquid crystal are presented which show that, although the new version of the Jeener-Broekaert experiment achieves no greater efficiency in practical application than the original, the new DQF experiment produces up to half of the expected improvement in efficiency. Alternative techniques to the

  8. NMR in rotating magnetic fields: Magic angle field spinning

    Energy Technology Data Exchange (ETDEWEB)

    Sakellariou, D.; Meriles, C.; Martin, R.; Pines, A.

    2004-09-10

    Magic angle sample spinning has been one of the cornerstones in high-resolution solid state NMR. Spinning frequencies nowadays have increased by at least one order of magnitude over the ones used in the first experiments and the technique has gained tremendous popularity. It is currently a routine procedure in solid-state NMR, high-resolution liquid-state NMR and solid-state MRI. The technique enhances the spectral resolution by averaging away rank 2 anisotropic spin interactions thereby producing isotropic-like spectra with resolved chemical shifts and scalar couplings. Andrew proposed that it should be possible to induce similar effects in a static sample if the direction of the magnetic field is varied, e.g., magic-angle rotation of the B0 field (B0-MAS) and this has been recently demonstrated using electromagnetic field rotation. Here we discuss on the possibilities to perform field rotation using alternative hardware, together with spectroscopic methods to recover isotropic resolution even in cases where the field is not rotating at the magic angle. Extension to higher magnetic fields would be beneficial in situations where the physical manipulation of the sample is inconvenient or impossible. Such situations occur often in materials or biomedical samples where ''ex-situ'' NMR spectroscopy and imaging analysis is needed.

  9. HR MAS 1H NMR spectroscopy analysis of marine microalgal whole cells

    OpenAIRE

    Chauton, Matilde S.; Optun, Odd Inge; Bathen, Tone F.; Volent, Zsolt; Gribbestad, Ingrid S.; Johnsen, Geir

    2003-01-01

    To study the use of nuclear magnetic resonance (NMR) spectroscopy as a method of classification, we performed high-resolution magic angle spinning proton (HR MAS 1H) NMR spectroscopy analysis of whole-cell samples of Dunaliella sp. (Chlorophyceae), Amphidinium carterae (Dinophyceae), Phaeodactylum tricornutum and Thalassiosira pseudonana (Bacillariophyceae). Emphasising the potential use of NMR spectroscopy as a routine analysis of microalgae we chose a straightforward procedure for culturing...

  10. Exotic spin phases in the one-dimensional spin-1/2 quantum magnet LiCuSbO{sub 4} as seen by high-field NMR and ESR spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Iakovleva, Margarita [IFW Dresden, Dresden (Germany); TU Dresden, Dresden (Germany); Zavoisky Physical Technical Institute, Kazan (Russian Federation); Grafe, Hans-Joachim; Kataev, Vladislav; Alfonsov, Alexey; Sturza, Mihai I.; Wurmehl, Sabine [IFW Dresden, Dresden (Germany); Vavilova, Evgeniia [Zavoisky Physical Technical Institute, Kazan (Russian Federation); Nojiri, Hiroyuki [Institute of Materials Research, Sendai (Japan); Buechner, Bernd [IFW Dresden, Dresden (Germany); TU Dresden, Dresden (Germany)

    2016-07-01

    We will present our recent results of high-field NMR and sub-THz ESR studies of the quantum magnet LiCuSbO{sub 4} (LCSO) that presents an excellent model system of a one-dimensional spin-1/2 quantum magnet with frustrated exchange interactions. Such networks are predicted to exhibit a plethora of novel ground states beyond classical ferro- or antiferromagnetic phases. In LCSO the absence of a long-range magnetic order down to sub-Kelvin temperatures is suggestive of the realization of a quantum spin liquid state. Our NMR and ESR measurements in strong magnetic fields up to 16 Tesla reveal clear indications for the occurrence of an exotic field-induced hidden phase which we will discuss in terms of multipolar physics.

  11. Spin dynamics in the strongly magnetically frustrated compounds YBaCo{sub 3}AlO{sub 7} and YBaCo{sub 3}FeO{sub 7} probed by NMR and ESR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Iakovleva, Margarita [IFW Dresden, Dresden (Germany); TU Dresden, Dresden (Germany); E. K. Zavoisky Physical-Technical Institute, Kazan (Russian Federation); Zeisner, Julian; Zimmermann, Stephan; Buechner, Bernd [IFW Dresden, Dresden (Germany); TU Dresden, Dresden (Germany); Valldor, Martin [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany); Vavilova, Evgeniia [E. K. Zavoisky Physical-Technical Institute, Kazan (Russian Federation); Grafe, Hans-Joachim; Alfonsov, Alexey; Kataev, Vladislav [IFW Dresden, Dresden (Germany)

    2016-07-01

    In the Swedenborgite type compounds YBaCo{sub 3}AlO{sub 7} and YBaCo{sub 3}FeO{sub 7} the magnetic lattice can be described as a stacking of kagome layers, where unconventional ground states such as a spin liquid state can be expected due to the strong geometrical frustration. We performed a combined experimental study of magnetic properties of single crystals of YBaCo{sub 3}AlO{sub 7} and YBaCo{sub 3}FeO{sub 7} with high field ESR and high field NMR spectroscopy. The experimental results show the occurrence of short-range quasi static electron spin correlations at T{sup *} ∼ 22 K for YBaCo{sub 3}AlO{sub 7} and T{sup *} ∼ 60K for YBaCo{sub 3}FeO{sub 7} but not a long-range antiferromagnetic order. We compare our results with AC and DC susceptibility measurements and discuss a possible competition between a spin glass-like state due to intrinsic structural disorder and a spin liquid state arising from strong magnetic frustration in this materials.

  12. 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.

  13. Broadband rotational resonance in solid state NMR spectroscopy.

    Science.gov (United States)

    Chan, Jerry C C; Tycko, Robert

    2004-05-08

    A new technique for restoring nuclear magnetic dipole-dipole couplings under magic-angle spinning (MAS) in solid state nuclear magnetic resonance (NMR) spectroscopy is described and demonstrated. In this technique, called broadband rotational resonance (BroBaRR), the coupling between a pair of nuclear spins with NMR frequency difference close (but not necessarily equal) to the MAS frequency is restored by the application of a train of weak radio-frequency pulses at a carrier frequency close to the average of the two NMR frequencies. Phase or amplitude modulation of the pulse train at half the MAS frequency splits the carrier into sidebands close to the two NMR frequencies. The pulse train then removes offsets from the exact rotational resonance condition, leading to dipolar recoupling over a bandwidth controlled by the amplitude of the pulse train. (13)C NMR experiments on uniformly (15)N,(13)C-labeled L-valineHClH(2)O powder validate the theoretical analysis. BroBaRR will be useful in studies of molecular structures by solid state NMR, for example in the detection of long-range couplings between carbons in uniformly labeled organic and biological materials.

  14. High spin spectroscopy of Pr

    Indian Academy of Sciences (India)

    2001-07-31

    Jul 31, 2001 ... c Indian Academy of Sciences. Vol. 57, No. 1. — journal of. July 2001 physics pp. 175–179. High spin spectroscopy of. 139. Pr. S CHANDA. ½. , SARMISHTHA BHATTACHARYYA. ¾. , TUMPA BHATTACHARJEE .... which is configured under LINUX platform. Around 90 x10 two and higher fold events were ...

  15. High-spin nuclear spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Diamond, R.M.

    1986-07-01

    High-spin spectroscopy is the study of the changes in nuclear structure, properties, and behavior with increasing angular momentum. It involves the complex interplay between collective and single-particle motion, between shape and deformation changes, particle alignments, and changes in the pairing correlations. A review of progress in theory, experimentation, and instrumentation in this field is given. (DWL)

  16. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Guangjin, E-mail: hou@udel.edu, E-mail: tpolenov@udel.edu; Lu, Xingyu, E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net; Vega, Alexander J., E-mail: luxingyu@udel.edu, E-mail: lexvega@comcast.net; Polenova, Tatyana, E-mail: hou@udel.edu, E-mail: tpolenov@udel.edu [Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA and Pittsburgh Center for HIV Protein Interactions, University of Pittsburgh School of Medicine, 1051 Biomedical Science Tower 3, 3501 Fifth Ave., Pittsburgh, Pennsylvania 15261 (United States)

    2014-09-14

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear {sup 1}H-X (X = {sup 13}C, {sup 15}N, {sup 31}P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the {sup 1}H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the {sup 1}H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from {sup 1}H chemical shift anisotropy, while keeping the {sup 1}H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [{sup 15}N]-N-acetyl-valine and [U-{sup 13}C,{sup 15}N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate {sup 1}H-{sup 15}N dipolar couplings in the context of 3D experiments is presented on U-{sup 13}C,{sup 15}N-enriched dynein light chain protein LC8.

  17. Diffusional behavior of n-paraffins with various chain lengths in urea adduct channels by pulsed field-gradient spin-echo NMR spectroscopy

    International Nuclear Information System (INIS)

    Kim, Sunmi; Kuroki, Shigeki; Ando, Isao

    2006-01-01

    The diffusion coefficients (D) of n-paraffin molecules (n-C n H 2n+2 ) with various chain-lengths (n = 8, 12, 21, 26, 28 and 32) in the long channels of a deuterated urea-d 4 adduct have been measured at 25 deg. C by means of pulsed field-gradient spin-echo 1 H NMR method. The aim is to clarify diffusional behavior of the n-paraffin molecules in the urea adduct channels. From the experimental results, it is found that n-paraffin molecules are diffusing in the long channels and have two kinds of diffusion components, namely a fast (D ∼ 10 -10 m 2 /s) and a slow diffusion component (D ∼ 10 -11 m 2 /s). The diffusing-time (Δ) dependence of the diffusion coefficients of the n-paraffins shows some likely evidence of restricted diffusion since the n-paraffin molecules are confined in the urea channel. The diffusion coefficients (D) decrease as the carbon number increases from 8 to 28, and very slowly decreases as the carbon number increases from 28 to 32

  18. High spin spectroscopy of Pr

    Indian Academy of Sciences (India)

    2001-07-31

    Jul 31, 2001 ... High spin states; nuclear structure; gamma-ray spectroscopy;. ½¿. Pr energy levels. PACS Nos 21.10.-k; 23.20.-g; 27.60.+j; 29.30.Kv. 1. Introduction. The transitional nuclei in the A. ½ ¼ region with N between 77 and 81 are interesting as it offer good scope to look for possible shape changes, similar to ...

  19. 31P MAS refocused INADEQUATE spin-echo (REINE) NMR spectroscopy: revealing J coupling and chemical shift two-dimensional correlations in disordered solids.

    Science.gov (United States)

    Guerry, Paul; Smith, Mark E; Brown, Steven P

    2009-08-26

    Two-dimensional (2D) variations in (2)J(P(1),P(1)), (2)J(P(1),P(2)), and (2)J(P(2),P(2)) are obtained--using the REINE (REfocused INADEQUATE spin-Echo) pulse sequence presented by Cadars et al. (Phys. Chem. Chem. Phys. 2007, 9, 92-103)--from pixel-by-pixel fittings of the spin-echo modulation for the 2D correlation peaks due to linked phosphate tetrahedra (P(1)-P(1), P(1)-P(2), P(2)-P(1), and P(2)-P(2)) in a (31)P refocused INADEQUATE solid-state MAS NMR spectrum of a cadmium phosphate glass, 0.575CdO-0.425P(2)O(5). In particular, separate variations for each 2D (31)P REINE peak are obtained which reveal correlations between the J couplings and the (31)P chemical shifts of the coupled nuclei that are much clearer than those evident in previously presented 2D z-filtered (31)P spin-echo spectra. Notably, such correlations between the J couplings and the (31)P chemical shifts are observed even though the conditional probability distributions extracted using the protocol of Cadars et al. (J. Am. Chem. Soc. 2005, 127, 4466-4476) indicate that there is no marked correlation between the (31)P chemical shifts of neighboring phosphate tetrahedra. For 2D peaks at the P(2) (31)P chemical shift in the direct dimension, there can be contributions from chains of three units (P(1)-P(2)-P(1)), chains of four units (P(1)-P(2)-P(2)-P(1)), or longer chains or rings (-P(2)-P(2)-P(2)-): for the representative glass considered here, best fits are obtained assuming a glass comprised predominantly of chains of four units. The following variations are found: (2)J(P(1),P(1)) = 13.4 +/- 0.3 to 14.8 +/- 0.5 Hz, (2)J(P(1),P(2)) = 15.0 +/- 0.3 to 18.2 +/- 0.3 Hz, and (2)J(P(2),P(2)) = 5.9 +/- 0.6 to 9.1 +/- 0.9 Hz from the fits to the P(1)-P(1), P(1)-P(2), and P(2)-P(2) peaks, respectively. The correlation of a particular J coupling with the (31)P chemical shifts of the considered nucleus and the coupled nucleus is quantified by the coefficients C(F(2)) and C(F(1)) that correspond to the

  20. Medical applications of NMR imaging and NMR spectroscopy with stable isotopes. Summary

    International Nuclear Information System (INIS)

    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

  1. 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.

  2. NMR spectroscopy applied to the eye: Drugs and metabolic studies

    International Nuclear Information System (INIS)

    Saether, Oddbjoern

    2005-01-01

    NMR spectroscopy has been extensively applied in biomedical research during the last decades. It has proved to be an analytical tool of great value. From being mainly used in chemistry, technological developments have expanded the application of NMR spectroscopy to a great wealth of disciplines. With this method, biochemical information can be obtained by analysing tissue extracts. Moreover, NMR spectroscopy is increasingly employed for pharmacokinetic studies and analysis of biofluids. Technological progress has provided increased sensitivity and resolution in the spectra, which enable even more of the complexity of biological samples to be elucidated. With the implementation of high-resolution magic angle spinning (HR-MAS) NMR spectroscopy in biomedicine, intact tissue samples or biopsies can be investigated. Thus, NMR spectroscopy has an ever-increasing impact in metabolic screening of human samples and in animal models, and methods are also increasingly realised in vivo. The present work, NMR spectroscopy applied to eye research, consists of two main parts. Firstly, the feasibility to monitor fluorinated ophthalmic drugs directly in the eye was assessed. Secondly, HR-MAS H1 NMR spectroscopy was applied for metabolic profiling of the anterior eye segment, specifically to analyse metabolic changes in intact corneal and lenticular samples after cataractogenic insults. This work included metabonomics with the application of pattern recognition methods to analyse HR-MAS spectra of eye tissues. Optimisation strategies were explored for F19 NMR detection of fluorinated drugs in a phantom eye. S/N gains in F19 NMR spectroscopy were achieved by implementing time-share H1 decoupling at 2.35 T. The method is advantageous for compounds displaying broad spectral coupling patterns, though detection of drugs at concentrations encountered in the anterior eye segment after topical application was not feasible. Higher magnetic fields and technological improvements could enable

  3. NMR spectroscopy applied to the eye: Drugs and metabolic studies

    Energy Technology Data Exchange (ETDEWEB)

    Saether, Oddbjoern

    2005-07-01

    NMR spectroscopy has been extensively applied in biomedical research during the last decades. It has proved to be an analytical tool of great value. From being mainly used in chemistry, technological developments have expanded the application of NMR spectroscopy to a great wealth of disciplines. With this method, biochemical information can be obtained by analysing tissue extracts. Moreover, NMR spectroscopy is increasingly employed for pharmacokinetic studies and analysis of biofluids. Technological progress has provided increased sensitivity and resolution in the spectra, which enable even more of the complexity of biological samples to be elucidated. With the implementation of high-resolution magic angle spinning (HR-MAS) NMR spectroscopy in biomedicine, intact tissue samples or biopsies can be investigated. Thus, NMR spectroscopy has an ever-increasing impact in metabolic screening of human samples and in animal models, and methods are also increasingly realised in vivo. The present work, NMR spectroscopy applied to eye research, consists of two main parts. Firstly, the feasibility to monitor fluorinated ophthalmic drugs directly in the eye was assessed. Secondly, HR-MAS H1 NMR spectroscopy was applied for metabolic profiling of the anterior eye segment, specifically to analyse metabolic changes in intact corneal and lenticular samples after cataractogenic insults. This work included metabonomics with the application of pattern recognition methods to analyse HR-MAS spectra of eye tissues. Optimisation strategies were explored for F19 NMR detection of fluorinated drugs in a phantom eye. S/N gains in F19 NMR spectroscopy were achieved by implementing time-share H1 decoupling at 2.35 T. The method is advantageous for compounds displaying broad spectral coupling patterns, though detection of drugs at concentrations encountered in the anterior eye segment after topical application was not feasible. Higher magnetic fields and technological improvements could enable

  4. An introduction to biological NMR spectroscopy

    International Nuclear Information System (INIS)

    Marion, Dominique

    2013-01-01

    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). (authors)

  5. High-resolution magic angle spinning proton NMR analysis of human prostate tissue with slow spinning rates.

    Science.gov (United States)

    Taylor, Jennifer L; Wu, Chin-Lee; Cory, David; Gonzalez, R Gilberto; Bielecki, Anthony; Cheng, Leo L

    2003-09-01

    The development of high-resolution magic angle spinning (HR-MAS) NMR spectroscopy for intact tissue analysis and the correlations between the measured tissue metabolites and disease pathologies have inspired investigations of slow-spinning methodologies to maximize the protection of tissue pathology structures from HR-MAS centrifuging damage. Spinning sidebands produced by slow-rate spinning must be suppressed to prevent their complicating the spectral region of metabolites. Twenty-two human prostatectomy samples were analyzed on a 14.1T spectrometer, with HR-MAS spinning rates of 600 Hz, 700 Hz, and 3.0 kHz, a repetition time of 5 sec, and employing various rotor-synchronized suppression methods, including DANTE, WATERGATE, TOSS, and PASS pulse sequences. Among them, DANTE, as the simplest scheme, has shown the most potential in suppression of tissue water signals and spinning sidebands, as well as in quantifying metabolic concentrations. Copyright 2003 Wiley-Liss, Inc.

  6. Selected topics in solution-phase biomolecular NMR spectroscopy

    Science.gov (United States)

    Kay, Lewis E.; Frydman, Lucio

    2017-05-01

    Solution bio-NMR spectroscopy continues to enjoy a preeminent role as an important tool in elucidating the structure and dynamics of a range of important biomolecules and in relating these to function. Equally impressive is how NMR continues to 'reinvent' itself through the efforts of many brilliant practitioners who ask increasingly demanding and increasingly biologically relevant questions. The ability to manipulate spin Hamiltonians - almost at will - to dissect the information of interest contributes to the success of the endeavor and ensures that the NMR technology will be well poised to contribute to as yet unknown frontiers in the future. As a tribute to the versatility of solution NMR in biomolecular studies and to the continued rapid advances in the field we present a Virtual Special Issue (VSI) that includes over 40 articles on various aspects of solution-state biomolecular NMR that have been published in the Journal of Magnetic Resonance in the past 7 years. These, in total, help celebrate the achievements of this vibrant field.

  7. Molecular and electron-spin structures of a ring-shaped mixed-valence polyoxovanadate (IV, V) studied by (11)B and (23)Na solid-state NMR spectroscopy and DFT calculations.

    Science.gov (United States)

    Iijima, Takahiro; Yamase, Toshihiro; Nishimura, Katsuyuki

    2016-01-01

    (11)B and (23)Na solid-state nuclear magnetic resonance (NMR) spectra of ring-shaped paramagnetic crystals of H15[V7(IV)V5(V)B32O84Na4]·13H2O containing seven d(1) electrons from V(IV) were studied. Magic-angle-spinning (MAS) and multiple-quantum MAS NMR experiments were performed at moderate (9.4T) and ultrahigh magnetic fields (21.6T). The NMR parameters for quadrupole and isotropic chemical shift interactions were estimated by simulation of the NMR spectra and from relativistic density functional theory (DFT) calculations. Four Na ions incorporated into the framework were found to occupy four distinct sites with different populations. The DFT calculation showed that d(1) electrons with effectively one up-spin caused by strong antiferromagnetic interactions were delocalized over the 12V ions. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Spin-polarized spin excitation spectroscopy

    International Nuclear Information System (INIS)

    Loth, Sebastian; Lutz, Christopher P; Heinrich, Andreas J

    2010-01-01

    We report on the spin dependence of elastic and inelastic electron tunneling through transition metal atoms. Mn, Fe and Cu atoms were deposited onto a monolayer of Cu 2 N on Cu(100) and individually addressed with the probe tip of a scanning tunneling microscope. Electrons tunneling between the tip and the substrate exchange energy and spin angular momentum with the surface-bound magnetic atoms. The conservation of energy during the tunneling process results in a distinct onset threshold voltage above which the tunneling electrons create spin excitations in the Mn and Fe atoms. Here we show that the additional conservation of spin angular momentum leads to different cross-sections for spin excitations depending on the relative alignment of the surface spin and the spin of the tunneling electron. For this purpose, we developed a technique for measuring the same local spin with a spin-polarized and a non-spin-polarized tip by exchanging the last apex atom of the probe tip between different transition metal atoms. We derive a quantitative model describing the observed excitation cross-sections on the basis of an exchange scattering process.

  9. Magic-angle-spinning NMR spectroscopy. January 1978-May 1988 (Citations from the INSPEC: Information Services for the Physics and Engineering Communities data base). Report for January 1978-May 1988

    International Nuclear Information System (INIS)

    1988-05-01

    This bibliography contains citations concerning the principles and applications of magic-angle spinning (MAS) nuclear magnetic resonance (NMR) in high-resolution spectra analysis of solids. Magic-angle spinning NMR is a very powerful spectrographic technique for the study of structures, dynamics, and reactivity of solids, and polcrystalline and amorphous solids. Studies of various materials are presented, including zeolites, organic compounds and polymers, liquid crystals, silicate and borate glasses, and alumina and oxide films. Applications in conductive polymers, biological systems, and organic matrixes of composite materials are presented. (Contains 89 citations fully indexed and including a title list.)

  10. High-resolution magic angle spinning (1)H NMR spectroscopy of metabolic changes in rabbit lens after treatment with dexamethasone combined with UVB exposure

    Czech Academy of Sciences Publication Activity Database

    Seather, O.; Risa, O.; Čejková, Jitka; Krane, J.; Midelfart, A.

    2004-01-01

    Roč. 242, - (2004), s. 1000-1007 ISSN 0721-832X R&D Projects: GA ČR GA304/03/0419 Institutional research plan: CEZ:AV0Z5008914 Keywords : HR-MAS 1H NMR Subject RIV: FF - HEENT, Dentistry Impact factor: 1.513, year: 2004

  11. NMR studies of selective population inversion and spin clustering

    Energy Technology Data Exchange (ETDEWEB)

    Baum, J.S.

    1986-02-01

    This work describes the development and application of selective excitation techniques in Nuclear Magnetic Resonance. Composite pulses and multiple-quantum methods are used to accomplish various goals, such as broadband and narrowband excitation in liquids, and collective excitation of groups of spins in solids. These methods are applied to a variety of problems, including non-invasive spatial localization, spin cluster size characterization in disordered solids and solid state NMR imaging.

  12. NMR studies of selective population inversion and spin clustering

    International Nuclear Information System (INIS)

    Baum, J.S.

    1986-02-01

    This work describes the development and application of selective excitation techniques in Nuclear Magnetic Resonance. Composite pulses and multiple-quantum methods are used to accomplish various goals, such as broadband and narrowband excitation in liquids, and collective excitation of groups of spins in solids. These methods are applied to a variety of problems, including non-invasive spatial localization, spin cluster size characterization in disordered solids and solid state NMR imaging

  13. Spin coherence transfer in chemical transformations monitoredNMR

    Energy Technology Data Exchange (ETDEWEB)

    Anwar, Sabieh M.; Hilty, Christian; Chu, Chester; Bouchard,Louis-S.; Pierce, Kimberly L.; Pines, Alexander

    2006-07-31

    We demonstrate the use of micro-scale nuclear magneticresonance (NMR) for studying the transfer of spin coherence innon-equilibrium chemical processes, using spatially separated NMRencoding and detection coils. As an example, we provide the map ofchemical shift correlations for the amino acid alanine as it transitionsfrom the zwitterionic to the anionic form. Our method is unique in thesense that it allows us to track the chemical migration of encodednuclear spins during the course of chemical transformations.

  14. SPINS: Standardized ProteIn NMR Storage. A data dictionary and object-oriented relational database for archiving protein NMR spectra

    International Nuclear Information System (INIS)

    Baran, Michael C.; Moseley, Hunter N.B.; Sahota, Gurmukh; Montelione, Gaetano T.

    2002-01-01

    Modern protein NMR spectroscopy laboratories have a rapidly growing need for an easily queried local archival system of raw experimental NMR datasets. SPINS (Standardized ProteIn Nmr Storage) is an object-oriented relational database that provides facilities for high-volume NMR data archival, organization of analyses, and dissemination of results to the public domain by automatic preparation of the header files required for submission of data to the BioMagResBank (BMRB). The current version of SPINS coordinates the process from data collection to BMRB deposition of raw NMR data by standardizing and integrating the storage and retrieval of these data in a local laboratory file system. Additional facilities include a data mining query tool, graphical database administration tools, and a NMRStar v2.1.1 file generator. SPINS also includes a user-friendly internet-based graphical user interface, which is optionally integrated with Varian VNMR NMR data collection software. This paper provides an overview of the data model underlying the SPINS database system, a description of its implementation in Oracle, and an outline of future plans for the SPINS project

  15. 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.

  16. Analysis of NMR shifts and spin-spin coupling constants in L-Alanyl-LAlanine zwitterion

    Czech Academy of Sciences Publication Activity Database

    Sychrovský, Vladimír; Špirko, Vladimír; Šebestík, Jaroslav; Kapitán, Josef; Buděšínský, Miloš; Bouř, Petr

    2005-01-01

    Roč. 59, 7/8 (2005), s. 453 ISSN 0009-4293. [International Conference on the Applications of Density Functional Theory in Chemistry and Physics /11./. 11.09.2005-15.09.2005, Geneva] Institutional research plan: CEZ:AV0Z40550506 Keywords : NMR shifts * spin-spin coupling Subject RIV: CF - Physical ; Theoretical Chemistry

  17. Investigating albendazole desmotropes by solid-state NMR spectroscopy.

    Science.gov (United States)

    Chattah, Ana K; Zhang, Rongchun; Mroue, Kamal H; Pfund, Laura Y; Longhi, Marcela R; Ramamoorthy, Ayyalusamy; Garnero, Claudia

    2015-03-02

    Characterization of the molecular structure and physicochemical solid-state properties of the solid forms of pharmaceutical compounds is a key requirement for successful commercialization as potential active ingredients in drug products. These properties can ultimately have a critical effect on the solubility and bioavailability of the final drug product. Here, the desmotropy of Albendazole forms I and II was investigated at the atomic level. Ultrafast magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectroscopy, together with powder X-ray diffraction, thermal analysis, and Fourier transform infrared spectroscopy, were performed on polycrystalline samples of the two solids in order to fully characterize and distinguish the two forms. High-resolution one-dimensional (1)H, (13)C, and (15)N together with two-dimensional (1)H/(1)H single quantum-single quantum, (1)H/(1)H single quantum-double quantum, and (1)H/(13)C chemical shift correlation solid-state NMR experiments under MAS conditions were extensively used to decipher the intramolecular and intermolecular hydrogen bonding interactions present in both solid forms. These experiments enabled the unequivocal identification of the tautomers of each desmotrope. Our results also revealed that both solid forms may be described as dimeric structures, with different intermolecular hydrogen bonds connecting the tautomers in each dimer.

  18. A New Spin on Photoemission Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Jozwiak, Chris [Univ. of California, Berkeley, CA (United States)

    2008-12-01

    The electronic spin degree of freedom is of general fundamental importance to all matter. Understanding its complex roles and behavior in the solid state, particularly in highly correlated and magnetic materials, has grown increasingly desirable as technology demands advanced devices and materials based on ever stricter comprehension and control of the electron spin. However, direct and efficient spin dependent probes of electronic structure are currently lacking. Angle Resolved Photoemission Spectroscopy (ARPES) has become one of the most successful experimental tools for elucidating solid state electronic structures, bolstered by-continual breakthroughs in efficient instrumentation. In contrast, spin-resolved photoemission spectroscopy has lagged behind due to a lack of similar instrumental advances. The power of photoemission spectroscopy and the pertinence of electronic spin in the current research climate combine to make breakthroughs in Spin and Angle Resolved Photoemission Spectroscopy (SARPES) a high priority . This thesis details the development of a unique instrument for efficient SARPES and represents a radical departure from conventional methods. A custom designed spin polarimeter based on low energy exchange scattering is developed, with projected efficiency gains of two orders of magnitude over current state-of-the-art polarimeters. For energy analysis, the popular hemispherical analyzer is eschewed for a custom Time-of-Flight (TOF) analyzer offering an additional order of magnitude gain in efficiency. The combined instrument signifies the breakthrough needed to perform the high resolution SARPES experiments necessary for untangling the complex spin-dependent electronic structures central to today's condensed matter physics.

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

    Science.gov (United States)

    Mills, Nancy S.; Shanklin, Michael

    2011-01-01

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

  20. Solid state NMR, basic theory and recent progress for quadrupole nuclei with half-integer spin

    International Nuclear Information System (INIS)

    Dieter, F.

    1998-01-01

    This review describes the basic theory and some recently developed techniques for the study of quadrupole nuclei with half integer spins in powder materials. The latter is connected to the introduction of the double rotation (DOR) by A. Samoson et al. (1) and to the introduction of the multiple quantum magic-angle spinning (MQ MAS) technique by L. Frydman et. al. (2). For integer spins, especially the solid-state deuterium magnetic resonance, we refer to the review of G.L. Hoatson and R.L. Vold: '' 2 H-NMR Spectroscopy of Solids and Liquid Crystals'' (3). For single crystals we refer to O. Kanert and M. Mehring: ''Static quadrupole effects in disordered cubic solids''(4) and we would like also to mention the ''classic'' review of M.H. Cohen and F. Reif: ''Quadrupole effects in NMR studies of solids'' (5). Some more recent reviews in the field under study are D. Freude and J. Haase ''Quadrupole effects in solid-state NMR'' (6). Ch. Jager: ''Satellite Transition Spectroscopy of Quadrupolar Nuclei'' (7) and B.F. Chmelka and J.W. Zwanziger: ''Solid State NMR Line Narrowing Methods for Quadrupolar Nuclei - Double Rotation and Dynamic-Angle Spinning'' (8). A survey of nuclear quadrupole frequency data published before the end of 1982 is given by H. Chihara and N. Nakamura in Landolt-Bornstein, Vol. 20 (9). Values of the chemical shift of quadrupole nuclei in solids can be found in books such as ''Multinuclear NMR'' edited by J. Mason (10). In section 9 of ref (6) some electric field gradient and chemical shift data published from 1983 to 1992 for the most studied quadrupole nuclei sup 27 Al, sup 23 Na, and sup 17 O are given

  1. NMR spectroscopy: a tool for conformational analysis

    Energy Technology Data Exchange (ETDEWEB)

    Tormena, Claudio F.; Cormanich, Rodrigo A.; Rittner, Roberto, E-mail: rittner@iqm.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica. Lab. de Fisico-Quimica Organica; Freitas, Matheus P. [Universidade Federal de Lavras (UFLA), MG (Brazil). Dept. de Qumica

    2011-07-01

    The present review deals with the application of NMR data to the conformational analysis of simple organic compounds, together with other experimental methods like infrared spectroscopy and with theoretical calculations. Each sub-section describes the results for a group of compounds which belong to a given organic function like ketones, esters, etc. Studies of a single compound, even of special relevance, were excluded since the main goal of this review is to compare the results for a given function, where different substituents were used or small structural changes were introduced in the substrate, in an attempt to disclose their effects in the conformational equilibrium. Moreover, the huge amount of data available in the literature, on this research field, imposed some limitations which will be detailed in the Introduction, but it can be reminded in advance that these limitations include mostly the period when these results were published. (author)

  2. NMR spectroscopy: a tool for conformational analysis

    International Nuclear Information System (INIS)

    Tormena, Claudio F.; Cormanich, Rodrigo A.; Rittner, Roberto; Freitas, Matheus P.

    2011-01-01

    The present review deals with the application of NMR data to the conformational analysis of simple organic compounds, together with other experimental methods like infrared spectroscopy and with theoretical calculations. Each sub-section describes the results for a group of compounds which belong to a given organic function like ketones, esters, etc. Studies of a single compound, even of special relevance, were excluded since the main goal of this review is to compare the results for a given function, where different substituents were used or small structural changes were introduced in the substrate, in an attempt to disclose their effects in the conformational equilibrium. Moreover, the huge amount of data available in the literature, on this research field, imposed some limitations which will be detailed in the Introduction, but it can be reminded in advance that these limitations include mostly the period when these results were published. (author)

  3. Picoliter NMR spectroscopy using nitrogen-vacancy centers in nanofabricated diamond

    Science.gov (United States)

    Kehayias, Pauli; Jarmola, Andrey; Mosavian, Nazanin; Fescenko, Ilja; Benito, Francisco; Laraoui, Abdelghani; Smits, Janis; Bougas, Lykourgos; Budker, Dmitry; Neumann, Alex; Brueck, Steven; Acosta, Victor

    2017-04-01

    Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for analytical chemistry, though one drawback is that its utility can be limited by poor sensitivity. This makes NMR characterization challenging for samples with few nuclear spins. Building on the recent advances of using nitrogen-vacancy (NV) color centers in diamond for NMR spectroscopy, we used an NV ensemble (a few-nm layer at the diamond surface) to improve sensitivity, which we further enhance by nanofabricating gratings for greater surface area. With nanofabricated diamond chips we detected the NMR signal from 1 molar 19F in glycerol in a 1 pL volume with nearly 100 × improvement in concentration sensitivity compared to previous reported works. We will present details on our recent findings and ongoing attempts to use this technique in practical applications.

  4. Spin noise spectroscopy of ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Horn, Hauke; Huebner, Jens; Oestreich, Michael [Institute for Solid State Physics, Gottfried Wilhelm Leibniz University Hannover (Germany); Marie, Xavier; Balocchi, Andrea [INSA-CNRS-UPS, LPCNO, Universite de Toulouse (France)

    2010-07-01

    ZnO is a promising material for optical spintronics showing long electron spin lifetimes due to the large band gap and low amount of nuclear spin isotopes. Here, we use spin noise spectroscopy to access the electron spin dynamics of this material in thermal equilibrium while avoiding carrier heating and excitation of electron hole pairs. A linear polarized laser beam (E{sub UV-Laser}=3.32 eV) close to the direct band gap of ZnO (E{sub D}{sup 0}{sub X}=3.36 eV) is used to detect the spin dynamics of neutral donors in ZnO with off-resonant, non-demolition Faraday rotation. The stochastic oriented electron spins induce polarization fluctuations of the transmitted laser beam. The fluctuation strength of N non-interacting, paramagnetic spins follow the Poisson statistics and generate measurable noise {proportional_to}{radical}(N) spins. These fluctuations are measured via a polarization bridge in the radio frequency regime and Fourier transformed in real-time. A magnetic field B is applied in Voigt-geometry and modulates the noise signal with the Larmor frequency of the electron spins {omega}{sub L}=g{mu}{sub B}B/{Dirac_h}. From the recorded noise spectra we can extract the electron g-factor, spin lifetimes, and densities.

  5. Fourier transform n.m.r. spectroscopy

    International Nuclear Information System (INIS)

    Shaw, D.

    1976-01-01

    This book is orientated to techniques rather than applications. The basic theory of n.m.r. is dealt with in a unified approach to the Fourier theory. The middle section of the book concentrates on the practical aspects of Fourier n.m.r., both instrumental and experimental. The final chapters briefly cover general application of n.m.r., but concentrate strongly on those areas where Fourier n.m.r. can give information which is not available by conventional techniques

  6. Spin noise spectroscopy in {sup 28}Si

    Energy Technology Data Exchange (ETDEWEB)

    Boentgen, Tammo; Huebner, Jens; Oestreich, Michael [Institute for Solid State Physics, Gottfried Wilhelm Leibniz University Hannover (Germany); Riemann, Helge [Institut fuer Kristallzuechtung, Berlin (Germany)

    2009-07-01

    We employ spin noise spectroscopy to examine the intrinsic spin lifetime of electrons bound to phosphorus donors in isotopically pure {sup 28}Si at low temperatures. The up to now reported spin lifetime of these electrons are already extremely long but no measurement of the intrinsic lifetime has been undertaken yet. In addition we will measure the ultra narrow exciton transition lines in {sup 28}Si. These transition lines scale with the isotopical purity of the sample and should be according to calculations as small as 100 neV in the studied silicon.

  7. Spectroscopy: Mapping spins in flatland

    Science.gov (United States)

    Aharonovich, Igor; Jelezko, Fedor

    2017-04-01

    Nuclear quadrupole resonance spectroscopy is used to map the properties of atomically thin hexagonal boron nitride, with the help of the nitrogen-vacancy colour centres engineered in a diamond layer placed under the 2D material.

  8. [Rapid analysis of suppositories by quantitative 1H NMR spectroscopy].

    Science.gov (United States)

    Abramovich, R A; Kovaleva, S A; Goriainov, S V; Vorob'ev, A N; Kalabin, G A

    2012-01-01

    Rapid analysis of suppositories with ibuprofen and arbidol by quantitative 1H NMR spectroscopy was performed. Optimal conditions for the analysis were developed. The results are useful for design of rapid methods for quality control of suppositories with different components

  9. New methods for the correction of 31P NMR spectra in in vivo NMR spectroscopy

    International Nuclear Information System (INIS)

    Starcuk, Z.; Bartusek, K.; Starcuk, Z. jr.

    1994-01-01

    The new methods for the correction of 31 P NMR spectra in vivo NMR spectroscopy have been performed. A method for the baseline correction of the spectra which represents a combination of time-domain and frequency-domain has been discussed.The method is very fast and efficient for minimization of base line artifacts of biological tissues impact

  10. Modeling optically pumped NMR and spin polarization in GaAs/AlGaAs quantum wells

    Science.gov (United States)

    Saha, D.; Wood, R.; Tokarski, J. T.; McCarthy, L. A.; Bowers, C. R.; Sesti, E. L.; Hayes, S. E.; Kuhns, P. L.; McGill, S. A.; Reyes, A. R.; Sanders, G. D.; Stanton, C. J.

    2014-08-01

    Optically-pumped nuclear magnetic resonance (OPNMR) spectroscopy is an emerging technique to probe electronic and nuclear spin properties in bulk and quantum well semiconductors. In OPNMR, one uses optical pumping with light to create spin-polarized electrons in a semiconductor. The electron spin can be transferred to the nuclear spin bath through the Fermi contact hyperfine interaction which can then be detected by conventional NMR. The resulting NMR signal can be enhanced four to five orders of magnitude or more over the thermal equilibrium signal. In previous work, we studied OPNMR in bulk GaAs where we investigated the strength of the OPNMR signal as a function of the pump laser frequency. This allowed us to study the spin-split valence band. Here we report on OPNMR studies in GaAs/AlGaAs quantum wells. We focus on theoretical calculations for the average electron spin polarization at different photon energies for different values of external magnetic field in both unstrained and strained quantum wells. Our calculations allow us to identify the Landau level transitions which are responsible for the peaks in the photon energy dependence of the OPNMR signal intensity. The calculations are based on the 8- band Pidgeon-Brown model generalized to include the effects of the quantum confinement potential as well as pseudomorphic strain at the interfaces. Optical properties are calculated within the golden rule approximation. Detailed comparison to experiment allows one to accurately determine valence band spin splitting in the quantum wells including the effects of strain.

  11. 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...

  12. Investigation of Sodium Distribution in Phosphate Glasses Using Spin-Echo {sup 23}Na NMR

    Energy Technology Data Exchange (ETDEWEB)

    ALAM, TODD M.; BOYLE, TIMOTHY J.; BROW, RICHARD K.; CLICK, CAROL C.; CONZONE, SAM; McLAUGHLIN, JAY; ZWANZIGER, JOE

    1999-09-16

    The spatial arrangement of sodium cations for a series of sodium phosphate glasses, xNa{sub 2}O(100-x)P{sub 2}O{sub 5} (x<55), were investigated using {sup 23}Na spin-echo NMR spectroscopy. The spin-echo decay rate is a function of the Na-Na homonuclear dipolar coupling and is related to the spatial proximity of neighboring Na nuclei. The spin-echo decay rate in these sodium phosphate glasses increases non-linearly with higher sodium number density, and thus provides a measure of the Na-Na extended range order. The results of these {sup 23}Na NMR experiments are discussed within the context of several structural models, including a decimated crystal lattice model, cubic dilation lattice model, a hard sphere (HS) random distribution model and a pair-wise cluster hard sphere model. While the experimental {sup 23}Na spin-echo M{sub 2} are described adequately by both the decimated lattice and the random HS model, it is demonstrated that the slight non-linear behavior of M{sub 2} as a function of sodium number density is more correctly described by the random distribution in the HS model. At low sodium number densities the experimental M{sub 2} is inconsistent with models incorporating Na-Na clustering. The ability to distinguish between Na-Na clusters and non-clustered distributions becomes more difficult at higher sodium concentrations.

  13. 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.

  14. 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....

  15. NMR spectroscopy in the characterization of asphalt

    Energy Technology Data Exchange (ETDEWEB)

    Jennings, P.W.; Desando, M.A.; Raub, M.F.; Hoberg, J.O.; Moats, R.; Stewart, F.F. (Montana State Univ., Bozeman (United States))

    1990-07-01

    NMR spectrometry represents a probe which can provide many details regarding the structure and functionality of asphalts. This is particularly true if it is combined with chromatography and/or chemical modifications. In this project {sup 1}H, {sup 2}H, {sup 13}C, {sup 19}F, {sup 29}Si, {sup 31}P nuclei and a variety of NMR techniques (1D, 2D, DEPT) have been used to describe a few chemical characteristics of the asphalts and chromatographic fractions therefrom.

  16. Probing oxidative degradation in polymers using {sup 17}O NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Alam, T.M.; Click, C.A.; Assink, R.A.

    1997-09-01

    Understanding the mechanism of oxidative degradation remains an important goal in being able to predict the aging process in polymer materials. Nuclear magnetic resonance (NMR) spectroscopy has previously been utilized to investigate polymer degradation, including both proton ({sup 1}H) and carbon ({sup 13}C) studies. These previous NMR studies, as well as other spectroscopic investigations, are complicated by the almost overwhelming signal arising from the native undegraded polymer. This makes the identification and quantification of degradation species at small concentrations difficult. In this note we discuss recent investigation into the use of oxygen ({sup 17}O) NMR spectroscopy to probe the oxidative degradation process in polymers at a molecular level. Due to the low natural abundance (0.037%) and a nuclear spin of I=5/2 possessing an appreciable quadrupolar moment, the use of {sup 17}O NMR in polymer investigations has been limited. By utilizing synthetically enriched oxygen gas during the accelerated aging process, both the difficulties of low natural abundance and background interference signals are eliminated. For enriched samples {sup 17}O NMR spectra now provide a unique probe since all of the observed NMR resonances are the direct result of oxidative degradation.

  17. NMR evidence for peculiar spin gaps in a doped S=1/2 Heisenberg spin chain

    Energy Technology Data Exchange (ETDEWEB)

    Utz, Yannic; Rudisch, Christian; Hammerath, Franziska; Grafe, Hans-Joachim; Mohan, Ashwin; Ribeiro, Patrick; Hess, Christian; Wolter, Anja; Kataev, Vladislav; Nishimoto, Satoshi; Drechsler, Stefan-Ludwig; Buechner, Bernd [IFW Dresden (Germany); Singh, Surjeet [Indian Institute of Science Education and Research, Pune (India); Saint-Martin, Romuald; Revcolevschi, Alexandre [Laboratoire de Physico-Chimie de l' Etat Solide, Universite Paris-Sud, Orsay (France)

    2012-07-01

    We present {sup 63}Cu Nuclear Magnetic Resonance (NMR) measurements on undoped, Ca-doped and Ni-doped SrCuO{sub 2} single crystals. SrCuO{sub 2} is a good realization of a one-dimensional S=1/2 Heisenberg spin chain. This is manifested by the theoretically-expected temperature-independent NMR spin-lattice relaxation rate T{sub 1}{sup -1}. In Sr{sub 0.9}Ca{sub 0.1}CuO{sub 2} an exponential decrease of T{sub 1}{sup -1} below 90 K evidences the opening of a gap in the spin excitation spectrum, which amounts to {Delta}=50 K. DMRG calculations are presented to discuss the origin of this spin gap. New results on SrCu{sub 0.99}Ni{sub 0.01}O{sub 2} also indicate the presence of a spin gap, which is twice as large as in Sr{sub 0.9}Ca{sub 0.1}CuO{sub 2}, despite the minor doping level of Ni compared to Ca. We discuss different possible impacts of Ca (S=0) and Ni (S=1) doping on structural and magnetic properties of the parent compound.

  18. Refocused continuous-wave decoupling: A new approach to heteronuclear dipolar decoupling in solid-state NMR spectroscopy

    DEFF Research Database (Denmark)

    Vinther, Joachim Møllesøe; Nielsen, Anders B.; Bjerring, Morten

    2012-01-01

    A novel strategy for heteronuclear dipolar decoupling in magic-angle spinning solid-state NMR spectroscopy is presented, which eliminates residual static high-order terms in the effective Hamiltonian originating from interactions between oscillating dipolar and anisotropic shielding tensors. The ...

  19. Cell signaling, post-translational protein modifications and NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Theillet, Francois-Xavier [In-cell NMR Group, Department of NMR-Supported Structural Biology, Leibniz Institute of Molecular Pharmacology (FMP Berlin) (Germany); Smet-Nocca, Caroline [Universite Lille Nord de France, CNRS UMR 8576 (France); Liokatis, Stamatios; Thongwichian, Rossukon; Kosten, Jonas [In-cell NMR Group, Department of NMR-Supported Structural Biology, Leibniz Institute of Molecular Pharmacology (FMP Berlin) (Germany); Yoon, Mi-Kyung; Kriwacki, Richard W. [St. Jude Children' s Research Hospital, Department of Structural Biology (United States); Landrieu, Isabelle; Lippens, Guy [Universite Lille Nord de France, CNRS UMR 8576 (France); Selenko, Philipp, E-mail: selenko@fmp-berlin.de [In-cell NMR Group, Department of NMR-Supported Structural Biology, Leibniz Institute of Molecular Pharmacology (FMP Berlin) (Germany)

    2012-11-15

    Post-translationally modified proteins make up the majority of the proteome and establish, to a large part, the impressive level of functional diversity in higher, multi-cellular organisms. Most eukaryotic post-translational protein modifications (PTMs) denote reversible, covalent additions of small chemical entities such as phosphate-, acyl-, alkyl- and glycosyl-groups onto selected subsets of modifiable amino acids. In turn, these modifications induce highly specific changes in the chemical environments of individual protein residues, which are readily detected by high-resolution NMR spectroscopy. In the following, we provide a concise compendium of NMR characteristics of the main types of eukaryotic PTMs: serine, threonine, tyrosine and histidine phosphorylation, lysine acetylation, lysine and arginine methylation, and serine, threonine O-glycosylation. We further delineate the previously uncharacterized NMR properties of lysine propionylation, butyrylation, succinylation, malonylation and crotonylation, which, altogether, define an initial reference frame for comprehensive PTM studies by high-resolution NMR spectroscopy.

  20. Spin-spin cross relaxation and spin-Hamiltonian spectroscopy by optical pumping of Pr/sup 3+/:LaF3

    International Nuclear Information System (INIS)

    Lukac, M.; Otto, F.W.; Hahn, E.L.

    1989-01-01

    We report the observation of an anticrossing in solid-state laser spectroscopy produced by cross relaxation. Spin-spin cross relaxation between the /sup 141/Pr- and /sup 19/F-spin reservoirs in Pr/sup 3+/:LaF 3 and its influence on the /sup 141/Pr NMR spectrum is detected by means of optical pumping. The technique employed combines optical pumping and hole burning with either external magnetic field sweep or rf resonance saturation in order to produce slow transient changes in resonant laser transmission. At a certain value of the external Zeeman field, where the energy-level splittings of Pr and F spins match, a level repulsion and discontinuity of the Pr/sup 3+/ NMR lines is observed. This effect is interpreted as the ''anticrossing'' of the combined Pr-F spin-spin reservoir energy states. The Zeeman-quadrupole-Hamiltonian spectrum of the hyperfine optical ground states of Pr/sup 3+/:LaF 3 is mapped out over a wide range of Zeeman magnetic fields. A new scheme is proposed for dynamic polarization of nuclei by means of optical pumping, based on resonant cross relaxation between rare spins and spin reservoirs

  1. High-Sensitivity Rheo-NMR Spectroscopy for Protein Studies.

    Science.gov (United States)

    Morimoto, Daichi; Walinda, Erik; Iwakawa, Naoto; Nishizawa, Mayu; Kawata, Yasushi; Yamamoto, Akihiko; Shirakawa, Masahiro; Scheler, Ulrich; Sugase, Kenji

    2017-07-18

    Shear stress can induce structural deformation of proteins, which might result in aggregate formation. Rheo-NMR spectroscopy has the potential to monitor structural changes in proteins under shear stress at the atomic level; however, existing Rheo-NMR methodologies have insufficient sensitivity to probe protein structure and dynamics. Here we present a simple and versatile approach to Rheo-NMR, which maximizes sensitivity by using a spectrometer equipped with a cryogenic probe. As a result, the sensitivity of the instrument ranks highest among the Rheo-NMR spectrometers reported so far. We demonstrate that the newly developed Rheo-NMR instrument can acquire high-quality relaxation data for a protein under shear stress and can trace structural changes in a protein during fibril formation in real time. The described approach will facilitate rheological studies on protein structural deformation, thereby aiding a physical understanding of shear-induced amyloid fibril formation.

  2. A primer to nutritional metabolomics by NMR spectroscopy and chemometrics

    DEFF Research Database (Denmark)

    Savorani, Francesco; Rasmussen, Morten Arendt; Mikkelsen, Mette Skau

    2013-01-01

    structures for multivariate pattern recognition methods and (3) NMR for providing a unique fingerprint of the lipoprotein status of the subject. For the first time in history, by combining NMR spectroscopy and chemometrics we are able to perform inductive nutritional research as a complement to the deductive......This paper outlines the advantages and disadvantages of using high throughput NMR metabolomics for nutritional studies with emphasis on the workflow and data analytical methods for generation of new knowledge. The paper describes one-by-one the major research activities in the interdisciplinary...

  3. Structures of Biomolecules by NMR Spectroscopy

    Indian Academy of Sciences (India)

    IAS Admin

    GENERAL | ARTICLE integral part of NMR-based structural biology research. A num- ber of computational tools are being developed which utilize such information from BMRB and PDB at various stages of the structure determination process. 2. An Overview of the Structure Determination Process. A flowchart of the different ...

  4. Spin-rotation and NMR shielding constants in HCl

    International Nuclear Information System (INIS)

    Jaszuński, Michał; Repisky, Michal; Demissie, Taye B.; Komorovsky, Stanislav; Malkin, Elena; Ruud, Kenneth; Garbacz, Piotr; Jackowski, Karol; Makulski, Włodzimierz

    2013-01-01

    The spin-rotation and nuclear magnetic shielding constants are analysed for both nuclei in the HCl molecule. Nonrelativistic ab initio calculations at the CCSD(T) level of approximation show that it is essential to include relativistic effects to obtain spin-rotation constants consistent with accurate experimental data. Our best estimates for the spin-rotation constants of 1 H 35 Cl are C Cl   = −53.914 kHz and C H   = 42.672 kHz (for the lowest rovibrational level). For the chlorine shielding constant, the ab initio value computed including the relativistic corrections, σ(Cl) = 976.202 ppm, provides a new absolute shielding scale; for hydrogen we find σ(H) = 31.403 ppm (both at 300 K). Combining the theoretical results with our new gas-phase NMR experimental data allows us to improve the accuracy of the magnetic dipole moments of both chlorine isotopes. For the hydrogen shielding constant, including relativistic effects yields better agreement between experimental and computed values

  5. High-resolution magnetic resonance spectroscopy using a solid-state spin sensor

    Science.gov (United States)

    Glenn, David R.; Bucher, Dominik B.; Lee, Junghyun; Lukin, Mikhail D.; Park, Hongkun; Walsworth, Ronald L.

    2018-03-01

    Quantum systems that consist of solid-state electronic spins can be sensitive detectors of nuclear magnetic resonance (NMR) signals, particularly from very small samples. For example, nitrogen–vacancy centres in diamond have been used to record NMR signals from nanometre-scale samples, with sensitivity sufficient to detect the magnetic field produced by a single protein. However, the best reported spectral resolution for NMR of molecules using nitrogen–vacancy centres is about 100 hertz. This is insufficient to resolve the key spectral identifiers of molecular structure that are critical to NMR applications in chemistry, structural biology and materials research, such as scalar couplings (which require a resolution of less than ten hertz) and small chemical shifts (which require a resolution of around one part per million of the nuclear Larmor frequency). Conventional, inductively detected NMR can provide the necessary high spectral resolution, but its limited sensitivity typically requires millimetre-scale samples, precluding applications that involve smaller samples, such as picolitre-volume chemical analysis or correlated optical and NMR microscopy. Here we demonstrate a measurement technique that uses a solid-state spin sensor (a magnetometer) consisting of an ensemble of nitrogen–vacancy centres in combination with a narrowband synchronized readout protocol to obtain NMR spectral resolution of about one hertz. We use this technique to observe NMR scalar couplings in a micrometre-scale sample volume of approximately ten picolitres. We also use the ensemble of nitrogen–vacancy centres to apply NMR to thermally polarized nuclear spins and resolve chemical-shift spectra from small molecules. Our technique enables analytical NMR spectroscopy at the scale of single cells.

  6. 1H to 13C Energy Transfer in Solid State NMR Spectroscopy of Natural Organic Systems

    Science.gov (United States)

    Berns, Anne E.; Conte, Pellegrino

    2010-05-01

    Cross polarization (CP) magic angle spinning (MAS) 13C-NMR spectroscopy is a solid state NMR technique widely used to study chemical composition of organic materials with low or no solubility in the common deuterated solvents used to run liquid state NMR experiments. Based on the magnetization transfer from abundant nuclei (with spin of 1 -2) having a high gyromagnetic ratio (γ), such as protons, to the less abundant 13C nuclei with low γ values, 13C-CPMAS NMR spectroscopy is often applied in environmental chemistry to obtain quantitative information on the chemical composition of natural organic matter (NOM) (Conte et al., 2004), although its quantitative assessment is still matter of heavy debates. Many authors (Baldock et al., 1997; Conte et al., 1997, 2002; Dria et al., 2002; Kiem et al., 2000; Kögel-Knabner, 2000; Preston, 2001), reported that the application of appropriate instrument setup as well as the use of special pulse sequences and correct spectra elaboration may provide signal intensities that are directly proportional to the amount of nuclei creating a NMR signal. However, many other papers dealt with the quantitative unsuitability of 13C-CPMAS NMR spectroscopy. Among those, Mao et al. (2000), Smernik and Oades (2000 a,b), and Preston (2001) reported that cross-polarized NMR techniques may fail in a complete excitation of the 13C nuclei. In fact, the amount of observable carbons via 13C-CPMAS NMR spectroscopy appeared, in many cases, lower than that measured by a direct observation of the 13C nuclei. As a consequence, cross-polarized NMR techniques may provide spectra where signal distribution may not be representative of the quantitative distribution of the different natural organic matter components. Cross-polarization is obtained after application of an initial 90° x pulse on protons and a further spin lock pulse (along the y axis) having a fixed length (contact time) for both nuclei (1H and 13C) once the Hartmann-Hahn condition is matched

  7. A General Protocol for Temperature Calibration of MAS NMR Probes at Arbitrary Spinning Speeds

    Science.gov (United States)

    Guan, Xudong; Stark, Ruth E.

    2010-01-01

    A protocol using 207Pb NMR of solid lead nitrate was developed to determine the temperature of magic-angle spinning (MAS) NMR probes over a range of nominal set temperatures and spinning speeds. Using BioMAS and fastMAS probes with typical sample spinning rates of 8 and 35 kHz, respectively, empirical equations were devised to predict the respective sample temperatures. These procedures provide a straightforward recipe for temperature calibration of any MAS probe. PMID:21036557

  8. Alternating spin chain compound AgVOAsO4 probed by 75As NMR

    Science.gov (United States)

    Ahmed, N.; Khuntia, P.; Ranjith, K. M.; Rosner, H.; Baenitz, M.; Tsirlin, A. A.; Nath, R.

    2017-12-01

    75As NMR measurements were performed on a polycrystalline sample of spin-1/2 alternating spin chain Heisenberg antiferromagnet AgVOAsO4. The temperature-dependent NMR shift K (T ) , which is a direct measure of the intrinsic spin susceptibility, agrees very well with the spin-1/2 alternating-chain model, justifying the assignment of the spin lattice. From the analysis of K (T ) , magnetic exchange parameters were estimated as follows: the leading exchange J /kB≃38.4 K and the alternation ratio α =J'/J ≃0.69 . The transferred hyperfine coupling between the 75As nucleus and V4 + spins obtained by comparing the NMR shift with the bulk susceptibility amounts to Ahf≃3.3 TμB. The effect of interchain couplings on the low-temperature activated behavior of K (T ) and the spin-lattice relaxation rate 1 /T1 is identified.

  9. Ground-state properties of K-isotopes from laser and $\\beta$-NMR spectroscopy

    CERN Multimedia

    Lievens, P; Rajabali, M M; Krieger, A R

    By combining high-resolution laser spectroscopy with $\\beta$-NMR spectroscopy on polarized K-beams we aim to establish the ground-state spins and magnetic moments of the neutron-rich $^{48,49,50,51}$K isotopes from N=29 to N=32. Spins and magnetic moments of the odd-K isotopes up to N=28 reveal an inversion of the ground-state, from the normal $\\,{I}$=3/2 ($\\pi{d}_{3/2}^{-1}$) in $^{41-45}$K$\\to\\,{I}$=1/2 ($\\pi{s}_{1/2}^{-1}$) in $^{47}$K. This inversion of the proton single particle levels is related to the strong proton $d_{3/2}$ - neutron $f_{7/2}$ interaction which lowers the energy of the $\\pi{d}_{3/2}$ single particle state when filling the $\

  10. Dynamics in photosynthetic transient complexes studied by paramagnetic NMR spectroscopy

    NARCIS (Netherlands)

    Scanu, Sandra

    2013-01-01

    This PhD thesis focuses on fundamental aspects of protein-protein interactions. A multidisciplinary methodology for the detection and visualization of transient, lowly-populated encounter protein complexes is described. The new methodology combined paramagnetic NMR spectroscopy with computational

  11. (Cicer arietinum L.) seeds during germination by NMR spectroscopy

    African Journals Online (AJOL)

    Experiments were conducted to characterize the changes in water status during imbibition by nuclear magnetic resonance (NMR) spectroscopy in chickpea seeds exposed to static magnetic fields of 100 mT for 1 h. Water uptake during seed germination showed three phases with rapid initial hydration phase I, followed by ...

  12. Brain 31P NMR spectroscopy in the conscious rat

    NARCIS (Netherlands)

    Deutz, N. E.; Bovée, W. M.; Chamuleau, R. A.

    1986-01-01

    Using a home-built head-body holder (HBH) which enables in vivo 31P NMR spectroscopy measurements on conscious rats, no significant changes were observed in the cerebral relative concentrations of ATP, phosphocreatine, phosphomonoesters, inorganic phosphate and intracellular pH during pentobarbital

  13. Low-frequency spin dynamics and NMR spin-lattice relaxation in antiferromagnetic rings

    Science.gov (United States)

    Itou, T.; Sagane, T.; Oyamada, A.; Maegawa, S.; Igarashi, S.; Yukawa, Y.

    2011-01-01

    We develop a general theory of the spin dynamics of Heisenberg antiferromagnetic rings (HAFRs) that explains the mechanism of NMR spin-lattice relaxation at low temperatures. In HAFRs, the imaginary parts of the q-summed dynamic spin susceptibilities parallel and perpendicular to an applied static field, χsum∥″(ω) and χsum⊥″(ω), are composed of the sum of many slightly broadened δ-functional modes at many frequencies. The NMR relaxation is caused by the quasielastic mode in χsum∥″(ω) at around zero frequency. This quasielastic mode is characterized by two physical quantities, intensity P0∥ and frequency width Γ0∥. Although P0∥ has to date been assumed to be identical to the uniform static susceptibility, we point out that the two quantities are not identical. Without making this unreliable assumption for P0∥, we demonstrate experimentally how P0∥ and Γ0∥ behave, by analyzing the NMR relaxation rates of two different nuclei, H1 and C13, in a real HAFR. This analysis is more rigorous and thus can be used to estimate Γ0∥ and P0∥ more precisely than previously possible. We find that the temperature dependence of P0∥ exhibits activation-type behavior reflecting the first excitation gap. We also find that Γ0∥ decreases monotonically on cooling but saturates to a nonzero value at zero temperature. This strongly suggests that Γ0∥ is dominated not only by the electron-phonon interactions but also by internanomagnet dipole interactions, which have been neglected to date.

  14. Magnetization and 13C NMR spin-lattice relaxation of nanodiamond powder

    Energy Technology Data Exchange (ETDEWEB)

    Levin, E.M.; Fang, X.W.; Bud' ko, S.L.; Straszheim, W.E.; McCallum, R.W.; Schmidt-Rohr, K.

    2008-02-15

    The bulk magnetization at temperatures of 1.8-400 K and in magnetic fields up to 70 kOe, the ambient temperature {sup 13}C NMR spin-lattice relaxation, T{sub 1,c}, and the elemental composition of three nanodiamond powder samples have been studied. The total magnetization of nanodiamond can be explained in terms of contributions from (1) the diamagnetic effect of carbon, (2) the paramagnetic effect of unpaired electrons present in nanodiamond grains, and (3) ferromagnetic-like and (4) superparamagnetic contributions from Fe-containing particles detected in spatially resolved energy-dispersive spectroscopy. Contributions (1) and (2) are intrinsic to nanodiamond, while contributions (3) and (4) arise from impurities naturally present in detonation nanodiamond samples. {sup 13}C NMR T{sub 1,c} relaxation would be unaffected by the presence of the ferromagnetic particles with the bulk magnetization of {approx} 0.01 emu/g at 300 K. Thus, a reduction of T{sub 1,c} by 3 orders of magnitude compared to natural and synthetic microdiamonds confirms the presence of unpaired electrons in the nanodiamond grains. The spin concentration in nanodiamond powder corresponds to {approx}30 unpaired electrons per {approx}4.6 nm diameter nanodiamond grain.

  15. NMR

    International Nuclear Information System (INIS)

    Kneeland, J.B.; Lee, B.C.P.; Whalen, J.P.; Knowles, R.J.R.; Cahill, P.T.

    1984-01-01

    Although still quite new, NMR imaging has already emerged as a safe, noninvasive, painless, and effective diagnostic modality requiring no ionizing radiation. Also, NMR appears already to have established itself as the method of choice for the examination of the brain spinal cord (excluding herniated disks). Another area in which NMR excels is in the examination of the pelvis. The use of surface coils offers the promise of visualizing structures with resolution unobtainable by any other means. In addition, NMR, with its superb visualization of vascular structures and potential ability to measure flow, may soon revolutionize the diagnosis of cardiovascular disease. Finally, NMR, through biochemically and physiologically based T/sub 1/ and T/sub 2/ indices or through spectroscopy, may provide a means of monitoring therapeutic response so as to permit tailoring of treatment to the individual patient. In short, NMR is today probably at the same stage as the x-ray was in Roentgen's day

  16. (S)Pinning down protein interactions by NMR

    DEFF Research Database (Denmark)

    Teilum, Kaare; Kunze, Micha Ben Achim; Erlendsson, Simon

    2017-01-01

    Protein molecules are highly diverse communication platforms and their interaction repertoire stretches from atoms over small molecules such as sugars and lipids to macromolecules. An important route to understanding molecular communication is to quantitatively describe their interactions....... These types of analyses determine the amounts and proportions of individual constituents that participate in a reaction as well as their rates of reactions and their thermodynamics. Although many different methods are available, there is currently no single method able to quantitatively capture and describe...... all types of protein reactions, which can span orders of magnitudes in affinities, reaction rates and lifetimes of states. As the more versatile technique, solution NMR spectroscopy offers a remarkable catalogue of methods that can be successfully applied to the quantitative as well as qualitative...

  17. 1H NMR spectroscopy-based interventional metabolic phenotyping

    DEFF Research Database (Denmark)

    Lauridsen, Michael B; Bliddal, Henning; Christensen, Robin

    2010-01-01

    -up with assessments of disease activity (DAS-28) and 1H NMR spectroscopy of plasma samples. Discriminant analysis provided evidence that the metabolic profiles predicted disease severity. Cholesterol, lactate, acetylated glycoprotein, and lipid signatures were found to be candidate biomarkers for disease severity.......0007). However, after 31 days of optimized therapy, the two patient groups were not significantly different (P=0.91). The metabolic profiles of both groups of RA patients were different from the healthy subjects. 1H NMR-based metabolic phenotyping of plasma samples in patients with RA is well suited...

  18. Laser spectroscopy and beta-NMR measurements of short-lived Mg isotopes

    CERN Document Server

    Kowalska, M

    2005-01-01

    The feasibility of studying the neutron-rich 29Mg, 31Mg and 33Mg isotopes has been demonstrated with the laser and beta-NMR spectroscopy setup at ISOLDE/CERN. The values of the magnetic moment and the nuclear spin of 31Mg are reported and reveal an intruder ground state. This proves the weakening of N=20 shell gap and places this nucleus inside the so called "island of inversion". The experimental setup and technique, as well as the results, are presented.

  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. In vivo NMR spectroscopy of the liver

    International Nuclear Information System (INIS)

    Jehenson, P.; Cuenod, C.A.; Syrota, A.

    1989-01-01

    The application of in vivo MR spectroscopy to the study of the liver is currently an expanding field of research. Owing to technical difficulties, the results obtained thus far were mainly those of animal observations. Several nuclei have been considered: hydrogen, phosphorus, carbon or fluorine. This non-traumatic method allows following and quantifying the various metabolic pathways, especially during hepatic diseases. The major metabolic pathways, i.e. neoglycogenesis, glycogenolysis, Krebs' cycle, etc., are studied, as well as their alterations during diseases such as ischemia, diabetes or alcoholism. The development of this promising technique requires the cooperation of various clinical and fundamental disciplines [fr

  1. Hydrogen and deuterium NMR of solids by magic angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Eckman, Richard Raymond [Univ. of California, Berkeley, CA (United States)

    1982-10-01

    The nuclear magnetic resonance of solids has long been characterized by very large spectral broadening which arises from internuclear dipole-dipole coupling or the nuclear electric quadrupole interaction. These couplings can obscure the smaller chemical shift interaction and make that information unavailable. Two important and difficult cases are that of hydrogen and deuterium. For example, the homonuclear dipolar broadening, HD, for hydrogen is usually several tens of kilohertz. For deuterium, HD is relatively small; however, the quadrupole interaction causes a broadening which can be hundreds of kilohertz in polycrystalline or amorphous solids. The development of cross polarization, heteronuclear radiofrequency decoupling, and coherent averaging of nuclear spin interactions has provided measurement of chemical shift tensors in solids. Recently, double quantum NMR and double quantum decoupling have led to measurement of deuterium and proton chemical shift tensors, respectively. A general problem of these experiments is the overlapping of the tensor powder pattern spectra of magnetically distinct sites which cannot be resolved. In this work, high resolution NMR of hydrogen and deuterium in solids is demonstrated. For both nuclei, the resonances are narrowed to obtain liquid-like isotropic spectra by high frequency rotation of the sample about an axis inclined at the magic angle, βm = Arccos(3-1/2), with respect to the direction of the external magnetic field. Two approaches have been developed for each nucleus. For deuterium, the powder spectra were narrowed by over three orders of magnitude by magic angle rotation with precise control of β. A second approach was the observation of deuterium double quantum transitions under magic angle rotation. For hydrogen, magic angle rotation alone could be applied to obtain the isotropic spectrum when HD was small. This often occurs naturally when the nuclei are semi-dilute or involved in

  2. NMR Spectroscopy in Glass Science: A Review of the Elements

    Directory of Open Access Journals (Sweden)

    Randall Youngman

    2018-03-01

    Full Text Available The study of inorganic glass structure is critically important for basic glass science and especially the commercial development of glasses for a variety of technological uses. One of the best means by which to achieve this understanding is through application of solid-state nuclear magnetic resonance (NMR spectroscopy, which has a long and interesting history. This technique is element specific, but highly complex, and thus, one of the many inquiries made by non-NMR specialists working in glass science is what type of information and which elements can be studied by this method. This review presents a summary of the different elements that are amenable to the study of glasses by NMR spectroscopy and provides examples of the type of atomic level structural information that can be achieved. It serves to inform the non-specialist working in glass science and technology about some of the benefits and challenges involved in the study of inorganic glass structure using modern, readily-available NMR methods.

  3. 103Rh NMR spectroscopy and its application to rhodium chemistry.

    Science.gov (United States)

    Ernsting, Jan Meine; Gaemers, Sander; Elsevier, Cornelis J

    2004-09-01

    Rhodium is used for a number of large processes that rely on homogeneous rhodium-catalyzed reactions, for instance rhodium-catalyzed hydroformylation of alkenes, carbonylation of methanol to acetic acid and hydrodesulfurization of thiophene derivatives (in crude oil). Many laboratory applications in organometallic chemistry and catalysis involve organorhodium chemistry and a wealth of rhodium coordination compounds is known. For these and other areas, 103Rh NMR spectroscopy appears to be a very useful analytical tool. In this review, most of the literature concerning 103Rh NMR spectroscopy published from 1989 up to and including 2003 has been covered. After an introduction to several experimental methods for the detection of the insensitive 103Rh nucleus, a discussion of factors affecting the transition metal chemical shift is given. Computational aspects and calculations of chemical shifts are also briefly addressed. Next, the application of 103Rh NMR in coordination and organometallic chemistry is elaborated in more detail by highlighting recent developments in measurement and interpretation of 103Rh NMR data, in relation to rhodium-assisted reactions and homogeneous catalysis. The dependence of the 103Rh chemical shift on the ligands at rhodium in the first coordination sphere, on the complex geometry, oxidation state, temperature, solvent and concentration is treated. Several classes of compounds and special cases such as chiral rhodium compounds are reviewed. Finally, a section on scalar coupling to rhodium is provided. 2004 John Wiley & Sons, Ltd.

  4. Multidimensional Solid-State NMR Spectroscopy of Plant Cell Walls

    OpenAIRE

    Wang, Tuo; Phyo, Pyae; Hong, Mei

    2016-01-01

    Plant biomass has become an important source of bio-renewable energy in modern society. The molecular structure of plant cell walls is difficult to characterize by most atomic-resolution techniques due to the insoluble and disordered nature of the cell wall. Solid-state NMR (SSNMR) spectroscopy is uniquely suited for studying native hydrated plant cell walls at the molecular level with chemical resolution. Significant progress has been made in the last five years to elucidate the molecular st...

  5. NMR clinical imaging and spectroscopy: Its impact on nuclear medicine

    International Nuclear Information System (INIS)

    1990-01-01

    This is a collection of four papers describing aspects of past and future use of nuclear magnetic resonance as a clinical diagnostic tool. The four papers are entitled (1) What Does NMR Offer that Nuclear Medicine Does Not? by Jerry W. Froelich, (2) Oncological Imaging: Now, Future and Impact Jerry W. Froelich, (3) Magnetic Resonance Spectroscopy/Spectroscopic Imaging and Nuclear Medicine: Past, Present and Future by H. Cecil Charles, and (4) MR Cardiology: Now, Future and Impact by Robert J. Herfkens

  6. NMR clinical imaging and spectroscopy: Its impact on nuclear medicine

    Energy Technology Data Exchange (ETDEWEB)

    1990-02-02

    This is a collection of four papers describing aspects of past and future use of nuclear magnetic resonance as a clinical diagnostic tool. The four papers are entitled (1) What Does NMR Offer that Nuclear Medicine Does Not? by Jerry W. Froelich, (2) Oncological Imaging: Now, Future and Impact Jerry W. Froelich, (3) Magnetic Resonance Spectroscopy/Spectroscopic Imaging and Nuclear Medicine: Past, Present and Future by H. Cecil Charles, and (4) MR Cardiology: Now, Future and Impact by Robert J. Herfkens.

  7. NMR clinical imaging and spectroscopy: Its impact on nuclear medicine

    Energy Technology Data Exchange (ETDEWEB)

    1990-02-02

    This is a collection of four papers describing aspects of past and future use of nuclear magnetic resonance as a clinical diagnostic tool. The four papers are entitled (1) What Does NMR Offer that Nuclear Medicine Does Not by Jerry W. Froelich, (2) Oncological Imaging: Now, Future and Impact Jerry W. Froelich, (3) Magnetic Resonance Spectroscopy/Spectroscopic Imaging and Nuclear Medicine: Past, Present and Future by H. Cecil Charles, and (4) MR Cardiology: Now, Future and Impact by Robert J. Herfkens.

  8. Improvements in localized proton NMR spectroscopy of human brain. Water suppression, short echo times, and 1 ml resolution

    Science.gov (United States)

    Frahm, J.; Michaelis, T.; Merboldt, K. D.; Bruhn, H.; Gyngell, M. L.; Hänicke, W.

    Considerable technical improvements are reported for localized proton NMR spectroscopy using stimulated echoes. When compared to previous results, proton NMR spectra of the human brain are now obtainable (i) with in vivo water suppression factors of ⩾1000, (ii) with only minor T2 losses and negligible distortions due to J modulation at short echo times of 10-20 ms, and (iii) from volumes of interest as small as 1-8 ml within measuring times of 1-10 min. As a consequence, the detection of cerebral metabolites is greatly facilitated. This particularly applies to the assignment of those resonances (e.g., glutamate, taurine, inositols) that suffer from strong spin-spin coupling at the field strengths commonly in use for NMR in man. Studies of regional metabolite differences, tissue heterogeneity, and focal lesions in patients benefit from the increased spatial resolution and a concomitant reduction of partial volume effects. Localized proton NMR spectroscopy was performed on young healthy volunteers. Experiments were carried out on a 2.0 T whole-body MRI/MRS system using the standard headcoil for both imaging and spectroscopy.

  9. Spin noise spectroscopy on donors in GaAs

    Energy Technology Data Exchange (ETDEWEB)

    Bernien, Hannes; Mueller, Georg; Roemer, Michael; Huebner, Jens; Oestreich, Michael [Institute for Solid State Physics, Gottfried Wilhelm Leibniz University Hannover (Germany)

    2009-07-01

    In recent experiments spin noise spectroscopy (SNS) has proven to be a very sensitive technique to study electron spin dynamics in semiconductors at thermal equilibrium. Here we present SNS-measurements on donor bound electrons in very low doped bulk GaAs. In this environment the donors do not interact with each other and form artificial atoms. We discuss the detection of single donor bound electron spins, which should have extremely long spin relaxation times compared to ensemble spin relaxation times. In further experiments the electron bound to the donor will be used to probe and study the local nuclear magnetic field at the donor site.

  10. Thermal and solvent effects on NMR spectroscopy parameters of a prototypical Chagas disease drug

    International Nuclear Information System (INIS)

    Ramalho, Teodorico C.; Cunha, Elaine F.F. da

    2011-01-01

    Full text. Hydrogen bonds in liquids can be of crucial importance for solvent effects in spectroscopy. We have herein computed the nuclear magnetic spin-spin coupling constants (SSCC) involving 15N and 1H nuclei motivated by the relevance of these couplings for the indirect detection of the 15N chemical shifts. Such nJ(N,H) couplings are now also taken as probes for obtaining structural information in proteins. In this work, we focus on the J-couplings; a complete analysis of the NMR spectral data for the compounds studied can be found in previous papers. Thermal and solvent effects on the SSCCs of metronidazole (1) were studied computationally with appropriate quantum-chemical methods. Metronidazole may serve as a model compound to investigate the influence of solvent molecules on the NMR spin-spin coupling constants in heterocyclic rings. We find a hydrogen bond between 1 and a solvent water molecule that is associated with a bond critical point between the imidazole N-3 atom and a water H atom. AIM analysis indicates this hydrogen bond to be mainly electrostatic in nature. Simple static SSCC calculations in vacuo underestimate the nJ(N-3,H) coupling constants because of the neglect of hydrogen bonding. PCM-based treatments perform reasonably well because of the electrostatic character of the hydrogen bond. For more reliable predictions, it is important to take into account the dynamics of the system and to include nearby solvent molecules explicitly. The reduction of the hyperconjugative interactions involving the sigma CH bond or the sigma * CH antibond (with the coupling nucleus H) that is found in solution appears to be correlated to the reduction of coupling pathways in the imidazole ring. Since nuclear spin orientation information is transferred electronically to the other nuclei in the molecule, experimentally determined J-couplings directly reflect the nature of the chemical bond involved.106,107 Unlike most other NMR properties, which can be understood

  11. Thermal and solvent effects on NMR spectroscopy parameters of a prototypical Chagas disease drug

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2011-07-01

    Full text. Hydrogen bonds in liquids can be of crucial importance for solvent effects in spectroscopy. We have herein computed the nuclear magnetic spin-spin coupling constants (SSCC) involving 15N and 1H nuclei motivated by the relevance of these couplings for the indirect detection of the 15N chemical shifts. Such nJ(N,H) couplings are now also taken as probes for obtaining structural information in proteins. In this work, we focus on the J-couplings; a complete analysis of the NMR spectral data for the compounds studied can be found in previous papers. Thermal and solvent effects on the SSCCs of metronidazole (1) were studied computationally with appropriate quantum-chemical methods. Metronidazole may serve as a model compound to investigate the influence of solvent molecules on the NMR spin-spin coupling constants in heterocyclic rings. We find a hydrogen bond between 1 and a solvent water molecule that is associated with a bond critical point between the imidazole N-3 atom and a water H atom. AIM analysis indicates this hydrogen bond to be mainly electrostatic in nature. Simple static SSCC calculations in vacuo underestimate the nJ(N-3,H) coupling constants because of the neglect of hydrogen bonding. PCM-based treatments perform reasonably well because of the electrostatic character of the hydrogen bond. For more reliable predictions, it is important to take into account the dynamics of the system and to include nearby solvent molecules explicitly. The reduction of the hyperconjugative interactions involving the sigma CH bond or the sigma {sup *}CH antibond (with the coupling nucleus H) that is found in solution appears to be correlated to the reduction of coupling pathways in the imidazole ring. Since nuclear spin orientation information is transferred electronically to the other nuclei in the molecule, experimentally determined J-couplings directly reflect the nature of the chemical bond involved.106,107 Unlike most other NMR properties, which can be

  12. Some new insights into biology and medicine through NMR spectroscopy

    International Nuclear Information System (INIS)

    Radda, G.K.

    1990-01-01

    The contributions to biology and medicine by NMR spectroscopy in vivo require careful definition of the problems that are studied. Temporal and spatial resolution of the biochemical information obtained are the key to success, although the latter is limited owing to low sensitivity and small concentrations of the metabolites studied. Using 31 P NMR investigations in four areas are described. Control of energetics by ADP in normal and diseased muscle is shown to be important. Enzyme catalysed fluxes are obtained for creatine kinase and ATP synthase in muscle and in the human brain enzyme activity maps are derived. The measurements on the ionic environment and fluxes for H + , Na + and K + (Rb + ) give us new information about the role of ions in cell proliferation (e.g. in cancer) and hypertension. Molecular architecture of phospholipids in vivo is readily observed and is perturbed in the brain in chronic head injury and demyelination. (author)

  13. 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.

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

    Science.gov (United States)

    Minch, Michael J.

    1998-02-01

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

  15. NMR with generalized dynamics of spin and spatial coordinates

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Chang Jae

    1987-11-01

    This work is concerned with theoretical and experimental aspects of the generalized dynamics of nuclear spin and spatial coordinates under magnetic-field pulses and mechanical motions. The main text begins with an introduction to the concept of ''fictitious'' interactions. A systematic method for constructing fictitious spin-1/2 operators is given. The interaction of spins with a quantized-field is described. The concept of the fictitious interactions under the irradiation of multiple pulses is utilized to design sequences for selectively averaging linear and bilinear operators. Relations between the low-field sequences and high-field iterative schemes are clarified. These relations and the transformation properties of the spin operators are exploited to develop schemes for heteronuclear decoupling of multi-level systems. The resulting schemes are evaluated for heteronuclear decoupling of a dilute spin-1/2 from a spin-1 in liquid crystal samples and from a homonuclear spin-1/2 pair in liquids. A relation between the spin and the spatial variables is discussed. The transformation properties of the spin operators are applied to spatial coordinates and utilized to develop methods for removing the orientational dependence responsible for line broadening in a powder sample. Elimination of the second order quadrupole effects, as well as the first order anisotropies is discussed. It is shown that various sources of line broadening can effectively be eliminated by spinning and/or hopping the sample about judiciously chosen axes along with appropriate radio-frequency pulse sequences.

  16. NMR with generalized dynamics of spin and spatial coordinates

    International Nuclear Information System (INIS)

    Lee, Chang Jae.

    1987-11-01

    This work is concerned with theoretical and experimental aspects of the generalized dynamics of nuclear spin and spatial coordinates under magnetic-field pulses and mechanical motions. The main text begins with an introduction to the concept of ''fictitious'' interactions. A systematic method for constructing fictitious spin-1/2 operators is given. The interaction of spins with a quantized-field is described. The concept of the fictitious interactions under the irradiation of multiple pulses is utilized to design sequences for selectively averaging linear and bilinear operators. Relations between the low-field sequences and high-field iterative schemes are clarified. These relations and the transformation properties of the spin operators are exploited to develop schemes for heteronuclear decoupling of multi-level systems. The resulting schemes are evaluated for heteronuclear decoupling of a dilute spin-1/2 from a spin-1 in liquid crystal samples and from a homonuclear spin-1/2 pair in liquids. A relation between the spin and the spatial variables is discussed. The transformation properties of the spin operators are applied to spatial coordinates and utilized to develop methods for removing the orientational dependence responsible for line broadening in a powder sample. Elimination of the second order quadrupole effects, as well as the first order anisotropies is discussed. It is shown that various sources of line broadening can effectively be eliminated by spinning and/or hopping the sample about judiciously chosen axes along with appropriate radio-frequency pulse sequences

  17. Spin noise spectroscopy from acoustic to GHz frequencies

    Science.gov (United States)

    Hübner, Jens

    2010-03-01

    Performing perturbation free measurements on semiconductor quantum systems has long been banished to textbooks on quantum mechanics. The emergent technique of spin noise spectroscopy is challenging this restriction. Empowered only by the ever present intrinsic spin fluctuation dynamics in thermal equilibrium, spin noise spectroscopy is capable to directly deduce several physical properties of carriers spins in semiconductors from these fluctuations. Originating from spin noise measurements on alkali metal vapors in quantum optics [1] the method has become a powerful technique to unravel the intrinsic spin dynamics in semiconductors [2]. In this talk I will present the recent progress of spin noise spectroscopy and how it is used to monitor the spin dynamic in semiconductor quantum wells at thermal equilibrium and as a consequence thereof directly detect the spatial dynamics of the carriers being marked with their own spin on a microscopic scale [3]. Further I will present measurements of how the non-perturbative nature of spin noise spectroscopy gives valuable insight into the delicate dependence of the spin relaxation time of electrons on doping density and temperature in semiconductors n-doped in the vicinity of the metal-insulator transition where hyperfine and intra-band depolarization compete [4]. Also the measurement bandwidth can be extended to GHz frequencies by ultrafast optical probing [5] yielding in conjunction with depth resolved spin noise measurements insights into the origin of inhomogeneous spin dephasing effects at high magnetic fields [5]. Additionally I will present how spin noise spectroscopy can be employed to spatially depth resolve doping profiles with optical resolution [6] and give a summary on easy to implement techniques of spin noise spectroscopy at acoustic frequencies in alkali metal vapors. [4pt] [1] E. Aleksandrov and V. Zapassky, Zh. Eksp. Teor. Fiz. 81, 132 (1981); S. A. Crooker, D. G. Rickel, A. V. Balatsky, and D. L. Smith

  18. 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.

  19. Theoretical investigations of quantum correlations in NMR multiple-pulse spin-locking experiments

    Science.gov (United States)

    Gerasev, S. A.; Fedorova, A. V.; Fel'dman, E. B.; Kuznetsova, E. I.

    2018-04-01

    Quantum correlations are investigated theoretically in a two-spin system with the dipole-dipole interactions in the NMR multiple-pulse spin-locking experiments. We consider two schemes of the multiple-pulse spin-locking. The first scheme consists of π /2-pulses only and the delays between the pulses can differ. The second scheme contains φ-pulses (0Quantum discord is obtained for the first scheme of the multiple-pulse spin-locking experiment at different temperatures.

  20. Toward high-resolution NMR spectroscopy of microscopic liquid samples

    Energy Technology Data Exchange (ETDEWEB)

    Butler, Mark C.; Mehta, Hardeep S.; Chen, Ying; Reardon, Patrick N.; Renslow, Ryan S.; Khbeis, Michael; Irish, Duane; Mueller, Karl T.

    2017-01-01

    A longstanding limitation of high-resolution NMR spectroscopy is the requirement for samples to have macroscopic dimensions. Commercial probes, for example, are designed for volumes of at least 5 mL, in spite of decades of work directed toward the goal of miniaturization. Progress in miniaturizing inductive detectors has been limited by a perceived need to meet two technical requirements: (1) minimal separation between the sample and the detector, which is essential for sensitivity, and (2) near-perfect magnetic-field homogeneity at the sample, which is typically needed for spectral resolution. The first of these requirements is real, but the second can be relaxed, as we demonstrate here. By using pulse sequences that yield high-resolution spectra in an inhomogeneous field, we eliminate the need for near-perfect field homogeneity and the accompanying requirement for susceptibility matching of microfabricated detector components. With this requirement removed, typical imperfections in microfabricated components can be tolerated, and detector dimensions can be matched to those of the sample, even for samples of volume << 5 uL. Pulse sequences that are robust to field inhomogeneity thus enable small-volume detection with optimal sensitivity. We illustrate the potential of this approach to miniaturization by presenting spectra acquired with a flat-wire detector that can easily be scaled to subnanoliter volumes. In particular, we report high-resolution NMR spectroscopy of an alanine sample of volume 500 pL.

  1. Potential of NMR Spectroscopy in the Characterization of Nonconventional Oils

    Directory of Open Access Journals (Sweden)

    Abdul Majid

    2014-01-01

    Full Text Available NMR spectroscopy was applied for the characterization of two biomass based pyrolysis oil samples. The samples were extracted in various solvents and the extracts were investigated by both 1H and 13C NMR spectroscopy. Subsequent evaluation of the integrated analytical data revealed chemical information regarding semiquantitative estimation of various functional groups. This information could not have been obtained readily from the individual spectroscopic techniques. Semiquantitative estimation of the various functional groups allowed a comparison of the extraction efficiency of these groups in various solvents. The method is based on the premise that although the number of individual molecular species in pyrolysis oil liquid is large, most of these species are composed of a limited number of functional groups. The methodology provided information on the concentration of chemical functionalities that are potentially useful for synthetic modifications and may help to guide the use of pyrolysis oil as a chemical feedstock. The approach described is expected to be generally applicable to complex mixture of hydrocarbon oils such as bio-oils, oil sands bitumen, and coal pyrolysis oils.

  2. Unilateral NMR, 13C CPMAS NMR spectroscopy and micro-analytical techniques for studying the materials and state of conservation of an ancient Egyptian wooden sarcophagus.

    Science.gov (United States)

    Proietti, Noemi; Presciutti, Federica; Di Tullio, Valeria; Doherty, Brenda; Marinelli, Anna Maria; Provinciali, Barbara; Macchioni, Nicola; Capitani, Donatella; Miliani, Costanza

    2011-03-01

    A multi-technique approach was employed to study a decorated Egyptian wooden sarcophagus (XXV-XXVI dynasty, Third Intermediate Period), belonging to the Museo del Vicino Oriente of the Sapienza University of Rome. Portable non-invasive unilateral NMR was applied to evaluate the conservation state of the sarcophagus. Moreover, using unilateral NMR, a non-invasive analytical protocol was established to detect the presence of organic substances on the surface and/or embedded in the wooden matrix. This protocol allowed for an educated sampling campaign aimed at further investigating the state of degradation of the wood and the presence of organic substances by (13)C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The composition of the painted layer was analysed by optical microscopy (OM), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), Raman and surface enhanced (resonance) Raman spectroscopy (SERS/SERRS), infrared and GC-MS techniques, evidencing original components such as clay minerals, Egyptian green, indigo, natural gums, and also highlighting restoration pigments and alteration compounds. The identification of the wood, of great value for the reconstruction of the history of the artwork, was achieved by means of optical microscopy.

  3. NMR in an electric field: A bulk probe of the hidden spin and orbital polarizations

    OpenAIRE

    Ramírez-Ruiz, Jorge; Boutin, Samuel; Garate, Ion

    2017-01-01

    Recent theoretical work has established the presence of hidden spin and orbital textures in non-magnetic materials with inversion symmetry. Here, we propose that these textures can be detected by nuclear magnetic resonance (NMR) measurements carried out in the presence of an electric field. In crystals with hidden polarizations, a uniform electric field produces a staggered magnetic field that points to opposite directions at atomic sites related by spatial inversion. As a result, the NMR res...

  4. Inelastic electron tunneling spectroscopy of a single nuclear spin.

    Science.gov (United States)

    Delgado, F; Fernández-Rossier, J

    2011-08-12

    Detection of a single nuclear spin constitutes an outstanding problem in different fields of physics such as quantum computing or magnetic imaging. Here we show that the energy levels of a single nuclear spin can be measured by means of inelastic electron tunneling spectroscopy (IETS). We consider two different systems, a magnetic adatom probed with scanning tunneling microscopy and a single Bi dopant in a silicon nanotransistor. We find that the hyperfine coupling opens new transport channels which can be resolved at experimentally accessible temperatures. Our simulations evince that IETS yields information about the occupations of the nuclear spin states, paving the way towards transport-detected single nuclear spin resonance.

  5. LipSpin: A New Bioinformatics Tool for Quantitative 1H NMR Lipid Profiling.

    Science.gov (United States)

    Barrilero, Rubén; Gil, Miriam; Amigó, Núria; Dias, Cintia B; Wood, Lisa G; Garg, Manohar L; Ribalta, Josep; Heras, Mercedes; Vinaixa, Maria; Correig, Xavier

    2018-02-06

    The structural similarity among lipid species and the low sensitivity and spectral resolution of nuclear magnetic resonance (NMR) have traditionally hampered the routine use of 1 H NMR lipid profiling of complex biological samples in metabolomics, which remains mostly manual and lacks freely available bioinformatics tools. However, 1 H NMR lipid profiling provides fast quantitative screening of major lipid classes (fatty acids, glycerolipids, phospholipids, and sterols) and some individual species and has been used in several clinical and nutritional studies, leading to improved risk prediction models. In this Article, we present LipSpin, a free and open-source bioinformatics tool for quantitative 1 H NMR lipid profiling. LipSpin implements a constrained line shape fitting algorithm based on voigt profiles and spectral templates from spectra of lipid standards, which automates the analysis of severely overlapped spectral regions and lipid signals with complex coupling patterns. LipSpin provides the most detailed quantification of fatty acid families and choline phospholipids in serum lipid samples by 1 H NMR to date. Moreover, analytical and clinical results using LipSpin quantifications conform with other techniques commonly used for lipid analysis.

  6. The eigenmode perspective of NMR spin relaxation in proteins

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, Yury E., E-mail: shapiro@nmrsgi4.ls.biu.ac.il, E-mail: eva.meirovitch@biu.ac.il; Meirovitch, Eva, E-mail: shapiro@nmrsgi4.ls.biu.ac.il, E-mail: eva.meirovitch@biu.ac.il [The Mina and Everard Goodman Faculty of Life Sciences, Bar-Ilan University, Ramat-Gan 52900-02 (Israel)

    2013-12-14

    We developed in recent years the two-body (protein and probe) coupled-rotator slowly relaxing local structure (SRLS) approach for elucidating protein dynamics from NMR spin relaxation. So far we used as descriptors the set of physical parameters that enter the SRLS model. They include the global (protein-related) diffusion tensor, D{sub 1}, the local (probe-related) diffusion tensor, D{sub 2}, and the local coupling/ordering potential, u. As common in analyzes based on mesoscopic dynamic models, these parameters have been determined with data-fitting techniques. In this study, we describe structural dynamics in terms of the eigenmodes comprising the SRLS time correlation functions (TCFs) generated by using the best-fit parameters as input to the Smoluchowski equation. An eigenmode is a weighted exponential with decay constant given by an eigenvalue of the Smoluchowski operator, and weighting factor determined by the corresponding eigenvector. Obviously, both quantities depend on the SRLS parameters as determined by the SRLS model. Unlike the set of best-fit parameters, the eigenmodes represent patterns of motion of the probe-protein system. The following new information is obtained for the typical probe, the {sup 15}N−{sup 1}H bond. Two eigenmodes, associated with the protein and the probe, dominate when the time scale separation is large (i.e., D{sub 2} ≫ D{sub 1}), the tensorial properties are simple, and the local potential is either very strong or very weak. When the potential exceeds these limits while the remaining conditions are preserved, new eigenmodes arise. The multi-exponentiality of the TCFs is associated in this case with the restricted nature of the local motion. When the time scale separation is no longer large, the rotational degrees of freedom of the protein and the probe become statistically dependent (coupled dynamically). The multi-exponentiality of the TCFs is associated in this case with the restricted nature of both the local and the

  7. The eigenmode perspective of NMR spin relaxation in proteins

    Science.gov (United States)

    Shapiro, Yury E.; Meirovitch, Eva

    2013-12-01

    We developed in recent years the two-body (protein and probe) coupled-rotator slowly relaxing local structure (SRLS) approach for elucidating protein dynamics from NMR spin relaxation. So far we used as descriptors the set of physical parameters that enter the SRLS model. They include the global (protein-related) diffusion tensor, D1, the local (probe-related) diffusion tensor, D2, and the local coupling/ordering potential, u. As common in analyzes based on mesoscopic dynamic models, these parameters have been determined with data-fitting techniques. In this study, we describe structural dynamics in terms of the eigenmodes comprising the SRLS time correlation functions (TCFs) generated by using the best-fit parameters as input to the Smoluchowski equation. An eigenmode is a weighted exponential with decay constant given by an eigenvalue of the Smoluchowski operator, and weighting factor determined by the corresponding eigenvector. Obviously, both quantities depend on the SRLS parameters as determined by the SRLS model. Unlike the set of best-fit parameters, the eigenmodes represent patterns of motion of the probe-protein system. The following new information is obtained for the typical probe, the 15N-1H bond. Two eigenmodes, associated with the protein and the probe, dominate when the time scale separation is large (i.e., D2 ≫ D1), the tensorial properties are simple, and the local potential is either very strong or very weak. When the potential exceeds these limits while the remaining conditions are preserved, new eigenmodes arise. The multi-exponentiality of the TCFs is associated in this case with the restricted nature of the local motion. When the time scale separation is no longer large, the rotational degrees of freedom of the protein and the probe become statistically dependent (coupled dynamically). The multi-exponentiality of the TCFs is associated in this case with the restricted nature of both the local and the global motion. The effects of local

  8. β -detected NMR spin relaxation in a thin film heterostructure of ferromagnetic EuO

    Science.gov (United States)

    MacFarlane, W. A.; Song, Q.; Ingle, N. J. C.; Chow, K. H.; Egilmez, M.; Fan, I.; Hossain, M. D.; Kiefl, R. F.; Levy, C. D. P.; Morris, G. D.; Parolin, T. J.; Pearson, M. R.; Saadaoui, H.; Salman, Z.; Wang, D.

    2015-08-01

    We present β -detected NMR measurements of the spin-lattice relaxation of +8Li implanted into an epitaxial heterostructure based on a 100 nm thick film of ferromagnetic (FM) EuO as a function of temperature through its FM transition. In the FM state, the spin-lattice relaxation rate follows the same temperature dependence, determined by magnon scattering mechanisms, observed in the bulk by 153Eu NMR, but above 40 K, the signal is wiped out. We also find that +8Li stopped in material adjacent to the magnetic layer exhibits spin relaxation related to the critical slowing of the Eu spins. A particularly strong relaxation in the Au overlayer suggests an unusual strong nonlocal coupling mechanism to 8Li in the metal.

  9. Homogenization of Doppler broadening in spin-noise spectroscopy

    Science.gov (United States)

    Petrov, M. Yu.; Ryzhov, I. I.; Smirnov, D. S.; Belyaev, L. Yu.; Potekhin, R. A.; Glazov, M. M.; Kulyasov, V. N.; Kozlov, G. G.; Aleksandrov, E. B.; Zapasskii, V. S.

    2018-03-01

    The spin-noise spectroscopy, being a nonperturbative linear optics tool, is still reputed to reveal a number of capabilities specific to nonlinear optics techniques. The effect of the Doppler broadening homogenization discovered in this work essentially widens these unique properties of spin-noise spectroscopy. We investigate spin noise of a classical system—cesium atoms vapor with admixture of buffer gas—by measuring the spin-induced Faraday rotation fluctuations in the region of D 2 line. The line, under our experimental conditions, is strongly inhomogeneously broadened due to the Doppler effect. Despite that, optical spectrum of the spin-noise power has the shape typical for the homogeneously broadened line with a dip at the line center. This fact is in stark contrast with the results of previous studies of inhomogeneous quantum dot ensembles and Doppler broadened atomic systems. In addition, the two-color spin-noise measurements have shown, in a highly spectacular way, that fluctuations of the Faraday rotation within the line are either correlated or anticorrelated depending on whether the two wavelengths lie on the same side or on different sides of the resonance. The experimental data are interpreted in the frame of the developed theoretical model which takes into account both kinetics and spin dynamics of Cs atoms. It is shown that the unexpected behavior of the Faraday rotation noise spectra and effective homogenization of the optical transition in the spin-noise measurements are related to smallness of the momentum relaxation time of the atoms as compared with their spin-relaxation time. Our findings demonstrate abilities of spin-noise spectroscopy for studying dynamic properties of inhomogeneously broadened ensembles of randomly moving spins.

  10. The Development of 460 GHz gyrotrons for 700 MHz DNP-NMR spectroscopy

    Science.gov (United States)

    Idehara, T.; Tatematsu, Y.; Yamaguchi, Y.; Khutoryan, E. M.; Kuleshov, A. N.; Ueda, K.; Matsuki, Y.; Fujiwara, T.

    2015-07-01

    Two demountable gyrotrons with internal mode converters were developded as sub-THz radiation sources for 700 MHz DNP (Dynamic Nuclear Polarization) enhanced NMR spectroscopy. Experimental study on the DNP-NMR spectroscopy will be carried out in Osaka University, Institute for Protein Research, as a collaboration with FIR UF. Both gyrotrons operate near 460 GHz and the output CW power measured at the end of transmission system made by circular waveguides is typically 20 to 30 watts. One of them named Gyrotron FU CW GVI (we are using "Gyrotron FU CW GO-1" as an official name in Osaka University) is designed to have a special function of high speed frequency modulation δ f within 100 MHz band. This will expand excitable band width of ESR and increase the number of electron spins contributing to DNP. The other gyrotron, Gyrotron FU CW GVIA ("Gyrotron FU CW GO-II") has a function of frequency tunability Δ f in the range of wider than 1.5 GHz, which is achieved in steady state by changing magnetic field intensity. This function should be used for adjusting the output frequency at the optimal value to achieve the highest enhancement factor of DNP.

  11. Effectively doubling the magnetic field in spin-1/2-spin-1, HSQC, HDQC, coupled HSQC, and coupled HDQC in solution NMR.

    Science.gov (United States)

    Shekar, S Chandra; Backer, Jonathan M; Girvin, Mark E

    2008-05-14

    Pulse sequences for spin-1/2-spin-1 pair heteronuclear single quantum correlation (HSQC), heteronuclear double quantum correlation (HDQC), and coupled-HSQC, and coupled-HDQC NMR spectroscopies are outlined, and experimental realization for a (13)C-(2)H pair is demonstrated in solution state. In both the coupled versions, conditions for generation of in-phase and antiphase multiplets in either dimension are arrived at. The patterns and the intensity ratios are explained. The double quantum (2Q) experiments confirm doubling of both the shift frequency and the splitting due to coupling (to spin 1/2) of the 2Q coherence emanating from spin 1. The frequency doubling is equivalent to the corresponding single quantum (1Q) coherence at double the magnetic field strength. The coupling doubling, however, is independent of the magnetic field strength and a signature feature of the 2Q coherence. The ramification of the relative relaxation rates of 1Q and 2Q coherences is discussed.

  12. Effectively doubling the magnetic field in spin-1∕2–spin-1, HSQC, HDQC, coupled HSQC, and coupled HDQC in solution NMR

    Science.gov (United States)

    Chandra Shekar, S.; Backer, Jonathan M.; Girvin, Mark E.

    2008-01-01

    Pulse sequences for spin-1∕2–spin-1 pair heteronuclear single quantum correlation (HSQC), heteronuclear double quantum correlation (HDQC), and coupled-HSQC, and coupled-HDQC NMR spectroscopies are outlined, and experimental realization for a 13C–2H pair is demonstrated in solution state. In both the coupled versions, conditions for generation of in-phase and antiphase multiplets in either dimension are arrived at. The patterns and the intensity ratios are explained. The double quantum (2Q) experiments confirm doubling of both the shift frequency and the splitting due to coupling (to spin 1∕2) of the 2Q coherence emanating from spin 1. The frequency doubling is equivalent to the corresponding single quantum (1Q) coherence at double the magnetic field strength. The coupling doubling, however, is independent of the magnetic field strength and a signature feature of the 2Q coherence. The ramification of the relative relaxation rates of 1Q and 2Q coherences is discussed. PMID:18532820

  13. 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…

  14. Determination of gluconeogenesis in man by the use of deuterium-NMR-spectroscopy

    CERN Document Server

    Rosian, E

    2000-01-01

    The aim of this dissertation is the quantification of the deuterium--distribution in human glucose by the use of the deuterium NMR spectroscopy of deuteriated water. The glucose production in human organism is composed of gluconeogenesis and glycolysis. The quantification of the part of gluconeogenesis on the total glucose production was determined by the use of deuterium NMR spectroscopy. (boteke)

  15. NMR Investigation of beta-Substituted High-Spin and Low-Spin Iron(III) Tetraphenylporphyrins.

    Science.gov (United States)

    Wojaczynski, Jacek; Latos-Grazynski, Lechoslaw; Hrycyk, Witold; Pacholska, Ewa; Rachlewicz, Krystyna; Szterenberg, Ludmila

    1996-11-06

    The NMR spectra of a series of beta-substituted iron(III) tetraphenylporphyrin (2-X-TPP) complexes have been studied to elucidate the relationship between the electron donating/withdrawing properties of the 2-substituent and the (1)H NMR spectral pattern. The electronic nature of the substituent has been significantly varied and covered the -0.6 to 0.8 Hammett constant range. Both high-spin and low-spin complexes of the general formula (2-X-TPP)Fe(III)Cl and [(2-X-TPP)Fe(III)(CN)(2)](-) have been investigated. The (1)H NMR data for the following substituents (X) have been reported: py(+), NO(2), CN, CH(3), BzO (C(6)H(5)COO), H, D, Br, Cl, CH(3), NH(2), NH(3)(+), NHCH(3), OH, and O(-). The (1)H NMR resonances for low-spin dicyano complexes have been completely assigned by a combination of two-dimensional COSY and NOESY experiments. In the case of selected high-spin complexes, the 3-H resonance has been identified by the selective deuteration of all but the 3-H position. The pattern of unambiguously assigned seven pyrrole resonances reflects the asymmetry imposed by 2-substitution and has been used as an unique (1)H NMR spectroscopic probe to map the spin density distribution. The pyrrole isotropic shifts of [(2-X-TPP)Fe(III)(CN)(2)](-) are dominated by the contact term. In order to quantify the substituent effect, the dependence of isotropic shift of all low-spin pyrrole resonances and 3-H high-spin pyrrole resonance versus Hammett constants has been studied. The electronic effect is strongly localized at the beta-substituted pyrrole. The major change of the isotropic shift has also been noted for only one of two adjacent pyrrole rings, i.e., at 7-H and 8-H positions. These neighboring protons, located on a single pyrrole ring, experienced opposite shift changes when electron withdrawing/donating properties were modified. Two other pyrrole rings for all investigated derivatives revealed considerably smaller, substituent related, isotropic shift changes. A long

  16. Microscopic Displacement Imaging with Pulsed Field Gradient Turbo Spin-Echo NMR

    NARCIS (Netherlands)

    Scheenen, T.W.J.; Dusschoten, van D.; Jager, de P.A.; As, van H.

    2000-01-01

    We present a pulse sequence that enables the accurate and spatially resolved measurements of the displacements of spins in a variety of (biological) systems. The pulse sequence combines pulsed field gradient (PFG) NMR with turbo spin–echo (TSE) imaging. It is shown here that by ensuring that the

  17. Recent trends in spin-resolved photoelectron spectroscopy

    Science.gov (United States)

    Okuda, Taichi

    2017-12-01

    Since the discovery of the Rashba effect on crystal surfaces and also the discovery of topological insulators, spin- and angle-resolved photoelectron spectroscopy (SARPES) has become more and more important, as the technique can measure directly the electronic band structure of materials with spin resolution. In the same way that the discovery of high-Tc superconductors promoted the development of high-resolution angle-resolved photoelectron spectroscopy, the discovery of this new class of materials has stimulated the development of new SARPES apparatus with new functions and higher resolution, such as spin vector analysis, ten times higher energy and angular resolution than conventional SARPES, multichannel spin detection, and so on. In addition, the utilization of vacuum ultra violet lasers also opens a pathway to the realization of novel SARPES measurements. In this review, such recent trends in SARPES techniques and measurements will be overviewed.

  18. Recovery of Underwater Resonances by Magnetization Transferred NMR Spectroscopy (RECUR-NMR)

    Science.gov (United States)

    Liu, Maili; Tang, Huiru; Nicholson, Jeremy K.; Lindon, John C.

    2001-11-01

    A method for detecting small molecule NMR resonances under a water peak in biological samples is presented. After high-efficiency solvent suppression using double WATERGATE, either a TOCSY- or ROESY-based coherence transfer sequence is applied to reestablish the resonances close to, or under, water through magnetization transfer using scalar or dipolar coupling, respectively. The use of the TOCSY and ROESY methods ensures an in-phase magnetization transfer, which makes the new approach readily extended for the measurement of transverse relaxation times, internuclear ROEs, and ROE buildup rates. An extension of the new approach for J-resolved spectroscopy is also presented and tested using a sample of human blood plasma.

  19. High spin spectroscopy of 70Ge

    International Nuclear Information System (INIS)

    Kumar Raju, M.; Sugathan, P.; Seshi Reddy, T.; Thirumala Rao, B.V.; Madhusudhana Rao, P.V.; Muralithar, S.; Singh, R.P.; Bhowmik, R.K.

    2011-01-01

    Structure of nuclei in mass 70 region is of interest due to presence of a variety of complex phenomenon. In these nuclei rapid change of nuclear shape with proton and neutron numbers, spin and excitation energy. Valance nucleons in f-p-g shell configuration will drive the nuclei towards high deformations. Relatively large values of quadrupole deformation are evident in the even-even nuclei in this region. Present study is aimed to explore the high spin structure of the 70 Ge nucleus. A negative parity structure was reported in an earlier study

  20. Manifestations of classical physics in the quantum evolution of correlated spin states in pulsed NMR experiments.

    Science.gov (United States)

    Ligare, Martin

    2016-05-01

    Multiple-pulse NMR experiments are a powerful tool for the investigation of molecules with coupled nuclear spins. The product operator formalism provides a way to understand the quantum evolution of an ensemble of weakly coupled spins in such experiments using some of the more intuitive concepts of classical physics and semi-classical vector representations. In this paper I present a new way in which to interpret the quantum evolution of an ensemble of spins. I recast the quantum problem in terms of mixtures of pure states of two spins whose expectation values evolve identically to those of classical moments. Pictorial representations of these classically evolving states provide a way to calculate the time evolution of ensembles of weakly coupled spins without the full machinery of quantum mechanics, offering insight to anyone who understands precession of magnetic moments in magnetic fields.

  1. Theory of single-spin inelastic tunneling spectroscopy.

    Science.gov (United States)

    Fernández-Rossier, J

    2009-06-26

    I show that recent experiments of inelastic scanning tunneling spectroscopy of single and a few magnetic atoms are modeled with a phenomenological spin-assisted tunneling Hamiltonian so that the inelastic dI/dV line shape is related to the spin spectral weight of the magnetic atom. This accounts for the spin selection rules and dI/dV spectra observed experimentally for single Fe and Mn atoms deposited on Cu2N. In the case of chains of Mn atoms it is found necessary to include both first and second-neighbor exchange interactions as well as single-ion anisotropy.

  2. Trans and surface membrane bound zervamicin IIB: 13C-MAOSS-NMR at high spinning speed

    International Nuclear Information System (INIS)

    Raap, J.; Hollander, J.; Ovchinnikova, T. V.; Swischeva, N. V.; Skladnev, D.; Kiihne, S.

    2006-01-01

    Interactions between 15 N-labelled peptides or proteins and lipids can be investigated using membranes aligned on a thin polymer film, which is rolled into a cylinder and inserted into the MAS-NMR rotor. This can be spun at high speed, which is often useful at high field strengths. Unfortunately, substrate films like commercially available polycarbonate or PEEK produce severe overlap with peptide and protein signals in 13 C-MAOSS NMR spectra. We show that a simple house hold foil support allows clear observation of the carbonyl, aromatic and C α signals of peptides and proteins as well as the ester carbonyl and choline signals of phosphocholine lipids. The utility of the new substrate is validated in applications to the membrane active peptide zervamicin IIB. The stability and macroscopic ordering of thin PC10 bilayers was compared with that of thicker POPC bilayers, both supported on the household foil. Sidebands in the 31 P-spectra showed a high degree of alignment of both the supported POPC and PC10 lipid molecules. Compared with POPC, the PC10 lipids are slightly more disordered, most likely due to the increased mobilities of the shorter lipid molecules. This mobility prevents PC10 from forming stable vesicles for MAS studies. The 13 C-peptide peaks were selectively detected in a 13 C-detected 1 H-spin diffusion experiment. Qualitative analysis of build-up curves obtained for different mixing times allowed the transmembrane peptide in PC10 to be distinguished from the surface bound topology in POPC. The 13 C-MAOSS results thus independently confirms previous findings from 15 N spectroscopy [Bechinger, B., Skladnev, D.A., Ogrel, A., Li, X., Rogozhkina, E.V., Ovchinnikova, T.V., O'Neil, J.D.J. and Raap, J. (2001) Biochemistry, 40, 9428-9437]. In summary, application of house hold foil opens the possibility of measuring high resolution 13 C-NMR spectra of peptides and proteins in well ordered membranes, which are required to determine the secondary and

  3. High resolution NMR spectroscopy of synthetic polymers in bulk

    International Nuclear Information System (INIS)

    Komorski, R.A.

    1986-01-01

    The contents of this book are: Overview of high-resolution NMR of solid polymers; High-resolution NMR of glassy amorphous polymers; Carbon-13 solid-state NMR of semicrystalline polymers; Conformational analysis of polymers of solid-state NMR; High-resolution NMR studies of oriented polymers; High-resolution solid-state NMR of protons in polymers; and Deuterium NMR of solid polymers. This work brings together the various approaches for high-resolution NMR studies of bulk polymers into one volume. Heavy emphasis is, of course, given to 13C NMR studies both above and below Tg. Standard high-power pulse and wide-line techniques are not covered

  4. PGI chicory (Cichorium intybus L.) traceability by means of HRMAS-NMR spectroscopy: a preliminary study.

    Science.gov (United States)

    Ritota, Mena; Casciani, Lorena; Valentini, Massimiliano

    2013-05-01

    Analytical traceability of PGI and PDO foods (Protected Geographical Indication and Protected Denomination Origin respectively) is one of the most challenging tasks of current applied research. Here we proposed a metabolomic approach based on the combination of (1)H high-resolution magic angle spinning-nuclear magnetic resonance (HRMAS-NMR) spectroscopy with multivariate analysis, i.e. PLS-DA, as a reliable tool for the traceability of Italian PGI chicories (Cichorium intybus L.), i.e. Radicchio Rosso di Treviso and Radicchio Variegato di Castelfranco, also known as red and red-spotted, respectively. The metabolic profile was gained by means of HRMAS-NMR, and multivariate data analysis allowed us to build statistical models capable of providing clear discrimination among the two varieties and classification according to the geographical origin. Based on Variable Importance in Projection values, the molecular markers for classifying the different types of red chicories analysed were found accounting for both the cultivar and the place of origin. © 2012 Society of Chemical Industry.

  5. In situ and ex situ low-field NMR spectroscopy and MRI endowed by SABRE hyperpolarization.

    Science.gov (United States)

    Barskiy, Danila A; Kovtunov, Kirill V; Koptyug, Igor V; He, Ping; Groome, Kirsten A; Best, Quinn A; Shi, Fan; Goodson, Boyd M; Shchepin, Roman V; Truong, Milton L; Coffey, Aaron M; Waddell, Kevin W; Chekmenev, Eduard Y

    2014-12-15

    By using 5.75 and 47.5 mT nuclear magnetic resonance (NMR) spectroscopy, up to 10(5)-fold sensitivity enhancement through signal amplification by reversible exchange (SABRE) was enabled, and subsecond temporal resolution was used to monitor an exchange reaction that resulted in the buildup and decay of hyperpolarized species after parahydrogen bubbling. We demonstrated the high-resolution low-field proton magnetic resonance imaging (MRI) of pyridine in a 47.5 mT magnetic field endowed by SABRE. Molecular imaging (i.e. imaging of dilute hyperpolarized substances rather than the bulk medium) was conducted in two regimes: in situ real-time MRI of the reaction mixture (in which pyridine was hyperpolarized), and ex situ MRI (in which hyperpolarization decays) of the liquid hyperpolarized product. Low-field (milli-Tesla range, e.g. 5.75 and 47.5 mT used in this study) parahydrogen-enhanced NMR and MRI, which are free from the limitations of high-field magnetic resonance (including susceptibility-induced gradients of the static magnetic field at phase interfaces), potentially enables new imaging applications as well as differentiation of hyperpolarized chemical species on demand by exploiting spin manipulations with static and alternating magnetic fields. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Detection of Taurine in Biological Tissues by 33S NMR Spectroscopy

    Science.gov (United States)

    Musio, Roberta; Sciacovelli, Oronzo

    2001-12-01

    The potential of 33S NMR spectroscopy for biochemical investigations on taurine (2-aminoethanesulfonic acid) is explored. It is demonstrated that 33S NMR spectroscopy allows the selective and unequivocal identification of taurine in biological samples. 33S NMR spectra of homogenated and intact tissues are reported for the first time, together with the spectrum of a living mollusc. Emphasis is placed on the importance of choosing appropriate signal processing methods to improve the quality of the 33S NMR spectra of biological tissues.

  7. Ion counting in supercapacitor electrodes using NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Griffin, John M. [Department of Chemistry; University of Cambridge; Cambridge, UK; Forse, Alexander C. [Department of Chemistry; University of Cambridge; Cambridge, UK; Wang, Hao [Department of Chemistry; University of Cambridge; Cambridge, UK; Trease, Nicole M. [Department of Chemistry; Stony Brook University; New York, USA; Taberna, Pierre-Louis [Université Paul Sabatier Toulouse III; CIRIMAT; F-31062 Toulouse, France; Simon, Patrice [Université Paul Sabatier Toulouse III; CIRIMAT; F-31062 Toulouse, France; Grey, Clare P. [Department of Chemistry; University of Cambridge; Cambridge, UK; Department of Chemistry; Stony Brook University

    2014-01-01

    19F NMR spectroscopy has been used to study the local environments of anions in supercapacitor electrodes and to quantify changes in the populations of adsorbed species during charging. In the absence of an applied potential, anionic species adsorbed within carbon micropores (in-pore) are distinguished from those in large mesopores and spaces between particles (ex-pore) by a characteristic nucleus-independent chemical shift (NICS). Adsorption experiments and two-dimensional exchange experiments confirm that anions are in dynamic equilibrium between the in- and ex-pore environments with an exchange rate in the order of tens of Hz.19Fin situNMR spectra recorded at different charge states reveal changes in the intensity and NICS of the in-pore resonances, which are interpreted in term of changes in the population and local environments of the adsorbed anions that arise due to the charge-storage process. A comparison of the results obtained for a range of electrolytes reveals that several factors influence the charging mechanism. For a tetraethylammonium tetrafluoroborate electrolyte, positive polarisation of the electrode is found to proceed by anion adsorption at a low concentration, whereas increased ion exchange plays a more important role for a high concentration electrolyte. In contrast, negative polarization of the electrode proceeds by cation adsorption for both concentrations. For a tetrabutylammonium tetrafluoroborate electrolyte, anion expulsion is observed in the negative charging regime; this is attributed to the reduced mobility and/or access of the larger cations inside the pores, which forces the expulsion of anions in order to build up ionic charge. Significant anion expulsion is also observed in the negative charging regime for alkali metal bis(trifluoromethane)sulfonimide electrolytes, suggesting that more subtle factors also affect the charging mechanism.

  8. Selectivity of alkyl radical formation from branched alkanes studied by electron spin resonance and electron spin echo spectroscopy

    International Nuclear Information System (INIS)

    Tsuneki, Ichikawa; Hiroshi, Yoshida

    1992-01-01

    Alkyl radicals generated from branched alkanes by γ radiation are being measuring by electron spin resonance and electron spin echo spectroscopy. This research is being conducted to determine the mechanism of selective alkyl radical formation in low-temperature solids

  9. Sealed magic angle spinning nuclear magnetic resonance probe and process for spectroscopy of hazardous samples

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Herman M.; Washton, Nancy M.; Mueller, Karl T.; Sears, Jr., Jesse A.; Townsend, Mark R.; Ewing, James R.

    2016-06-14

    A magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) probe is described that includes double containment enclosures configured to seal and contain hazardous samples for analysis. The probe is of a modular design that ensures containment of hazardous samples during sample analysis while preserving spin speeds for superior NMR performance and convenience of operation.

  10. Thermolysin-inhibitor complexes examined by 31P and 113Cd NMR spectroscopy.

    Science.gov (United States)

    Gettins, P

    1988-07-25

    Complexes between phosphoramidon (N-(alpha-rhamnopyranosyloxyhydroxyphosphinyl)-L-leucyl-L-tryptoph an) and zinc thermolysin and between phosphoramidon or N-phosphoryl-L-leucineamide and 113Cd-substituted thermolysin have been examined by 31P and 113Cd NMR spectroscopy. 113Cd resonances are observed at 168 and 152 ppm for the phosphoramidon and N-phosphoryl-L-leucineamide complexes, respectively. There are large but different chemical shift anisotropy contributions to the 113Cd line widths for the two complexes, which reflect the known structural differences for the zinc-enzyme complexes. 113Cd-31P spin-spin coupling is also seen and differs for the two cadmium complexes, being larger, 28 Hz, for the bidentate N-phosphoryl-L-leucineamide ligand than for the monodentate phosphoramidon, 16 Hz. Large changes in chemical shift, 7.5-10.9 ppm, are seen for the 31P resonances of the inhibitors upon binding to the enzyme reflecting direct phosphoryl-metal ligation. Chemical shift anisotropy is the dominant relaxation mechanism for the 31P nuclei at 9.4 T, while the dipole-dipole contribution seems to be unaffected by a change of solvent from H2O to D2O.

  11. Fast method of NMR imaging based on trains of spin echoes

    International Nuclear Information System (INIS)

    Hennel, F.

    1993-01-01

    A theoretical introduction to Fourier NMR imaging and a discussion of fast methods are presented. Then an application of the method of echo-planar imaging (EPI) with spin echoes in a micro-imaging system is described together with introduced modifications of the sequence. A new technique for the measurement of flow profiles in liquids which results from a modification of x-pulsed EPI is presented. The development of new software for a NMR micro-imaging system is described, too. 51 refs, 29 refs

  12. Coexistence of spin frozen state and persistent spin dynamics in NaSrCo{sub 2}F{sub 7} as probed by μSR and NMR

    Energy Technology Data Exchange (ETDEWEB)

    Dengre, Shanu; Sarkar, Rajib; Braeuninger, Sascha Albert; Brueckner, Felix; Materne, Philipp; Klauss, Hans-Henning [Institute for Solid State Physics, TU Dresden (Germany); Krizan, Jason W.; Cava, Robert J. [Department of Chemistry, Princeton University, Princeton, NJ (United States); Luetkens, Hubertus; Baines, Chris [Laboratory for Muon-Spin Spectroscopy, Paul Scherrer Institute, Villigen (Switzerland)

    2016-07-01

    {sup 23}Na -and {sup 19}F NMR, and μSR experiments are performed to explore the microscopic properties of NaSrCo{sub 2}F{sub 7}, which is a newly discovered magnetically frustrated pyrochlore with weak bond disorder and with a frustration index of f = 42. While {sup 23}Na and {sup 19}F NMR experiments clearly suggest the presence of quasi static field distribution below ∝3 K as reflected in the huge NMR line broadening and wipe out effect of NMR signal intensity, μSR experiments on the other hand remains passive to this spin frozen state. Both NMR and μSR results indicate the slowing down of the magnetic (spin) fluctuations upon cooling towards the NMR spin frozen state. μSR relaxation rate increases slightly below ∝ 3 K, and remains not only constant down to 20 mK, but also stands independent in longitudinal magnetic field upto 4000 G implying that the spin fluctuations are dynamic. These observations suggest the coexistence of partial spin frozen state and persistent spin dynamics in NaSrCo{sub 2}F{sub 7}.

  13. Communication: Phase incremented echo train acquisition in NMR spectroscopy.

    Science.gov (United States)

    Baltisberger, Jay H; Walder, Brennan J; Keeler, Eric G; Kaseman, Derrick C; Sanders, Kevin J; Grandinetti, Philip J

    2012-06-07

    We present an improved and general approach for implementing echo train acquisition (ETA) in magnetic resonance spectroscopy, particularly where the conventional approach of Carr-Purcell-Meiboom-Gill (CPMG) acquisition would produce numerous artifacts. Generally, adding ETA to any N-dimensional experiment creates an N + 1 dimensional experiment, with an additional dimension associated with the echo count, n, or an evolution time that is an integer multiple of the spacing between echo maxima. Here we present a modified approach, called phase incremented echo train acquisition (PIETA), where the phase of the mixing pulse and every other refocusing pulse, φ(P), is incremented as a single variable, creating an additional phase dimension in what becomes an N + 2 dimensional experiment. A Fourier transform with respect to the PIETA phase, φ(P), converts the φ(P) dimension into a Δp dimension where desired signals can be easily separated from undesired coherence transfer pathway signals, thereby avoiding cumbersome or intractable phase cycling schemes where the receiver phase must follow a master equation. This simple modification eliminates numerous artifacts present in NMR experiments employing CPMG acquisition and allows "single-scan" measurements of transverse relaxation and J-couplings. Additionally, unlike CPMG, we show how PIETA can be appended to experiments with phase modulated signals after the mixing pulse.

  14. Impurity effects in a S=1/2 Heisenberg spin chain probed by {sup 63}Cu NMR

    Energy Technology Data Exchange (ETDEWEB)

    Utz, Yannic; Bruening, Eva Maria; Hammerath, Franziska; Rudisch, Christian; Grafe, Hans-Joachim; Mohan, Ashwin; Hess, Christian; Nishimoto, Satoshi; Drechsler, Stefan-Ludwig; Buechner, Bernd [IFW Dresden (Germany); Saint-Martin, Romuald; Revcolevschi, Alexandre [LPCES, Orsay (France)

    2013-07-01

    We present {sup 63}Cu NMR measurements on undoped, Ni doped and Mg doped SrCuO{sub 2} single crystals. SrCuO{sub 2} is a good realization of a one-dimensional S=1/2 Heisenberg spin chain. This is confirmed by the theoretically-expected temperature independent NMR spin-lattice relaxation rate T{sup -1}{sub 1}. Doping with Ni, which can be regarded as a S=1 impurity, has a major impact on the magnetic properties of the spin chains. On the one hand, this is manifested by unusual features in the NMR spectra below 100 K, revealing the existence of an impurity-induced local alternating magnetisation. On the other hand, exponentially decaying spin lattice relaxation rates towards low temperatures indicate the opening of a spin gap similar to Ca doped SrCuO{sub 2}. Mg doping (S=0) has, however, no influence on the magnetic properties of the spin chains. Neither the NMR spectra nor the spin lattice relaxation rates differ from those measured on pure SrCuO{sub 2}. While the different impact of Ni and Mg doping on the spin chains could be explained by their different impurity spins, the opening of a spin gap in case of Ni doping is totally unexpected and not yet understood.

  15. Solid and liquid 129Xe NMR signals enhanced by spin-exchange optical pumping under flow

    International Nuclear Information System (INIS)

    Zhou Xin; Luo Jun; Sun Xianping; Zeng Xizhi; Liu Maili; Liu Wuyang

    2002-01-01

    Laser-polarized 129 Xe gas was produced by spin-exchange with Cs atom optically pumped with diode laser array in a low field under flow. The nuclear spin polarizations of the solid and liquid 129 Xe frozen from the laser-polarized 129 Xe gas were 2.16% and 1.45% respectively in the SY-80M NMR spectrometer, which corresponded to the enhancements of 6000 and 5000 compared to those without optical pumping under the same conditions. It could provide the base and possibility for quantum computers using laser-enhanced solid and liquid 129 Xe. Polarization loss of transport and state change was also discussed

  16. Structure of the Alanine Hydration Shell as Probed by NMR Chemical Shifts and Indirect Spin-Spin Coupling

    Czech Academy of Sciences Publication Activity Database

    Dračínský, Martin; Kaminský, Jakub; Bouř, Petr

    2009-01-01

    Roč. 113, č. 44 (2009), s. 14698-14707 ISSN 1520-6106 R&D Projects: GA ČR GA202/07/0732; GA AV ČR IAA400550702 Institutional research plan: CEZ:AV0Z40550506 Keywords : NMR spectroscopy * CPMD * molecular dynamics * solvent effects Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.471, year: 2009

  17. Measurement and Characterization of Hydrogen-Deuterium Exchange Chemistry Using Relaxation Dispersion NMR Spectroscopy.

    Science.gov (United States)

    Khirich, Gennady; Holliday, Michael J; Lin, Jasper C; Nandy, Aditya

    2018-03-01

    One-dimensional heteronuclear relaxation dispersion NMR spectroscopy at 13 C natural abundance successfully characterized the dynamics of the hydrogen-deuterium exchange reaction occurring at the N ε position in l-arginine by monitoring C δ in varying amounts of D 2 O. A small equilibrium isotope effect was observed and quantified, corresponding to ΔG = -0.14 kcal mol -1 . A bimolecular rate constant of k D = 5.1 × 10 9 s -1 M -1 was determined from the pH*-dependence of k ex (where pH* is the direct electrode reading of pH in 10% D 2 O and k ex is the nuclear spin exchange rate constant), consistent with diffusion-controlled kinetics. The measurement of ΔG serves to bridge the millisecond time scale lifetimes of the detectable positively charged arginine species with the nanosecond time scale lifetime of the nonobservable low-populated neutral arginine intermediate species, thus allowing for characterization of the equilibrium lifetimes of the various arginine species in solution as a function of fractional solvent deuterium content. Despite the system being in fast exchange on the chemical shift time scale, the magnitude of the secondary isotope shift due to the exchange reaction at N ε was accurately measured to be 0.12 ppm directly from curve-fitting D 2 O-dependent dispersion data collected at a single static field strength. These results indicate that relaxation dispersion NMR spectroscopy is a robust and general method for studying base-catalyzed hydrogen-deuterium exchange chemistry at equilibrium.

  18. Integration of screening and identifying ligand(s) from medicinal plant extracts based on target recognition by using NMR spectroscopy

    OpenAIRE

    sprotocols

    2015-01-01

    Authors: Yalin Tang, Qian Shang, Junfeng Xiang, Qianfan Yang, Qiuju Zhou, Lin Li, Hong Zhang, Qian Li, Hongxia Sun, Aijiao Guan, Wei Jiang & Wei Gai ### Abstract This protocol presents the screening of ligand(s) from medicinal plant extracts based on target recognition by using NMR spectroscopy. A detailed description of sample preparation and analysis process is provided. NMR spectroscopies described here are 1H NMR, diffusion-ordered spectroscopy (DOSY), relaxation-edited NMR, 1H–1...

  19. Development of a micro flow-through cell for high field NMR spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Alam, Todd Michael; McIntyre, Sarah K.

    2011-05-01

    A highly transportable micro flow-through detection cell for nuclear magnetic resonance (NMR) spectroscopy has been designed, fabricated and tested. This flow-through cell allows for the direct coupling between liquid chromatography (LC) and gel permeation chromatography (GPC) resulting in the possibility of hyphenated LC-NMR and GPC-NMR. The advantage of the present flow cell design is that it is independent and unconnected to the detection probe electronics, is compatible with existing commercial high resolution NMR probes, and as such can be easily implemented at any NMR facility. Two different volumes were fabricated corresponding to between {approx}3.8 and 10 {micro}L detection volume. Examples of the performance of the cell on different NMR instruments, and using different NMR detection probes were demonstrated.

  20. .sup.57./sup.Fe NMR and spin structure of manganese ferrite

    Czech Academy of Sciences Publication Activity Database

    Štěpánková, H.; Sedlák, B.; Chlan, V.; Novák, Pavel; Šimša, Zdeněk

    2008-01-01

    Roč. 77, č. 9 (2008), 092416/1-092419/4 ISSN 1098-0121 R&D Projects: GA ČR GA202/08/0541; GA ČR GA202/06/0051 Institutional research plan: CEZ:AV0Z10100521 Keywords : NMR * manganese ferrite * spin structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.322, year: 2008

  1. 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…

  2. pH control and rapid mixing in spinning NMR samples

    Science.gov (United States)

    Yesinowski, James P.; Sunberg, Richard J.; Benedict, James J.

    An apparatus is described which permits the acquisition of NMR spectra from spinning 20-mm sample tubes while: (1) constantly monitoring the pH; (2) adding reagents to maintain constant pH (pH-statting); (3) efficiently mixing the added reagent. The apparatus was built to study the spontaneous precipitation of calcium phosphates from supersaturated solutions using 31P NMR. Other applications include the rapid determination of NMR titration curves, and the minimization of temperature gradients in large sample tubes. The apparatus was used to measure the 31P chemical shift titration of dilute phosphoric acid, which yielded accurate shifts for the three species of protonated orthophosphate ion. The bulk magnetic susceptibility of 85% H 3PO 4 relative to a dilute aqueous sample was also measured, and is shown to contribute significantly to chemical shift measurements.

  3. Exploring the Structure of a DNA Hairpin with the Help of NMR Spin-Spin Coupling Constants: An Experimental and Quantum Chemical Investigation

    Czech Academy of Sciences Publication Activity Database

    Sychrovský, Vladimír; Vacek, Jaroslav; Hobza, Pavel; Žídek, L.; Sklenář, V.; Cremer, D.

    2002-01-01

    Roč. 106, - (2002), s. 10242-10250 ISSN 1089-5639 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : DNA * help of NMR spin-spin coupling constants * quantum chemical investigation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.765, year: 2002

  4. Sensitivity and Resolution Enhanced Solid-State NMR for Paramagnetic Systems and Biomolecules under Very Fast Magic Angle Spinning

    KAUST Repository

    Parthasarathy, Sudhakar

    2013-09-17

    Recent research in fast magic angle spinning (MAS) methods has drastically improved the resolution and sensitivity of NMR spectroscopy of biomolecules and materials in solids. In this Account, we summarize recent and ongoing developments in this area by presenting (13)C and (1)H solid-state NMR (SSNMR) studies on paramagnetic systems and biomolecules under fast MAS from our laboratories. First, we describe how very fast MAS (VFMAS) at the spinning speed of at least 20 kHz allows us to overcome major difficulties in (1)H and (13)C high-resolution SSNMR of paramagnetic systems. As a result, we can enhance both sensitivity and resolution by up to a few orders of magnitude. Using fast recycling (∼ms/scan) with short (1)H T1 values, we can perform (1)H SSNMR microanalysis of paramagnetic systems on the microgram scale with greatly improved sensitivity over that observed for diamagnetic systems. Second, we discuss how VFMAS at a spinning speed greater than ∼40 kHz can enhance the sensitivity and resolution of (13)C biomolecular SSNMR measurements. Low-power (1)H decoupling schemes under VFMAS offer excellent spectral resolution for (13)C SSNMR by nominal (1)H RF irradiation at ∼10 kHz. By combining the VFMAS approach with enhanced (1)H T1 relaxation by paramagnetic doping, we can achieve extremely fast recycling in modern biomolecular SSNMR experiments. Experiments with (13)C-labeled ubiquitin doped with 10 mM Cu-EDTA demonstrate how effectively this new approach, called paramagnetic assisted condensed data collection (PACC), enhances the sensitivity. Lastly, we examine (13)C SSNMR measurements for biomolecules under faster MAS at a higher field. Our preliminary (13)C SSNMR data of Aβ amyloid fibrils and GB1 microcrystals acquired at (1)H NMR frequencies of 750-800 MHz suggest that the combined use of the PACC approach and ultrahigh fields could allow for routine multidimensional SSNMR analyses of proteins at the 50-200 nmol level. Also, we briefly discuss the

  5. Non-polymeric asymmetric binary glass-formers. II. Secondary relaxation studied by dielectric, 2H NMR, and 31P NMR spectroscopy

    Science.gov (United States)

    Pötzschner, B.; Mohamed, F.; Bächer, C.; Wagner, E.; Lichtinger, A.; Bock, D.; Kreger, K.; Schmidt, H.-W.; Rössler, E. A.

    2017-04-01

    We investigate the secondary (β-) relaxations of an asymmetric binary glass former consisting of a spirobichroman derivative (SBC; Tg = 356 K) as the high-Tg component and the low-Tg component tripropyl phosphate (TPP; Tg = 134 K). The main relaxations are studied in Paper I [B. Pötzschner et al., J. Chem. Phys. 146, 164503 (2017)]. A high Tg contrast of ΔTg = 222 K is put into effect in a non-polymeric system. Component-selective studies are carried out by combining results from dielectric spectroscopy (DS) for mass concentrations cTPP ≥ 60% and those from different methods of 2H and 31P NMR spectroscopy. In the case of NMR, the full concentration range (10% ≤ cTPP ≤ 100%) is covered. The neat components exhibit a β-relaxation (β1 (SBC) and β2 (TPP)). The latter is rediscovered by DS in the mixtures for all concentrations with unchanged time constants. NMR spectroscopy identifies the β-relaxations as being alike to those in neat glasses. A spatially highly restricted motion with angular displacement below ±10° encompassing all molecules is involved. In the low temperature range, where TPP shows the typical 31P NMR echo spectra of the β2-process, very similar spectral features are observed for the (deuterated) SBC component by 2H NMR, in addition to its "own" β1-process observed at high temperatures. Apparently, the small TPP molecules enslave the large SBC molecules to perform a common hindered reorientation. The temperature dependence of the spin-lattice relaxation time of both components is the same and reveals an angular displacement of the SBC molecules somewhat smaller than that of TPP, though the time constants τβ2 are the same. Furthermore, T1(T) of TPP in the temperature region of the β2-process is absolutely the same as in the mixture TPP/polystyrene investigated previously. It appears that the manifestations of the β-process introduced by one component are essentially independent of the second component. Finally, at cTPP ≤ 20% one

  6. Aspects of solid state 13C CPMAS NMR spectroscopy in coals from the Balkan peninsula

    Directory of Open Access Journals (Sweden)

    ANDREAS GEORGAKOPOULOS

    2003-09-01

    Full Text Available The cross-polarized magic-angle-spinning NMR (CPMAS-NMR technique was used in this work to assess the carbon distribution in coals of different rank (peat, lignite, xylite, sub-bituminous coal from important deposits in Greece and Bulgaria. The technique is assumed to be only semiquantitative, due to a number of interferences, such as spinning side bands (SSB in the spectra, paramagnetic species in the samples, and low or remote protonation of aromatic carbons. The Bulgarian sub-bituminous coal shows the greatest amounts of aromatic structures. The lignite sample from the Drama basin, Northern Greece, is relatively unaltered and largely unweathered, and shows the greatest amounts of aliphatic groups. The 13C-NMR spectra of Pliocene lignites from endemic areas in Serbia and Montenegro and Bosnia, taken from published papers, show significantly more intense resonances for methoxyl, phenolic, and polysaccharide moieties compared to the Drama lignite NMR spectrum. Xylite reveals high contents of carbohydrates.

  7. Identification of Li-Ion Battery SEI Compounds through (7)Li and (13)C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry.

    Science.gov (United States)

    Huff, Laura A; Tavassol, Hadi; Esbenshade, Jennifer L; Xing, Wenting; Chiang, Yet-Ming; Gewirth, Andrew A

    2016-01-13

    Solid-state (7)Li and (13)C MAS NMR spectra of cycled graphitic Li-ion anodes demonstrate SEI compound formation upon lithiation that is followed by changes in the SEI upon delithiation. Solid-state (13)C DPMAS NMR shows changes in peaks associated with organic solvent compounds (ethylene carbonate and dimethyl carbonate, EC/DMC) upon electrochemical cycling due to the formation of and subsequent changes in the SEI compounds. Solid-state (13)C NMR spin-lattice (T1) relaxation time measurements of lithiated Li-ion anodes and reference poly(ethylene oxide) (PEO) powders, along with MALDI-TOF mass spectrometry results, indicate that large-molecular-weight polymers are formed in the SEI layers of the discharged anodes. MALDI-TOF MS and NMR spectroscopy results additionally indicate that delithiated anodes exhibit a larger number of SEI products than is found in lithiated anodes.

  8. 1H HRMAS NMR spectroscopy and chemometrics for evaluation of metabolic changes in citrus sinensis Caused by Xanthomonas axonopodis pv. citri

    International Nuclear Information System (INIS)

    Silva, Lorena M.A.; Alves Filho, Elenilson G.; Choze, Rafael; Liao, Luciano M.; Alcantara, Glaucia B.

    2012-01-01

    Xanthomonas axonopodis (Xac) bacterium causes one of the most feared and untreatable diseases in citriculture: citrus canker. To understand the response mechanisms of orange trees when attacked by Xac, leaves and fruits of Citrus sinensis were directly evaluated by HRMAS NMR (high resolution magic angle spinning nuclear magnetic resonance) spectroscopy. This technique allows the analysis of samples without laborious pre-treatments and also allows access to important information about chemical composition of samples. The orange tree leaves and fruit peels investigated in this study demonstrated the biochemical changes caused by Xac. Aided by chemometric analysis, the HRMAS NMR results show relevant changes in amino acids, carbohydrates, organic acids and terpenoids content. (author)

  9. Hydration kinetics for the alite, belite, and calcium aluminate phase in Portland cements from 27Al and 29Si MAS NMR spectroscopy

    DEFF Research Database (Denmark)

    Skibsted, Jørgen; Jensen, Ole Mejlhede; Jakobsen, Hans Jørgen

    1997-01-01

    29Si magic-angle spinning (MAS) NMR spectroscopy is shown to be a valuable tool for obtaining the quantities of alite and belite in hydrated Portland cements. The hydration (1-180 days) of a white Portland cement with 10 wt.% silica fume added is investigated and the degrees of hydration for alite...... belite, and silica fume are determined. It is demonstrated that 27Al MAS NMR spectra of hydrated Portland cements can give quantitative information about the formation of ettringite and the conversion of this phase to monosulphate during hydration....

  10. 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…

  11. A Spin-Flip Cavity for Microwave Spectroscopy of Antihydrogen

    CERN Document Server

    Federmann, Silke; Widmann, Eberhard

    The present thesis is a contribution to the Asacusa (Atomic Spectroscopy And Collisions Using Slow Antiprotons) experiment. The aim of this experiment is to measure the ground-state hyperfine structure of antihydrogen. This is done using a Rabi-like spectrometer line consisting of an antihydrogen source, a microwave cavity, a sextupole magnet and a detector. The cavity induces spin-flip transitions in the ground-state hyperfine levels of antihydrogen whereas the sextupole magnet selects the antihydrogen atoms according to their spin state. Such a configuration allows the measurements of the hyperfine transition in antihydrogen with very high precision. A comparison with the corresponding transitions in hydrogen would thus provide a very sensitive test of the charge-parity-time (Cpt) symmetry. In the context of this thesis, the central piece of this spectrometer line, the spin flip cavity, was designed and implemented. The delicacy of this task was achieving the required field homogeneity: It needs to be bette...

  12. 1H HR-MAS NMR Spectroscopy and the Metabolite Determination of Typical Foods in Mediterranean Diet

    Directory of Open Access Journals (Sweden)

    Carmelo Corsaro

    2015-01-01

    Full Text Available NMR spectroscopy has become an experimental technique widely used in food science. The experimental procedures that allow precise and quantitative analysis on different foods are relatively simple. For a better sensitivity and resolution, NMR spectroscopy is usually applied to liquid sample by means of extraction procedures that can be addressed to the observation of particular compounds. For the study of semisolid systems such as intact tissues, High-Resolution Magic Angle Spinning (HR-MAS has received great attention within the biomedical area and beyond. Metabolic profiling and metabolism changes can be investigated both in animal organs and in foods. In this work we present a proton HR-MAS NMR study on the typical vegetable foods of Mediterranean diet such as the Protected Geographical Indication (PGI cherry tomato of Pachino, the PGI Interdonato lemon of Messina, several Protected Designation of Origin (PDO extra virgin olive oils from Sicily, and the Traditional Italian Food Product (PAT red garlic of Nubia. We were able to identify and quantify the main metabolites within the studied systems that can be used for their characterization and authentication.

  13. Signal interferences from turbulent spin dynamics in solution nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Huang, Susie Y.; Lin, Yung-Ya; Lisitza, Natalia; Warren, Warren S.

    2002-06-01

    Artifacts arising from aperiodic turbulent spin dynamics in gradient-based nuclear magnetic resonance (NMR) applications are comprehensively surveyed and numerically simulated by a nonlinear Bloch equation. The unexpected dynamics, triggered by the joint action of radiation damping and the distant dipolar field, markedly deteriorate the performance of certain pulse sequences incorporating weak pulsed-field gradients and long evolution times. The effects are demonstrated in three general classes of gradient NMR applications: solvent signal suppression, diffusion measurements, and coherence pathway selection. Gradient-modulated solvent transverse magnetization can be partially rephased in a series of self-refocusing gradient echoes that blank out solute resonances in the CHESS (chemical-shift-selective spectroscopy) and WATERGATE (gradient-tailored water suppression) solvent suppression schemes. In addition, the discovered dynamics contribute to erratic echo attenuation in pulsed gradient spin echo (PGSE) and PGSE stimulated echo diffusion measurements and produce coherence leakage in gradient-selected DQFCOSY and HMQC experiments. Specific remedies for minimizing unwanted effects are presented.

  14. Frequency-domain method based on the singular value decomposition for frequency-selective NMR spectroscopy.

    Science.gov (United States)

    Stoica, Petre; Sandgren, Niclas; Selén, Yngve; Vanhamme, Leentje; Van Huffel, Sabine

    2003-11-01

    In several applications of NMR spectroscopy the user is interested only in the components lying in a small frequency band of the spectrum. A frequency selective analysis deals precisely with this kind of NMR spectroscopy: parameter estimation of only those spectroscopic components that lie in a preselected frequency band of the NMR data spectrum, with as little interference as possible from the out-of-band components and in a computationally efficient way. In this paper we introduce a frequency-domain singular value decomposition (SVD)-based method for frequency selective spectroscopy that is computationally simple, statistically accurate, and which has a firm theoretical basis. To illustrate the good performance of the proposed method we present a number of numerical examples for both simulated and in vitro NMR data.

  15. High resolution NMR spectroscopy of physiological fluids: from metabolism to physiology

    International Nuclear Information System (INIS)

    Vion-Dury, J.; Nicoli, F.; Torri, G.; Torri, J.; Kriat, M.; Sciaky, M.; Davin, A.; Viout, P.; Confort-Gouny, S.; Cozzone, P.J.

    1992-01-01

    High resolution NMR spectroscopy of physiological fluids provides quantitative, qualitative and dynamic information on the metabolic status of the interstitial and plasma compartments under a variety of pathophysiological conditions. The simultaneous detection and quantitation by NMR spectroscopy of numerous compounds of the intermediary metabolism offers a new insight in the understanding of the 'milieu interieur'.NMR spectroscopy of physiological fluids offers a unique way to define and monitor the global metabolic homeostasis in humans. The development of this analytical approach is still limited by the scarcity of pluridisciplinary teams able to fully exploit the wealth of information present on the NMR spectrum of a fluid. While application in pharmacology and toxicology is already established, the main areas of current development are cancer, hereditary metabolic disorders, organ transplantation and neurological diseases

  16. Spin polarized Auger electron spectroscopy of Fe and Ni

    Science.gov (United States)

    Anilturk, O. S.; Koymen, A. R.

    2001-06-01

    Surface sensitive experiments, in which the spin-polarized electrons are involved, play an important role for magnetic characterization, since the spin-polarized electrons are fingerprints for the local magnetization. Scanning electron microscope with polarization analysis (SEMPA) is one of the most powerful tools to investigate the surface magnetic domain structure of magnetic materials. On the other hand, at energies high enough to generate a two-hole final state arising from Auger transitions, it is possible to observe the spin polarization of the Auger electrons. These electrons reveal element-specific local magnetic information, particularly valuable for surface magnetic studies with composite systems. By using the uniqueness of the UTA-SEMPA tool, one can obtain the magnetic domain picture and also perform spin-polarized Auger electron spectroscopy studies by probing a single domain at the surface. In this study, precisely knowing the probed domain, spin polarization of electrons from super Coster-Kronig MMM Auger emissions on Fe and Ni samples have been investigated. The polarization enhancement above the 3p(M23) threshold is observed on both samples.

  17. Spin polarized Auger electron spectroscopy of Fe and Ni

    International Nuclear Information System (INIS)

    Anilturk, O. S.; Koymen, A. R.

    2001-01-01

    Surface sensitive experiments, in which the spin-polarized electrons are involved, play an important role for magnetic characterization, since the spin-polarized electrons are fingerprints for the local magnetization. Scanning electron microscope with polarization analysis (SEMPA) is one of the most powerful tools to investigate the surface magnetic domain structure of magnetic materials. On the other hand, at energies high enough to generate a two-hole final state arising from Auger transitions, it is possible to observe the spin polarization of the Auger electrons. These electrons reveal element-specific local magnetic information, particularly valuable for surface magnetic studies with composite systems. By using the uniqueness of the UTA-SEMPA tool, one can obtain the magnetic domain picture and also perform spin-polarized Auger electron spectroscopy studies by probing a single domain at the surface. In this study, precisely knowing the probed domain, spin polarization of electrons from super Coster - Kronig MMM Auger emissions on Fe and Ni samples have been investigated. The polarization enhancement above the 3p(M 23 ) threshold is observed on both samples. [copyright] 2001 American Institute of Physics

  18. Photochromism of indolino-benzopyrans studied by NMR and UV-visible spectroscopy

    OpenAIRE

    Delbaere, S.; Berthet, J.; Salvador, M. A.; Vermeersch, G.; Oliveira, M. M.

    2006-01-01

    The synthesis of photochromic 3,3-di(4′-fluorophenyl)-3H-benzopyrans fused to an indole moiety is described. The structures of photomerocyanines elucidated by NMR spectroscopy and spectrokinetic data (λmax⁡ of colored form, colorability, and rate constant of bleaching) obtained by UV-visible spectroscopy are reported.

  19. Cross-linking and 1H n.m.r. spectroscopy of the pyruvate dehydrogenase complex of Escherichia coli.

    Science.gov (United States)

    Packman, L C; Perham, R N; Roberts, G C

    1982-08-01

    The pyruvate dehydrogenase complex of Escherichia coli was treated with o-phenylene bismaleimide in the presence of the substrate pyruvate, producing almost complete cross-linking of the lipoate acetyltransferase polypeptide chains as judged by sodium dodecyl sulphate/polyacrylamide-gel electrophoresis. This took place without effect on the catalytic activities of the other two component enzymes and with little evidence of cross-links being formed with other types of protein subunit. Limited proteolysis with trypsin indicated that the cross-links were largely confined to the lipoyl domains of the lipoate acetyltransferase component of the same enzyme particle. This intramolecular cross-linking had no effect on the very sharp resonances observed in the (1)H n.m.r. spectrum of the enzyme complex, which derive from regions of highly mobile polypeptide chain in the lipoyl domains. Comparison of the spin-spin relaxation times, T(2), with the measured linewidths supported the idea that the highly mobile region is best characterized as a random coil. Intensity measurements in spin-echo spectra showed that it comprises a significant proportion (probably not less than one-third) of a lipoyl domain and is thus much more than a small hinge region, but there was insufficient intensity in the resonances to account for the whole lipoyl domain. On the other hand, no evidence was found in the (1)H n.m.r. spectrum for a substantial structured region around the lipoyl-lysine residues that was free to move on the end of this highly flexible connection. If such a structured region were bound to other parts of the enzyme complex for a major part of its time, its resonances might be broadened sufficiently to evade detection by (1)H n.m.r. spectroscopy.

  20. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Shmyreva, Anna A. [Center for Magnetic Resonance, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Safdari, Majid; Furó, István [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Dvinskikh, Sergey V., E-mail: sergeid@kth.se [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 199034 (Russian Federation)

    2016-06-14

    Orders of magnitude decrease of {sup 207}Pb and {sup 199}Hg NMR longitudinal relaxation times T{sub 1} upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX{sub 2} (Me = Pb, Hg and X = Cl, Br, I). In lead(II) halides, the most dramatic decrease of T{sub 1} relative to that in a static sample is in PbI{sub 2}, while it is smaller but still significant in PbBr{sub 2}, and not detectable in PbCl{sub 2}. The effect is magnetic-field dependent but independent of the spinning speed in the range 200–15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  1. Distribution and mobility of phosphates and sodium ions in cheese by solid-state 31P and double-quantum filtered 23Na NMR spectroscopy.

    Science.gov (United States)

    Gobet, Mallory; Rondeau-Mouro, Corinne; Buchin, Solange; Le Quéré, Jean-Luc; Guichard, Elisabeth; Foucat, Loïc; Moreau, Céline

    2010-04-01

    The feasibility of solid-state magic angle spinning (MAS) (31)P nuclear magnetic resonance (NMR) spectroscopy and (23)Na NMR spectroscopy to investigate both phosphates and Na(+) ions distribution in semi-hard cheeses in a non-destructive way was studied. Two semi-hard cheeses of known composition were made with two different salt contents. (31)P Single-pulse excitation and cross-polarization MAS experiments allowed, for the first time, the identification and quantification of soluble and insoluble phosphates in the cheeses. The presence of a relatively 'mobile' fraction of colloidal phosphates was evidenced. The detection by (23)Na single-quantum NMR experiments of all the sodium ions in the cheeses was validated. The presence of a fraction of 'bound' sodium ions was evidenced by (23)Na double-quantum filtered NMR experiments. We demonstrated that NMR is a suitable tool to investigate both phosphates and Na(+) ions distributions in cheeses. The impact of the sodium content on the various phosphorus forms distribution was discussed and results demonstrated that NMR would be an important tool for the cheese industry for the processes controls. Copyright 2010 John Wiley & Sons, Ltd.

  2. Probing the flexibility of internal rotation in silylated phenols with the NMR scalar spin-spin coupling constants

    Czech Academy of Sciences Publication Activity Database

    Sychrovský, Vladimír; Benda, Ladislav; Prokop, Alexandr; Blechta, Vratislav; Schraml, Jan; Špirko, Vladimír

    2008-01-01

    Roč. 112, č. 23 (2008), s. 5167-5174 ISSN 1089-5639 R&D Projects: GA AV ČR IAA400550701; GA AV ČR IAA400550702; GA AV ČR IAA400720706; GA ČR GA203/06/0738; GA MŠk LC512 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40720504 Keywords : dynamical averaging * Si-29 NMR spectroscopy * ab-initio calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.871, year: 2008

  3. Detection of Anisotropy in Cartilage Using 2H Double-Quantum-Filtered NMR-Spectroscopy

    Science.gov (United States)

    Sharf, Y.; Eliav, U.; Shinar, H.; Navon, G.

    Double-quantum-filtered (DQF) NMR spectroscopy of I = 1 spin systems is a diagnostic tool for the detection of anisotropy in macroscopically disordered systems. For deuterium, this method reveals the presence of a residual quadrupolar interaction for D 2O in bovine nasal cartilage. This tissue is not macroscopically ordered and the quadrupolar splitting is not resolved. Fitting the calculated spectral lineshapes to the experimental results was possible only when a distribution of the residual quadrupolar interaction, omega(q), was assumed. The series of DQF lineshapes obtained for different creation times in the DQF experiment could be fitted using a single set of three parameters: the average residual quadrupolar interaction overlineω q/2π = 110 Hz, its standard deviation Δω q/2π = 73 Hz, and the transverse relaxation rate of 63 s -1. Separate deuterium DQF measurements for the constituents of the cartilage, collagen, and chondroitin sulfate indicated that the DQF spectra of cartilage are the result of anisotropic motion of D 2O due to binding to the fibrous collagen in the tissue.

  4. I. Advances in NMR Signal Processing. II. Spin Dynamics in Quantum Dissipative Systems

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Yung-Ya [Univ. of California, Berkeley, CA (United States)

    1998-11-01

    Part I. Advances in IVMR Signal Processing. Improvements of sensitivity and resolution are two major objects in the development of NMR/MRI. A signal enhancement method is first presented which recovers signal from noise by a judicious combination of a priordmowledge to define the desired feasible solutions and a set theoretic estimation for restoring signal properties that have been lost due to noise contamination. The effect of noise can be significantly mitigated through the process of iteratively modifying the noisy data set to the smallest degree necessary so that it possesses a collection of prescribed properties and also lies closest to the original data set. A novel detection-estimation scheme is then introduced to analyze noisy and/or strongly damped or truncated FIDs. Based on exponential modeling, the number of signals is detected based on information estimated using the matrix pencil method. theory and the spectral parameters are Part II. Spin Dynamics in body dipole-coupled systems Quantum Dissipative Systems. Spin dynamics in manyconstitutes one of the most fundamental problems in magnetic resonance and condensed-matter physics. Its many-spin nature precludes any rigorous treatment. ‘Therefore, the spin-boson model is adopted to describe in the rotating frame the influence of the dipolar local fields on a tagged spin. Based on the polaronic transform and a perturbation treatment, an analytical solution is derived, suggesting the existence of self-trapped states in the. strong coupling limit, i.e., when transverse local field >> longitudinal local field. Such nonlinear phenomena originate from the joint action of the lattice fluctuations and the reaction field. Under semiclassical approximation, it is found that the main effect of the reaction field is the renormalization of the Hamiltonian of interest. Its direct consequence is the two-step relaxation process: the spin is initially localized in a quasiequilibrium state, which is later detrapped by

  5. 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.

  6. International school on high field NMR spectroscopy for solids and liquids

    Energy Technology Data Exchange (ETDEWEB)

    Marion, D.; Meier, B.; Keeler, J.; Berthault, P.; Vedrine, P.; Grandinetti, P.; Delsuc, M.A.; Spiess, H

    2006-07-01

    The aim of the school is to offer high-level pedagogical courses on a wide range of liquid- and solid-state NMR concepts and techniques: theory, instrumentation (magnets and probes), data acquisition, processing and analysis, measurement of dipolar and quadrupolar couplings, spin relaxation and hyper-polarization. This document gathers only the slides of most presentations.

  7. 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.

  8. Determination of the three-dimensional structure for weakly aligned biomolecules by NMR spectroscopy

    International Nuclear Information System (INIS)

    Shahkhatuni, Astghik A; Shahkhatuni, Aleksan G

    2002-01-01

    The key achievements and the potential of NMR spectroscopy for weakly aligned biomolecules are considered. Due to weak alignment, it becomes possible to determine a number of NMR parameters dependent on the orientation of biomolecules, which are averaged to zero in usual isotropic media. The addition of new orientational constraints to standard procedures of 3D structure determination markedly increases the achievable accuracy. The possibility of structure determination for biomolecules using only orientation-dependent parameters without invoking other NMR data is discussed. The methods of orientation, experimental techniques, and calculation methods are systematised. The main results obtained and the prospects of using NMR spectroscopy of weakly aligned systems to study different classes of biomolecules and to solve various problems of molecular biology are analysed. Examples of biomolecules whose structures have been determined using orientation-dependent parameters are given. The bibliography includes 508 references.

  9. Comparison of soil organic carbon speciation using C NEXAFS and CPMAS 13C NMR spectroscopy.

    Science.gov (United States)

    Prietzel, Jörg; Müller, Svenja; Kögel-Knabner, Ingrid; Thieme, Jürgen; Jaye, Cherno; Fischer, Daniel

    2018-07-01

    We compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS 13 C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15-30 OC mgg -1 , Podzol: 0.9-7 OC mgg -1 ). CPMAS 13 C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96-103%) than C NEXAFS spectroscopy (mean recovery 92-113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS 13 C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS 13 C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10mgOCg -1 . Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9-10mgg -1 ). Copyright © 2018 Elsevier B.V. All rights reserved.

  10. Characterization of functional LB films using electron spin resonance spectroscopy

    International Nuclear Information System (INIS)

    Kuroda, Shin-ichi

    1995-01-01

    The role of ESR spectroscopy in the characterization of functional LB films is discussed. Unpaired electrons in LB films are associated with isolated radical molecules produced by charge transfer, paramagnetic metallic ions such as Cu 2+ , strongly interacting spins in the mixed valence states in charge-transfer salts, and so on. These spins often manifest the functions of materials. They can also act as microscopic probes in the ESR analysis devoted for the elucidation of characteristic properties of LB films. In structural studies, ESR is of particular importance in the analysis of molecular orientation of LB films. ESR can unambiguously determine the orientation of molecules through g-value anisotropy: different g value, different resonance field. Two types of new control methods of molecular orientation in LB films originated from the ESR analysis: study of in-plane orientation in dye LB films which led to the discovery of flow-orientation effect, and observation of drastic change of orientation of Cu-porphyrin in LB films using the trigger molecule, n-hexatriacontane. In the studies of electronic properties, hyperfine interactions between electron and nuclear spins provide information about molecular orbitals and local structures. Stable isotopes have been successfully applied to the stable radicals in merocyanine LB films to identify hyperfine couplings. In conducting LB films composed of charge-transfer salts, quasi-one-dimensional antiferromagnetism in semiconducting films and spin resonance of conduction electrons in metallic films are observed. Results provide microscopic evidence for the development of columnar structures of constituent molecules. Development of new functional LB films may provide more cases where ESR spectroscopy will clarify the nature of such films. (author)

  11. Solid-state 13C NMR spectroscopy studies of xylans in the cell wall of Palmaria palmata (L. Kuntze, Rhodophyta).

    Science.gov (United States)

    Lahaye, Marc; Rondeau-Mouro, Corinne; Deniaud, Estelle; Buléon, Alain

    2003-07-22

    The chemical structure and interactions of the cell wall polysaccharides from the red edible seaweed Palmaria palmata were studied by liquid-like magic-angle-spinning (MAS) and cross-polarization MAS (CPMAS) solid-state 13C NMR spectroscopy. The liquid-like MAS and CPMAS 13C NMR spectra of the rehydrated algal powder revealed the presence of beta-(1-->4)/beta-(1-->3)-linked D-xylan with chemical shifts close to those observed in the solution 13C NMR spectrum of the polysaccharide. Observation of mix-linked xylan in the liquid-like MAS 13C NMR spectrum indicated that part of this cell wall polysaccharide is loosely held in the alga. The CPMAS NMR spectrum of the dry algal powder alcohol insoluble residue (AIR) showed broad peaks most of which corresponded to the mix-linked xylan. Hydration of AIR induced a marked increase in the signal resolution also in the CPMAS NMR spectra together with a shift of the C-3 and C-4 signals of the (1-->3)- and (1-->4)-linked xylose, respectively. Such modifications were present in the spectrum of hydrated (1-->3)-linked xylan from the green seaweed Caulerpa taxifolia and absent in that of (1-->4)-linked xylan from P. palmata. This result emphasizes the important role of (1-->3) linkages on the mix-linked xylan hydration-induced conformational rearrangement. The mix-linked xylan signals were observed in the CPMAS NMR spectrum of hydrated residues obtained after extensive extractions by NaOH or strong chaotropic solutions indicating strong hydrogen bonds or covalent linkages. T(1 rho) relaxations were measured close or above 10 ms for the mix-linked xylan in the dry and hydrated state in AIR and indicated that the overall xylan chains likely remain rigid. Rehydration of the mix-linked xylan lead to a decrease in the motion of protons bounded to the C-1 and C-4 carbons of the (1-->4)-linked xylose supporting the re-organization of the xylan chains under hydration involving junction-zones held by hydrogen bonds between adjacent (1

  12. Multiple acquisitions via sequential transfer of orphan spin polarization (MAeSTOSO): How far can we push residual spin polarization in solid-state NMR?

    Science.gov (United States)

    Gopinath, T; Veglia, Gianluigi

    2016-06-01

    Conventional multidimensional magic angle spinning (MAS) solid-state NMR (ssNMR) experiments detect the signal arising from the decay of a single coherence transfer pathway (FID), resulting in one spectrum per acquisition time. Recently, we introduced two new strategies, namely DUMAS (DUal acquisition Magic Angle Spinning) and MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), that enable the simultaneous acquisitions of multidimensional ssNMR experiments using multiple coherence transfer pathways. Here, we combined the main elements of DUMAS and MEIOSIS to harness both orphan spin operators and residual polarization and increase the number of simultaneous acquisitions. We show that it is possible to acquire up to eight two-dimensional experiments using four acquisition periods per each scan. This new suite of pulse sequences, called MAeSTOSO for Multiple Acquisitions via Sequential Transfer of Orphan Spin pOlarization, relies on residual polarization of both (13)C and (15)N pathways and combines low- and high-sensitivity experiments into a single pulse sequence using one receiver and commercial ssNMR probes. The acquisition of multiple experiments does not affect the sensitivity of the main experiment; rather it recovers the lost coherences that are discarded, resulting in a significant gain in experimental time. Both merits and limitations of this approach are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Spin Liquid State in the 3D Frustrated Antiferromagnet PbCuTe_{2}O_{6}: NMR and Muon Spin Relaxation Studies.

    Science.gov (United States)

    Khuntia, P; Bert, F; Mendels, P; Koteswararao, B; Mahajan, A V; Baenitz, M; Chou, F C; Baines, C; Amato, A; Furukawa, Y

    2016-03-11

    PbCuTe_{2}O_{6} is a rare example of a spin liquid candidate featuring a three-dimensional magnetic lattice. Strong geometric frustration arises from the dominant antiferromagnetic interaction that generates a hyperkagome network of Cu^{2+} ions although additional interactions enhance the magnetic lattice connectivity. Through a combination of magnetization measurements and local probe investigations by NMR and muon spin relaxation down to 20 mK, we provide robust evidence for the absence of magnetic freezing in the ground state. The local spin susceptibility probed by the NMR shift hardly deviates from the macroscopic one down to 1 K pointing to a homogeneous magnetic system with a low defect concentration. The saturation of the NMR shift and the sublinear power law temperature (T) evolution of the 1/T_{1} NMR relaxation rate at low T point to a nonsinglet ground state favoring a gapless fermionic description of the magnetic excitations. Below 1 K a pronounced slowing down of the spin dynamics is witnessed, which may signal a reconstruction of spinon Fermi surface. Nonetheless, the compound remains in a fluctuating spin liquid state down to the lowest temperature of the present investigation.

  14. NMR spectroscopy of muscle proteins; Spektroskopia MRJ bialek miesniowych

    Energy Technology Data Exchange (ETDEWEB)

    Slosarek, G. [Inst. Fizyki, Univ. A. Mickiewicza, Poznan (Poland)

    1995-12-31

    Author reviews various experimental techniques used for study of the structure of muscle proteins. Difficulties of application of NMR are described. Studies of the influence of Ca{sup 2+} on flexibility of actin polymer are presented. 11 refs, 3 figs.

  15. SOPPA and CCSD vibrational corrections to NMR indirect spin-spin coupling constants of small hydrocarbons

    Science.gov (United States)

    Faber, Rasmus; Sauer, Stephan P. A.

    2015-12-01

    We present zero-point vibrational corrections to the indirect nuclear spin-spin coupling constants in ethyne, ethene, cyclopropene and allene. The calculations have been carried out both at the level of the second order polarization propagator approximation (SOPPA) employing a new implementation in the DALTON program, at the density functional theory level with the B3LYP functional employing also the Dalton program and at the level of coupled cluster singles and doubles (CCSD) theory employing the implementation in the CFOUR program. Specialized coupling constant basis sets, aug-cc-pVTZ-J, have been employed in the calculations. We find that on average the SOPPA results for both the equilibrium geometry values and the zero-point vibrational corrections are in better agreement with the CCSD results than the corresponding B3LYP results. Furthermore we observed that the vibrational corrections are in the order of 5 Hz for the one-bond carbon-hydrogen couplings and about 1 Hz or smaller for the other couplings apart from the one-bond carbon-carbon coupling (11 Hz) and the two-bond carbon-hydrogen coupling (4 Hz) in ethyne. However, not for all couplings lead the inclusion of zero-point vibrational corrections to better agreement with experiment.

  16. SOPPA and CCSD vibrational corrections to NMR indirect spin-spin coupling constants of small hydrocarbons

    International Nuclear Information System (INIS)

    Faber, Rasmus; Sauer, Stephan P. A.

    2015-01-01

    We present zero-point vibrational corrections to the indirect nuclear spin-spin coupling constants in ethyne, ethene, cyclopropene and allene. The calculations have been carried out both at the level of the second order polarization propagator approximation (SOPPA) employing a new implementation in the DALTON program, at the density functional theory level with the B3LYP functional employing also the Dalton program and at the level of coupled cluster singles and doubles (CCSD) theory employing the implementation in the CFOUR program. Specialized coupling constant basis sets, aug-cc-pVTZ-J, have been employed in the calculations. We find that on average the SOPPA results for both the equilibrium geometry values and the zero-point vibrational corrections are in better agreement with the CCSD results than the corresponding B3LYP results. Furthermore we observed that the vibrational corrections are in the order of 5 Hz for the one-bond carbon-hydrogen couplings and about 1 Hz or smaller for the other couplings apart from the one-bond carbon-carbon coupling (11 Hz) and the two-bond carbon-hydrogen coupling (4 Hz) in ethyne. However, not for all couplings lead the inclusion of zero-point vibrational corrections to better agreement with experiment

  17. 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.

  18. A High-Resolution Magic Angle Spinning NMR Study of the Enantiodiscrimination of 3,4-Methylenedioxymethamphetamine (MDMA by an Immobilized Polysaccharide-Based Chiral Phase.

    Directory of Open Access Journals (Sweden)

    Juliana C Barreiro

    Full Text Available This paper reports the investigation of the chiral interaction between 3,4-methylenedioxy-methamphetamine (MDMA enantiomers and an immobilized polysaccharide-based chiral phase. For that, suspended-state high-resolution magic angle spinning nuclear magnetic resonance spectroscopy (1H HR-MAS NMR was used. 1H HR-MAS longitudinal relaxation time and Saturation Transfer Difference (STD NMR titration experiments were carried out yielding information at the molecular level of the transient diastereoisomeric complexes of MDMA enantiomers and the chiral stationary phase. The interaction of the enantiomers takes place through the aromatic moiety of MDMA and the aromatic group of the chiral selector by π-π stacking for both enantiomers; however, a stronger interaction was observed for the (R-enantiomer, which is the second one to elute at the chromatographic conditions.

  19. Probing the flexibility of internal rotation in silylated phenols with the NMR scalar spin-spin coupling constants.

    Science.gov (United States)

    Sychrovský, Vladimír; Benda, Ladislav; Prokop, Alexandr; Blechta, Vratislav; Schraml, Jan; Spirko, Vladimír

    2008-06-12

    The rotation of a trimethylsiloxy (TMSO) group in three silylated phenols (with three different ortho substituents -H, -CH3, and -C(CH3)3) was studied with the NMR (n)J(Si,C), n = 2, 3, 4, 5, scalar spin-spin coupling between the (29)Si nucleus of the TMSO group and the (13)C nuclei of the phenyl ring. The internal rotation potential calculated with the B3LYP and MP2 calculation methods including the effect of a solvent environment (gas phase, chloroform, and water) was used for the calculation of the dynamical averages of the scalar coupling constants in the framework of the rigid-bender formalism. Solvent effects, the quality of the rotational potential, and the applicability of the classical molecular dynamic to the problem is discussed. Quantum effects have a sizable impact on scalar couplings, particularly for the internal rotational states well localized within the wells of the potential surfaces for the TMSO group. The overall difference between the experimental and theoretical scalar couplings calculated for the global energy-minima structures (static model) decreases substantially for both model potentials (B3LYP, MP2) when the molecular motion of the TMSO group is taken into account. The calculated data indicate that the inclusion of molecular motion is necessary for the accurate calculation of the scalar coupling constants and their reliable structural interpretation for any system which possesses a large-amplitude motion.

  20. Resonant pinning spectroscopy with spin-vortex pairs

    Science.gov (United States)

    Holmgren, E.; Bondarenko, A.; Ivanov, B. A.; Korenivski, V.

    2018-03-01

    Vortex pairs in magnetic nanopillars with strongly coupled cores and pinning of one of the cores by a morphological defect, are used to perform resonant pinning spectroscopy, in which a microwave excitation applied to the nanopillar produces pinning or depinning of the cores only when the excitation is in resonance with the rotational or gyrational eigenmodes of the specific initial state of the core-core pair. The shift in the eigenmode frequencies between the pinned and depinned states is determined experimentally and explained theoretically, and illustrates the potential for multicore spin-vortex memory with resonant writing of information onto various stable vortex pair states. Further, it is shown how the same resonant spectroscopy techniques applied to a vortex pair can be used as a sensitive nanoscale probe for characterizing morphological defects in magnetic films.

  1. Broadband MAS NMR spectroscopy in the low-power limit

    Science.gov (United States)

    Sanders, Kevin J.; Pell, Andrew J.; Wegner, Sebastian; Grey, Clare P.; Pintacuda, Guido

    2018-04-01

    We investigate the performance of broadband adiabatic inversion pulses in the high-power (short high-powered adiabatic pulse, SHAP) and low-power (single-sideband-selective adiabatic pulse, S3AP) RF regimes on a spin system subjected to large anisotropic interactions. We show by combined experimental results and spin dynamics simulations that when the magic-angle spinning rate exceeds 100 kHz S3APs begin outperforming SHAPs. This is especially true for low-gamma nuclei, such as 6 Li in paramagnetic Li-ion battery materials. Finally, we show how S3APs can be improved by combining multiple waveforms sweeping over multiple sidebands simultaneously, in order to produce inverted sideband profiles free from intensity biasing.

  2. [Detection of peranesthetic malignant hyperthermia by muscle contracture tests and NMR spectroscopy].

    Science.gov (United States)

    Kozak-Reiss, G; Gascard, J P; Redouane-Bénichou, K

    1986-01-01

    To diagnose malignant hyperthermia susceptibility (MHS), caffeine and halothane contracture tests were performed on six patients. One of them, who presented a peroperative crisis, was recognized as MHS; the five others were negative (MHN). By means of 31P-NMR spectroscopy, the muscular energetic metabolism of these patients was studied during and after moderate exercise in normal and moderate ischaemic conditions. Metabolic abnormalities appeared in the MHS patient. It must be concluded therefore that malignant hyperthermia is a latent myopathy. 31P-NMR spectroscopy appeared to be a useful non-invasive tool for screening for this affliction.

  3. Solid-State NMR Spectroscopy of Metal–Organic Framework Compounds (MOFs

    Directory of Open Access Journals (Sweden)

    Stefan Kaskel

    2012-11-01

    Full Text Available Nuclear Magnetic Resonance (NMR spectroscopy is a well-established method for the investigation of various types of porous materials. During the past decade, metal–organic frameworks have attracted increasing research interest. Solid-state NMR spectroscopy has rapidly evolved into an important tool for the study of the structure, dynamics and flexibility of these materials, as well as for the characterization of host–guest interactions with adsorbed species such as xenon, carbon dioxide, water, and many others. The present review introduces and highlights recent developments in this rapidly growing field.

  4. Use of earth field spin echo NMR to search for liquid minerals

    Science.gov (United States)

    Stoeffl, Wolfgang

    2001-01-01

    An instrument for measuring the spatial, qualitative and quantitative parameters of an underground nuclear magnetic resonance (NMR) active liquid mineral deposit, including oil and water. A phased array of excitation and receiver antennas on the surface and/or in a borehole excites the NMR active nuclei in the deposit, and using known techniques from magnetic resonance imaging (MRI), the spatial and quantitative distribution of the deposit can be measured. A surface array may utilize, for example, four large (50-500 diameter) diameter wire loops laid on the ground surface, and a weak (1.5-2.5 kHz) alternating current (AC) field applied, matching the NMR frequency of hydrogen in the rather flat and uniform earth magnetic field. For a short duration (a few seconds) an additional gradient field can be generated, superimposed to the earth field, by applying direct current (DC) to the grid (wire loops), enhancing the position sensitivity of the spin-echo and also suppressing large surface water signals by shifting them to a different frequency. The surface coil excitation can be combined with downhole receivers, which are much more radio-quiet compared to surface receivers, and this combination also enhances the position resolution of the MRI significantly. A downhole receiver module, for example, may have a 5.5 inch diameter and fit in a standard six inch borehole having a one-quarter inch thick stainless steel casing. The receiver module may include more than one receiver units for improved penetration and better position resolution.

  5. A low-E magic angle spinning probe for biological solid state NMR at 750 MHz

    Science.gov (United States)

    McNeill, Seth A.; Gor'kov, Peter L.; Shetty, Kiran; Brey, William W.; Long, Joanna R.

    2009-04-01

    Crossed-coil NMR probes are a useful tool for reducing sample heating for biological solid state NMR. In a crossed-coil probe, the higher frequency 1H field, which is the primary source of sample heating in conventional probes, is produced by a separate low-inductance resonator. Because a smaller driving voltage is required, the electric field across the sample and the resultant heating is reduced. In this work we describe the development of a magic angle spinning (MAS) solid state NMR probe utilizing a dual resonator. This dual resonator approach, referred to as "low-E," was originally developed to reduce heating in samples of mechanically aligned membranes. The study of inherently dilute systems, such as proteins in lipid bilayers, via MAS techniques requires large sample volumes at high field to obtain spectra with adequate signal-to-noise ratio under physiologically relevant conditions. With the low-E approach, we are able to obtain homogeneous and sufficiently strong radiofrequency fields for both 1H and 13C frequencies in a 4 mm probe with a 1H frequency of 750 MHz. The performance of the probe using windowless dipolar recoupling sequences is demonstrated on model compounds as well as membrane-embedded peptides.

  6. NMR investigations of surfaces and interfaces using spin-polarized xenon

    Energy Technology Data Exchange (ETDEWEB)

    Gaede, Holly Caroline [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1995-07-01

    129Xe NMR is potentially useful for the investigation of material surfaces, but has been limited to high surface area samples in which sufficient xenon can be loaded to achieve acceptable signal to noise ratios. In Chapter 2 conventional 129Xe NMR is used to study a high surface area polymer, a catalyst, and a confined liquid crystal to determine the topology of these systems. Further information about the spatial proximity of different sites of the catalyst and liquid crystal systems is determined through two dimensional exchange NMR in Chapter 3. Lower surface area systems may be investigated with spin-polarized xenon, which may be achieved through optical pumping and spin exchange. Optically polarized xenon can be up to 105times more sensitive than thermally polarized xenon. In Chapter 4 highly polarized xenon is used to examine the surface of poly(acrylonitrile) and the formation of xenon clathrate hydrates. An attractive use of polarized xenon is as a magnetization source in cross polarization experiments. Cross polarization from adsorbed polarized xenon may allow detection of surface nuclei with drastic enhancements. A non-selective low field thermal mixing technique is used to enhance the 13C signal of CO2 of xenon occluded in solid CO2 by a factor of 200. High-field cross polarization from xenon to proton on the surface of high surface area polymers has enabled signal enhancements of ~1,000. These studies, together with investigations of the efficiency of the cross polarization process from polarized xenon, are discussed in Chapter 5. Another use of polarized xenon is as an imaging contrast agent in systems that are not compatible with traditional contrast agents. The resolution attainable with this method is determined through images of structured phantoms in Chapter 6.

  7. High-resolution 1H NMR spectroscopy of fish muscle, eggs and small whole fish via Hadamard-encoded intermolecular multiple-quantum coherence.

    Directory of Open Access Journals (Sweden)

    Honghao Cai

    Full Text Available BACKGROUND AND PURPOSE: Nuclear magnetic resonance (NMR spectroscopy has become an important technique for tissue studies. Since tissues are in semisolid-state, their high-resolution (HR spectra cannot be obtained by conventional NMR spectroscopy. Because of this restriction, extraction and high-resolution magic angle spinning (HR MAS are widely applied for HR NMR spectra of tissues. However, both of the methods are subject to limitations. In this study, the feasibility of HR (1H NMR spectroscopy based on intermolecular multiple-quantum coherence (iMQC technique is explored using fish muscle, fish eggs, and a whole fish as examples. MATERIALS AND METHODS: Intact salmon muscle tissues, intact eggs from shishamo smelt and a whole fish (Siamese algae eater are studied by using conventional 1D one-pulse sequence, Hadamard-encoded iMQC sequence, and HR MAS. RESULTS: When we use the conventional 1D one-pulse sequence, hardly any useful spectral information can be obtained due to the severe field inhomogeneity. By contrast, HR NMR spectra can be obtained in a short period of time by using the Hadamard-encoded iMQC method without shimming. Most signals from fatty acids and small metabolites can be observed. Compared to HR MAS, the iMQC method is non-invasive, but the resolution and the sensitivity of resulting spectra are not as high as those of HR MAS spectra. CONCLUSION: Due to the immunity to field inhomogeneity, the iMQC technique can be a proper supplement to HR MAS, and it provides an alternative for the investigation in cases with field distortions and with samples unsuitable for spinning. The acquisition time of the proposed method is greatly reduced by introduction of the Hadamard-encoded technique, in comparison with that of conventional iMQC method.

  8. Polarisation of a spin- {1}/{2} β-NMR probe 11Be using collinear laser optical pumping

    Science.gov (United States)

    Levy, C. D. P.; Pearson, M. R.; Morris, G. D.; Lassen, J.; Chow, K. H.; Hossain, M. D.; Kiefl, R. F.; Labbé, R.; MacFarlane, W. A.; Parolin, T. J.; Root, L.; Saadaoui, H.; Smadella, M.; Wang, D.

    2009-04-01

    Spin {1}/{2} probes have special importance in the field of NMR, since they have no electric quadrupole moment and are thus pure magnetic sensors. The absence of quadrupolar splittings greatly simplifies the NMR frequency spectrum. That the muon is spin {1}/{2} is one of the reasons it has become so useful as a magnetic probe. Until now there has been no spin {1}/{2} probe suitable for beta-detected NMR. Such a probe would be particularly useful in complex materials, which are in general non-cubic. In this paper we describe the development of a low energy beam of spin-polarised 11Be, which is the lightest spin {1}/{2} isotope suitable for β-NMR. The intensity of the 11Be+ beam-generated by a laser ionisation source-is about 106/s. The 11Be nuclei are polarised by collinear laser optical pumping with an externally frequency doubled dye laser tuned to the 2S- 2P transition of 11Be+ at 313 nm.

  9. O17 and V51 NMR for the zigzag spin-1 chain compound CaV2O4

    Science.gov (United States)

    Zong, X.; Suh, B. J.; Niazi, A.; Yan, J. Q.; Schlagel, D. L.; Lograsso, T. A.; Johnston, D. C.

    2008-01-01

    V51 NMR studies on CaV2O4 single crystals and O17 NMR studies on O17 -enriched powder samples are reported. The temperature dependences of the O17 NMR linewidth and nuclear spin-lattice relaxation rate give strong evidence for a long-range antiferromagnetic transition at TN=78K in the powder. Magnetic susceptibility measurements show that TN=69K in the crystals. A zero-field V51 NMR signal was observed at low temperatures ( f≈237MHz at 4.2K ) in the crystals. The field-swept spectra with the field in different directions suggest the presence of two antiferromagnetic substructures. Each substructure is collinear, with the easy axes of the two substructures separated by an angle of 19(1)°, and with their average direction pointing approximately along the b axis of the crystal structure. The two spin substructures contain equal numbers of spins. The temperature dependence of the ordered moment, measured up to 45K , shows the presence of an energy gap EG in the antiferromagnetic spin wave excitation spectrum. Antiferromagnetic spin wave theory suggests that EG/kB lies between 64 and 98K .

  10. Polarisation of a spin-1/2 beta-NMR probe {sup 11}Be using collinear laser optical pumping

    Energy Technology Data Exchange (ETDEWEB)

    Levy, C.D.P., E-mail: levy@triumf.c [TRIUMF, Wesbrook Mall 4004, Vancouver, British Columbia, V6T 2A3 (Canada); Pearson, M.R.; Morris, G.D.; Lassen, J. [TRIUMF, Wesbrook Mall 4004, Vancouver, British Columbia, V6T 2A3 (Canada); Chow, K.H. [Department of Physics, University of Alberta, Edmonton, Alberta, T6G 2G7 (Canada); Hossain, M.D. [Department of Physics and Astronomy, University of British Columbia, Vancouver, British Columbia, V6T 1Z1 (Canada); Kiefl, R.F. [TRIUMF, Wesbrook Mall 4004, Vancouver, British Columbia, V6T 2A3 (Canada); Department of Physics and Astronomy, University of British Columbia, Vancouver, British Columbia, V6T 1Z1 (Canada); Canadian Institute for Advanced Research, 180 Dundas Street West, Toronto, Ontario, M5G 1Z8 (Canada); Labbe, R. [Departement de Physique, Universite Laval, Quebec, G1K 7P4 (Canada); MacFarlane, W.A.; Parolin, T.J. [Chemistry Department, University of British Columbia, Vancouver, British Columbia, V6T 1Z1 (Canada); Root, L. [TRIUMF, Wesbrook Mall 4004, Vancouver, British Columbia, V6T 2A3 (Canada); Saadaoui, H.; Smadella, M.; Wang, D. [Department of Physics and Astronomy, University of British Columbia, Vancouver, British Columbia, V6T 1Z1 (Canada)

    2009-04-15

    Spin 1/2 probes have special importance in the field of NMR, since they have no electric quadrupole moment and are thus pure magnetic sensors. The absence of quadrupolar splittings greatly simplifies the NMR frequency spectrum. That the muon is spin 1/2 is one of the reasons it has become so useful as a magnetic probe. Until now there has been no spin 1/2 probe suitable for beta-detected NMR. Such a probe would be particularly useful in complex materials, which are in general non-cubic. In this paper we describe the development of a low energy beam of spin-polarised {sup 11}Be, which is the lightest spin 1/2 isotope suitable for beta-NMR. The intensity of the {sup 11}Be{sup +} beam-generated by a laser ionisation source-is about 10{sup 6}/s. The {sup 11}Be nuclei are polarised by collinear laser optical pumping with an externally frequency doubled dye laser tuned to the {sup 2}S{sub 1/2}-{sup 2}P{sub 1/2} transition of {sup 11}Be{sup +} at 313 nm.

  11. New insights into glycopeptide antibiotic binding to cell wall precursors using SPR and NMR spectroscopy.

    Science.gov (United States)

    Treviño, Juan; Bayón, Carlos; Ardá, Ana; Marinelli, Flavia; Gandolfi, Raffaella; Molinari, Francesco; Jimenez-Barbero, Jesús; Hernáiz, María J

    2014-06-10

    Glycopeptide antibiotics, such as vancomycin and teicoplanin, are used to treat life-threatening infections caused by multidrug-resistant Gram-positive pathogens. They inhibit bacterial cell wall biosynthesis by binding to the D-Ala-D-Ala C-terminus of peptidoglycan precursors. Vancomycin-resistant bacteria replace the dipeptide with the D-Ala-D-Lac depsipeptide, thus reducing the binding affinity of the antibiotics with their molecular targets. Herein, studies of the interaction of teicoplanin, teicoplanin-like A40926, and of their semisynthetic derivatives (mideplanin, MDL63,246, dalbavancin) with peptide analogues of cell-wall precursors by NMR spectroscopy and surface plasmon resonance (SPR) are reported. NMR spectroscopy revealed the existence of two different complexes in solution, when the different glycopeptides interact with Ac2KdAlaDAlaOH. Despite the NMR experimental conditions, which are different from those employed for the SPR measurements, the NMR spectroscopy results parallel those deduced in the chip with respect to the drastic binding difference existing between the D-Ala and the D-Lac terminating analogues, confirming that all these antibiotics share the same primary molecular mechanism of action and resistance. Kinetic analysis of the interaction between the glycopeptide antibiotics and immobilized AcKdAlaDAlaOH by SPR suggest a dimerization process that was not observed by NMR spectroscopy in DMSO solution. Moreover, in SPR, all glycopeptides with a hydrophobic acyl chain present stronger binding with a hydrophobic surface than vancomycin, indicating that additional interactions through the employed surface are involved. In conclusion, SPR provides a tool to differentiate between vancomycin and other glycopeptides, and the calculated binding affinities at the surface seem to be more relevant to in vitro antimicrobial activity than the estimations from NMR spectroscopy analysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Edén, Mattias

    2010-05-01

    Three two-dimensional (2D) NMR homonuclear correlation techniques invoking double-quantum (2Q) filtration of the central transitions of half-integer spins are evaluated numerically and experimentally. They correlate directly detected single-quantum (1Q) coherences in the t2 domain with either of 1Q, two-spin 2Q or single-spin multiple-quantum coherence-evolutions in the indirect (t1) dimension. We employ experimental 23Na and 27Al NMR on sodium sulfite and the natural mineral sillimanite (SiAl2O5), in conjunction with simulated 2D spectra from pairs of dipolar-recoupled spins-3/2 and 5/2 at different external magnetic fields, to compare the correlation strategies from the viewpoints of 2D spectral resolution, signal sensitivity, implementational aspects and their relative merits for establishing internuclear proximities and quadrupolar tensor orientations.

  13. NMR in an electric field: A bulk probe of the hidden spin and orbital polarizations

    Science.gov (United States)

    Ramírez-Ruiz, Jorge; Boutin, Samuel; Garate, Ion

    2017-12-01

    Recent theoretical work has established the presence of hidden spin and orbital textures in nonmagnetic materials with inversion symmetry. Here, we propose that these textures can be detected by nuclear magnetic resonance (NMR) measurements carried out in the presence of an electric field. In crystals with hidden polarizations, a uniform electric field produces a staggered magnetic field that points to opposite directions at atomic sites related by spatial inversion. As a result, the NMR resonance peak corresponding to inversion partner nuclei is split into two peaks. The magnitude of the splitting is proportional to the electric field and depends on the orientation of the electric field with respect to the crystallographic axes and the external magnetic field. As a case study, we present a theory of electric-field-induced splitting of NMR peaks for 77Se,125Te, and 209Bi in Bi2Se3 and Bi2Te3 . In conducting samples with current densities of ≃106A/cm 2 , the splitting for Bi can reach 100 kHz , which is comparable to or larger than the intrinsic width of the NMR lines. In order to observe the effect experimentally, the peak splitting must also exceed the linewidth produced by the Oersted field. In Bi2Se3 , this requires narrow wires of radius ≲1 μ m . We also discuss other potentially more promising candidate materials, such as SrRuO3 and BaIr2Ge2 , whose crystal symmetry enables strategies to suppress the linewidth produced by the Oersted field.

  14. Magic Angle Spinning NMR Structure Determination of Proteins from Pseudocontact Shifts

    KAUST Repository

    Li, Jianping

    2013-06-05

    Magic angle spinning solid-state NMR is a unique technique to study atomic-resolution structure of biomacromolecules which resist crystallization or are too large to study by solution NMR techniques. However, difficulties in obtaining sufficient number of long-range distance restraints using dipolar coupling based spectra hamper the process of structure determination of proteins in solid-state NMR. In this study it is shown that high-resolution structure of proteins in solid phase can be determined without the use of traditional dipolar-dipolar coupling based distance restraints by combining the measurements of pseudocontact shifts (PCSs) with Rosetta calculations. The PCSs were generated by chelating exogenous paramagnetic metal ions to a tag 4-mercaptomethyl-dipicolinic acid, which is covalently attached to different residue sites in a 56-residue immunoglobulin-binding domain of protein G (GB1). The long-range structural restraints with metal-nucleus distance of up to ∼20 Å are quantitatively extracted from experimentally observed PCSs, and these are in good agreement with the distances back-calculated using an X-ray structure model. Moreover, we demonstrate that using several paramagnetic ions with varied paramagnetic susceptibilities as well as the introduction of paramagnetic labels at different sites can dramatically increase the number of long-range restraints and cover different regions of the protein. The structure generated from solid-state NMR PCSs restraints combined with Rosetta calculations has 0.7 Å root-mean-square deviation relative to X-ray structure. © 2013 American Chemical Society.

  15. Interaction study of polyisobutylene with paraffins by NMR using the evaluation of spin-lattice relaxation times for hydrogen nuclei

    International Nuclear Information System (INIS)

    Marques, Rosana G.G.; Tavares, Maria I.B.

    2001-01-01

    The evaluation of spin-lattice relaxation times of 1 H for polyisobutylene/paraffin systems, were obtained using the classic inversion recovery technique, and also through Cross Polarization Magic Angle Spinning (CP/MAS) techniques varying the contact time and also by the delayed contact time pulse sequence. NMR results showed that the polyisobutylene/paraffin systems in which high molecular weight paraffins were used, is heterogeneous. However, for paraffins with low molecular weight, the system presents good homogeneity. (author)

  16. An in vivo statistical total correlation NMR spectroscopy approach

    Indian Academy of Sciences (India)

    statistical total correlation spectroscopy' analysis (STOCSY), are valuable tools to collect and interpret the metabolic responses of a living organism to external stimuli. In this study, we applied this approach to evaluate the effects of increasing ...

  17. Gaussian-approximation formalism for evaluating decay of NMR spin echoes

    International Nuclear Information System (INIS)

    Recchia, C.H.; Gorny, K.; Pennington, C.H.

    1996-01-01

    We present a formalism for evaluating the amplitude of the NMR spin echo and stimulated echo as a function of pulse spacings, for situations in which the nuclear spins experience an effective longitudinal magnetic field h z (t) resulting from an arbitrary number of independent sources, each characterized by its own arbitrary time correlation function. The distribution of accumulated phase angles for the ensemble of nuclear spins at the time of the echo is approximated as a Gaussian. The development of the formalism is motivated by the need to understand the transverse relaxation of 89 Y in YBa 2 Cu 3 O 7 , in which the 89 Y experiences 63,65 Cu dipolar fields which fluctuate due to 63,65 Cu T 1 processes. The formalism is applied successfully to this example, and to the case of nuclei diffusing in a spatially varying magnetic field. Then we examine a situation in which the approximation fails emdash the classic problem of chemical exchange in dimethylformamide, where the methyl protons experience a chemical shift which fluctuates between two discrete values. In this case the Gaussian approximation yields a monotonic decay of the echo amplitude with increasing pulse spacing, while the exact solution yields distinct open-quote open-quote beats close-quote close-quote in the echo height, which we confirm experimentally. In light of this final example the limits of validity of the approximation are discussed. copyright 1996 The American Physical Society

  18. Recent developments and applications of saturation transfer difference nuclear magnetic resonance (STD NMR) spectroscopy.

    Science.gov (United States)

    Wagstaff, Jane L; Taylor, Samantha L; Howard, Mark J

    2013-04-05

    This review aims to illustrate that STD NMR is not simply a method for drug screening and discovery, but has qualitative and quantitative applications that can answer fundamental and applied biological and biomedical questions involving molecular interactions between ligands and proteins. We begin with a basic introduction to the technique of STD NMR and report on recent advances and biological applications of STD including studies to follow the interactions of non-steroidal anti-inflammatories, minimum binding requirements for virus infection and understating inhibition of amyloid fibre formation. We expand on this introduction by reporting recent STD NMR studies of live-cell receptor systems, new methodologies using scanning STD, magic-angle spinning STD and approaches to use STD NMR in a quantitative fashion for dissociation constants and group epitope mapping (GEM) determination. We finish by outlining new approaches that have potential to influence future applications of the technique; NMR isotope-editing, heteronuclear multidimensional STD and (19)F STD methods that are becoming more amenable due to the latest NMR equipment technologies.

  19. Probing acid-amide intermolecular hydrogen bonding by NMR spectroscopy and DFT calculations

    Science.gov (United States)

    Chaudhari, Sachin Rama; Suryaprakash, N.

    2012-05-01

    Benzene carboxylic acids and benzamide act as their self-complement in molecular recognition to form inter-molecular hydrogen bonded dimers between amide and carboxylic acid groups, which have been investigated by 1H, 13C and 15N NMR spectroscopy. Extensive NMR studies using diffusion ordered spectroscopy (DOSY), variable temperature 1D, 2D NMR, established the formation of heterodimers of benzamide with benzoic acid, salicylic acid and phenyl acetic acid in deuterated chloroform solution. Association constants for the complex formation in the solution state have been determined. The results are ascertained by X-ray diffraction in the solid state. Intermolecular interactions in solution and in solid state were found to be similar. The structural parameters obtained by X-ray diffraction studies are compared with those obtained by DFT calculations.

  20. Structure determination of helical filaments by solid-state NMR spectroscopy

    Science.gov (United States)

    Ahmed, Mumdooh; Spehr, Johannes; König, Renate; Lünsdorf, Heinrich; Rand, Ulfert; Lührs, Thorsten; Ritter, Christiane

    2016-01-01

    The controlled formation of filamentous protein complexes plays a crucial role in many biological systems and represents an emerging paradigm in signal transduction. The mitochondrial antiviral signaling protein (MAVS) is a central signal transduction hub in innate immunity that is activated by a receptor-induced conversion into helical superstructures (filaments) assembled from its globular caspase activation and recruitment domain. Solid-state NMR (ssNMR) spectroscopy has become one of the most powerful techniques for atomic resolution structures of protein fibrils. However, for helical filaments, the determination of the correct symmetry parameters has remained a significant hurdle for any structural technique and could thus far not be precisely derived from ssNMR data. Here, we solved the atomic resolution structure of helical MAVSCARD filaments exclusively from ssNMR data. We present a generally applicable approach that systematically explores the helical symmetry space by efficient modeling of the helical structure restrained by interprotomer ssNMR distance restraints. Together with classical automated NMR structure calculation, this allowed us to faithfully determine the symmetry that defines the entire assembly. To validate our structure, we probed the protomer arrangement by solvent paramagnetic resonance enhancement, analysis of chemical shift differences relative to the solution NMR structure of the monomer, and mutagenesis. We provide detailed information on the atomic contacts that determine filament stability and describe mechanistic details on the formation of signaling-competent MAVS filaments from inactive monomers. PMID:26733681

  1. Influence of water on stability of geopolymers investigated by NMR solid state spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Kobera, Libor; Brus, Jiří; Urbanová, Martina; Slavík, R.

    2008-01-01

    Roč. 33, - (2008), s. 86 ISSN 1896-2203. [Mid-European Clay Conference MECC 08 /4./. 22.09.2008-27.09.2008, Zakopane] R&D Projects: GA AV ČR IAA400500602 Institutional research plan: CEZ:AV0Z40500505 Keywords : stability * NMR * solid state spectroscopy * geopolymer Subject RIV: CD - Macromolecular Chemistry

  2. Structural investigation of bistrifluron using x-ray crystallography, NMR spectroscopy, and molecular modeling

    CERN Document Server

    Moon, J K; Rhee, S K; Kim, G B; Yun, H S; Chung, B J; Lee, S S; Lim, Y H

    2002-01-01

    A new insecticide, bistrifluron acts as an inhibitor of insect development and interferes with the cuticle formation of insects. Since it shows low acute oral and dermal toxicities, it can be one of potent insecticides. Based on X-ray crystallography, NMR spectroscopy and molecular modeling, the structural studies of bistrifluron have been carried out.

  3. Structural analysis of the carbohydrate chains of glycoproteins by 500-MHz 1H-NMR spectroscopy

    International Nuclear Information System (INIS)

    Mutsaers, J.H.G.M.

    1986-01-01

    This thesis deals with the structural analysis by 500-MHz 1 H-NMR spectroscopy of carbohydrate chains obtained from glycoproteins. In the chapters 1 to 6 the structural analysis of N-glycosidically linked carbohydrate chains is described. The chapters 7 to 10 describe the structural analysis of O-glycosidically linked carbohydrate chains. 381 refs.; 44 figs.; 24 tabs.; 7 schemes

  4. High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound

    Science.gov (United States)

    Pacilio, Julia E.; Tokarski, John T.; Quiñones, Rosalynn; Iuliucci, Robbie J.

    2014-01-01

    High-resolution solid-state NMR (SSNMR) spectroscopy has many advantages as a tool to characterize solid-phase material that finds applications in polymer chemistry, nanotechnology, materials science, biomolecular structure determination, and others, including the pharmaceutical industry. The technology associated with achieving high resolution…

  5. Simultaneous 31P NMR spectroscopy and EMG in exercising and recovering human skeletal muscle: technical aspects

    DEFF Research Database (Denmark)

    Vestergaard-Poulsen, P; Thomsen, C; Sinkjaer, T

    1994-01-01

    The bioenergetics of human skeletal muscle can be studied by 31P NMR spectroscopy (31P-MRS) and by surface electromyography (SEMG). Simultaneous 31P-MRS and SEMG permit accurate and noninvasive studies of the correlation between metabolic and electrical changes in exercising and recovering human...

  6. NMR imaging and spectroscopy of the mammalian central nervous system after heavy ion radiation

    International Nuclear Information System (INIS)

    Richards, T.

    1984-09-01

    NMR imaging, NMR spectroscopic, and histopathologic techniques were used to study the proton relaxation time and related biochemical changes in the central nervous system after helium beam in vivo irradiation of the rodent brain. The spectroscopic observations reported in this dissertation were made possible by development of methods for measuring the NMR parameters of the rodent brain in vivo and in vitro. The methods include (1) depth selective spectroscopy using an optimization of rf pulse energy based on a priori knowledge of N-acetyl aspartate and lipid spectra of the normal brain, (2) phase-encoded proton spectroscopy of the living rodent using a surface coil, and (3) dual aqueous and organic tissue extraction technique for spectroscopy. Radiation induced increases were observed in lipid and p-choline peaks of the proton spectrum, in vivo. Proton NMR spectroscopy measurements on brain extracts (aqueous and organic solvents) were made to observe chemical changes that could not be seen in vivo. Radiation-induced changes were observed in lactate, GABA, glutamate, and p-choline peak areas of the aqueous fraction spectra. In the organic fraction, decreases were observed in peak area ratios of the terminal-methyl peaks, the N-methyl groups of choline, and at a peak at 2.84 ppM (phosphatidyl ethanolamine and phosphatidyl serine resonances) relative to TMS. With histology and Evans blue injections, blood-brain barrier alternations were seen as early as 4 days after irradiation. 83 references, 53 figures

  7. Determination of the Nucleic Acid Adducts Structure at the Nucleoside/Nucleotide Level by NMR Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Dračínský, Martin; Pohl, Radek

    2015-01-01

    Roč. 28, č. 2 (2015), s. 155-165 ISSN 0893-228X R&D Projects: GA ČR GA13-24880S Institutional support: RVO:61388963 Keywords : NMR spectroscopy * nucleic acids * nucleotides Subject RIV: CC - Organic Chemistry Impact factor: 3.025, year: 2015

  8. Near constant loss regime in fast ionic conductors analyzed by impedance and NMR spectroscopies

    Czech Academy of Sciences Publication Activity Database

    Bucheli, W.; Arbi, K.; Sanz, J.; Nuzhnyy, Dmitry; Kamba, Stanislav; Várez, A.; Jimenez, R.

    2014-01-01

    Roč. 16, č. 29 (2014), s. 15346-15354 ISSN 1463-9076 R&D Projects: GA ČR GAP204/12/0232 Institutional support: RVO:68378271 Keywords : microwave impedance spectroscopy * NMR * ionic conductivity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.493, year: 2014

  9. Role of hydration in the phase transition of polypeptides investigated by NMR and Raman spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Dybal, Jiří; Schmidt, Pavel; Kříž, Jaroslav; Kurková, Dana; Rodriguez-Cabello, J. C.; Alonso, M.

    2004-01-01

    Roč. 205, - (2004), s. 143-150 ISSN 1022-1360 R&D Projects: GA AV ČR IAA4050208 Institutional research plan: CEZ:AV0Z4050913 Keywords : NMR * quantum chemistry * Raman spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.691, year: 2004

  10. Structure Determination of Unknown Organic Liquids Using NMR and IR Spectroscopy: A General Chemistry Laboratory

    Science.gov (United States)

    Pavel, John T.; Hyde, Erin C.; Bruch, Martha D.

    2012-01-01

    This experiment introduced general chemistry students to the basic concepts of organic structures and to the power of spectroscopic methods for structure determination. Students employed a combination of IR and NMR spectroscopy to perform de novo structure determination of unknown alcohols, without being provided with a list of possible…

  11. Conformational Properties and orientational order of a de Vries liquid crystal investigated through NMR spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Domenici, V.; Lelli, M.; Cifelli, M.; Hamplová, Věra; Marchetti, A.; Veracini, C.A.

    2014-01-01

    Roč. 15, č. 7 (2014), s. 1485-1495 ISSN 1439-4235 Institutional support: RVO:68378271 Keywords : conformations * liquid crystals * orientational order * phase transitions * solid-state NMR spectroscopy Subject RIV: CC - Organic Chemistry Impact factor: 3.419, year: 2014

  12. Partial linear fit : a new NMR spectroscopy preprocessing tool for pattern recognition applications

    NARCIS (Netherlands)

    Vogels, J.T.W.E.; Tas, A.C.; Venekamp, J.; Greef, J. van der

    1996-01-01

    NMR spectroscopy is increasingly used in combination with multivariate analysis applications. Especially in the analysis of food products and the study of natural processes it has proved its usefulness. The samples used in these evaluations are however, often difficult to control. 'Positional'

  13. NMR imaging and spectroscopy of the mammalian central nervous system after heavy ion radiation

    Energy Technology Data Exchange (ETDEWEB)

    Richards, T.

    1984-09-01

    NMR imaging, NMR spectroscopic, and histopathologic techniques were used to study the proton relaxation time and related biochemical changes in the central nervous system after helium beam in vivo irradiation of the rodent brain. The spectroscopic observations reported in this dissertation were made possible by development of methods for measuring the NMR parameters of the rodent brain in vivo and in vitro. The methods include (1) depth selective spectroscopy using an optimization of rf pulse energy based on a priori knowledge of N-acetyl aspartate and lipid spectra of the normal brain, (2) phase-encoded proton spectroscopy of the living rodent using a surface coil, and (3) dual aqueous and organic tissue extraction technique for spectroscopy. Radiation induced increases were observed in lipid and p-choline peaks of the proton spectrum, in vivo. Proton NMR spectroscopy measurements on brain extracts (aqueous and organic solvents) were made to observe chemical changes that could not be seen in vivo. Radiation-induced changes were observed in lactate, GABA, glutamate, and p-choline peak areas of the aqueous fraction spectra. In the organic fraction, decreases were observed in peak area ratios of the terminal-methyl peaks, the N-methyl groups of choline, and at a peak at 2.84 ppM (phosphatidyl ethanolamine and phosphatidyl serine resonances) relative to TMS. With histology and Evans blue injections, blood-brain barrier alternations were seen as early as 4 days after irradiation. 83 references, 53 figures.

  14. Photoswitchable Intramolecular Hydrogen Bonds in 5-Phenylazopyrimidines Revealed By In Situ Irradiation NMR Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Procházková, Eliška; Čechová, Lucie; Kind, J.; Janeba, Zlatko; Thiele, C. M.; Dračínský, Martin

    2018-01-01

    Roč. 24, č. 2 (2018), s. 492-498 ISSN 0947-6539 R&D Projects: GA ČR GA15-11223S Institutional support: RVO:61388963 Keywords : azopyrimidines * heterocycles * hydrogen bonds * NMR spectroscopy * UV/Vis in situ irradiation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 5.317, year: 2016

  15. Water Behavior in Bacterial Spores by Deuterium NMR Spectroscopy

    Science.gov (United States)

    2015-01-01

    Dormant bacterial spores are able to survive long periods of time without nutrients, withstand harsh environmental conditions, and germinate into metabolically active bacteria when conditions are favorable. Numerous factors influence this hardiness, including the spore structure and the presence of compounds to protect DNA from damage. It is known that the water content of the spore core plays a role in resistance to degradation, but the exact state of water inside the core is a subject of discussion. Two main theories present themselves: either the water in the spore core is mostly immobile and the core and its components are in a glassy state, or the core is a gel with mobile water around components which themselves have limited mobility. Using deuterium solid-state NMR experiments, we examine the nature of the water in the spore core. Our data show the presence of unbound water, bound water, and deuterated biomolecules that also contain labile deuterons. Deuterium–hydrogen exchange experiments show that most of these deuterons are inaccessible by external water. We believe that these unreachable deuterons are in a chemical bonding state that prevents exchange. Variable-temperature NMR results suggest that the spore core is more rigid than would be expected for a gel-like state. However, our rigid core interpretation may only apply to dried spores whereas a gel core may exist in aqueous suspension. Nonetheless, the gel core, if present, is inaccessible to external water. PMID:24950158

  16. Water behavior in bacterial spores by deuterium NMR spectroscopy.

    Science.gov (United States)

    Friedline, Anthony W; Zachariah, Malcolm M; Johnson, Karen; Thomas, Kieth J; Middaugh, Amy N; Garimella, Ravindranath; Powell, Douglas R; Vaishampayan, Parag A; Rice, Charles V

    2014-07-31

    Dormant bacterial spores are able to survive long periods of time without nutrients, withstand harsh environmental conditions, and germinate into metabolically active bacteria when conditions are favorable. Numerous factors influence this hardiness, including the spore structure and the presence of compounds to protect DNA from damage. It is known that the water content of the spore core plays a role in resistance to degradation, but the exact state of water inside the core is a subject of discussion. Two main theories present themselves: either the water in the spore core is mostly immobile and the core and its components are in a glassy state, or the core is a gel with mobile water around components which themselves have limited mobility. Using deuterium solid-state NMR experiments, we examine the nature of the water in the spore core. Our data show the presence of unbound water, bound water, and deuterated biomolecules that also contain labile deuterons. Deuterium-hydrogen exchange experiments show that most of these deuterons are inaccessible by external water. We believe that these unreachable deuterons are in a chemical bonding state that prevents exchange. Variable-temperature NMR results suggest that the spore core is more rigid than would be expected for a gel-like state. However, our rigid core interpretation may only apply to dried spores whereas a gel core may exist in aqueous suspension. Nonetheless, the gel core, if present, is inaccessible to external water.

  17. SIMPSON: A general simulation program for solid-state NMR spectroscopy

    Science.gov (United States)

    Bak, Mads; Rasmussen, Jimmy T.; Nielsen, Niels Chr.

    2011-12-01

    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 Tel 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. Basicly, 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 ID 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.

  18. In situ structural characterization of a recombinant protein in native Escherichia coli membranes with solid-state magic-angle-spinning NMR.

    Science.gov (United States)

    Fu, Riqiang; Wang, Xingsheng; Li, Conggang; Santiago-Miranda, Adriana N; Pielak, Gary J; Tian, Fang

    2011-08-17

    The feasibility of using solid-state magic-angle-spinning NMR spectroscopy for in situ structural characterization of the LR11 (sorLA) transmembrane domain (TM) in native Escherichia coli membranes is presented. LR11 interacts with the human amyloid precursor protein (APP), a central player in the pathology of Alzheimer's disease. The background signals from E. coli lipids and membrane proteins had only minor effects on the LR11 TM resonances. Approximately 50% of the LR11 TM residues were assigned by using (13)C PARIS data. These assignments allowed comparisons of the secondary structure of the LR11 TM in native membrane environments and commonly used membrane mimics (e.g., micelles). In situ spectroscopy bypasses several obstacles in the preparation of membrane proteins for structural analysis and offers the opportunity to investigate how membrane heterogeneity, bilayer asymmetry, chemical gradients, and macromolecular crowding affect the protein structure.

  19. J-Modulation in ID NMR 1H Spectrum of Taurine and Aspartate Using Spin-Echo Technique

    Science.gov (United States)

    Oturak, Halil; Sağlam, Adnan; Bahçeli, Semiha

    1999-05-01

    This study reports on a theoretical calculation of Hahn's spin-echo experiment in case of a model A2B2 spin system with a strongly coupling character and gives the experimental results of one-dimension 1H high-resolution NMR spectra of taurine and aspartate. The calculated amplitudes of the spin-echoes for two different proton groups of taurine are given. Using results of our calculations for taurine, the computer simulations of J-modulation are implemented. It is shown that the agreement be-tween the experimental and simulated spectra is good.

  20. Characterization of partitioning relevant lanthanide and actinide complexes by NMR spectroscopy; Charakterisierung von partitioningrelevanten Lanthaniden- und Actinidenkomplexen mittels NMR-Spektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Adam, Christian

    2016-01-15

    In the present work the interaction of N-donor ligands, such as 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPrBTP) and 2,6-Bis(5-(2,2-dimethylpropyl)1H-pyrazol)-3-yl-pyridine (C5-BPP), with trivalent lanthanide and actinide ions was studied. Ligands of this type show a high selectivity for the separation of trivalent actinide ions over lanthanides from nitric acid solutions. However, the reason for this selectivity, which is crucial for future partitioning and transmutation strategies for radioactive wastes, is still unknown. So far, the selectivity of some N-donor ligands is supposed to be an effect of an increased covalency in the actinide-ligand bond, compared to the lanthanide compounds. NMR spectroscopy on paramagnetic metal complexes is an excellent tool for the elucidation of bonding modes. The overall paramagnetic chemical shift consists of two contributions, the Fermi Contact Shift (FCS), due to electron spin delocalisation through covalent bonds, and the Pseudo Contact Shift (PCS), which describes the dipolar coupling of the electron magnetic moment and the nuclear spin. By assessing the FCS share in the paramagnetic shift, the degree of covalency in the metal-ligand bond can be gauged. Several methods to discriminate FCS and PCS have been used on the data of the nPrBTP- and C5-BPP-complexes and were evaluated regarding their applicability on lanthanide and actinide complexes with N-donor ligands. The study comprised the synthesis of all Ln(III) complexes with the exceptions of Pm(III) and Gd(III) as well as the Am(III) complex as a representative of the actinide series with both ligands. All complexes were fully characterised ({sup 1}H, {sup 13}C and {sup 15}N spectra) using NMR spectroscopy. By isotope enrichment with the NMR-active {sup 15}N in positions 8 and 9 in both ligands, resonance signals of these nitrogen atoms were detected for all complexes. The Bleaneymethod relies on different temperature dependencies for FCS (T{sup -1}) and PCS (T

  1. NMRbot: Python scripts enable high-throughput data collection on current Bruker BioSpin NMR spectrometers.

    Science.gov (United States)

    Clos, Lawrence J; Jofre, M Fransisca; Ellinger, James J; Westler, William M; Markley, John L

    2013-06-01

    To facilitate the high-throughput acquisition of nuclear magnetic resonance (NMR) experimental data on large sets of samples, we have developed a simple and straightforward automated methodology that capitalizes on recent advances in Bruker BioSpin NMR spectrometer hardware and software. Given the daunting challenge for non-NMR experts to collect quality spectra, our goal was to increase user accessibility, provide customized functionality, and improve the consistency and reliability of resultant data. This methodology, NMRbot, is encoded in a set of scripts written in the Python programming language accessible within the Bruker BioSpin TopSpin ™ software. NMRbot improves automated data acquisition and offers novel tools for use in optimizing experimental parameters on the fly. This automated procedure has been successfully implemented for investigations in metabolomics, small-molecule library profiling, and protein-ligand titrations on four Bruker BioSpin NMR spectrometers at the National Magnetic Resonance Facility at Madison. The investigators reported benefits from ease of setup, improved spectral quality, convenient customizations, and overall time savings.

  2. Improved WATERGATE Pulse Sequences for Solvent Suppression in NMR Spectroscopy

    Science.gov (United States)

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

    1998-05-01

    Modifications to the WATERGATE method for removing the solvent resonance from1H NMR spectra are presented. In the conventional WATERGATE, a pulse train with three pairs of symmetric pulses in the form 3α-τ-9α-τ-19α-τ-19α-τ-9α-τ-3α (designated here W3), where 26α = 180°, is used, while the improved versions use four and five pairs of symmetric pulses (designated here W4 and W5), respectively. The modified methods provide narrower noninversion regions and hence enhance the sensitivities of the peaks close to the water resonance. The inversion and suppression profiles of the pulse trains W3, W4, and W5 are compared theoretically and experimentally and good agreement is obtained.

  3. Magic-angle spinning NMR of intact bacteriophages: Insights into the capsid, DNA and their interface

    Science.gov (United States)

    Abramov, Gili; Morag, Omry; Goldbourt, Amir

    2015-04-01

    Bacteriophages are viruses that infect bacteria. They are complex macromolecular assemblies, which are composed of multiple protein subunits that protect genomic material and deliver it to specific hosts. Various biophysical techniques have been used to characterize their structure in order to unravel phage morphogenesis. Yet, most bacteriophages are non-crystalline and have very high molecular weights, in the order of tens of MegaDaltons. Therefore, complete atomic-resolution characterization on such systems that encompass both capsid and DNA is scarce. In this perspective article we demonstrate how magic-angle spinning solid-state NMR has and is used to characterize in detail bacteriophage viruses, including filamentous and icosahedral phage. We discuss the process of sample preparation, spectral assignment of both capsid and DNA and the use of chemical shifts and dipolar couplings to probe the capsid-DNA interface, describe capsid structure and dynamics and extract structural differences between viruses.

  4. Segmental dynamics of polyethylene-alt-propylene studied by NMR spin echo techniques

    Science.gov (United States)

    Lozovoi, A.; Mattea, C.; Hofmann, M.; Saalwaechter, K.; Fatkullin, N.; Stapf, S.

    2017-06-01

    Segmental dynamics of a highly entangled melt of linear polyethylene-alt-propylene with a molecular weight of 200 kDa was studied with a novel proton nuclear magnetic resonance (NMR) approach based upon 1H → 2H isotope dilution as applied to a solid-echo build-up function ISE(t), which is constructed from the NMR spin echo signals arising from the Hahn echo (HE) and two variations of the solid-echo pulse sequence. The isotope dilution enables the separation of inter- and intramolecular contributions to this function and allows one to extract the segmental mean-squared displacements in the millisecond time range, which is hardly accessible by other experimental methods. The proposed technique in combination with time-temperature superposition yields information about segmental translation in polyethylene-alt-propylene over 6 decades in time from 10-6 s up to 1 s. The time dependence of the mean-squared displacement obtained in this time range clearly shows three regimes of power law with exponents, which are in good agreement with the tube-reptation model predictions for the Rouse model, incoherent reptation and coherent reptation regimes. The results at short times coincide with the fast-field cycling relaxometry and neutron spin echo data, yet, significantly extending the probed time range. Furthermore, the obtained data are verified as well by the use of the dipolar-correlation effect on the Hahn echo, which was developed before by the co-authors. At the same time, the amplitude ratio of the intermolecular part of the proton dynamic dipole-dipole correlation function over the intramolecular part obtained from the experimental data is not in agreement with the predictions of the tube-reptation model for the regimes of incoherent and coherent reptation.

  5. Equilibrium forms of vitisin B pigments in an aqueous system studied by NMR and visible spectroscopy.

    Science.gov (United States)

    Oliveira, Joana; Mateus, Nuno; Silva, Artur M S; de Freitas, Victor

    2009-08-13

    The main species in the acid-base equilibria of two pyranoanthocyanins (vitisins B), pyranomalvidin-3-glucoside I and pyranomalvidin-3-O-coumaroylglucoside II, and the respective pK(a) were determined using NMR, visible spectroscopy, and mass spectrometry techniques. The three equilibria involve protonation of the pyranoflavylium cation of vitisin B (pK(a1)) and two deprotonations (pK(a2) and pK(a3)). For pigment I, the values obtained through the titration curves of the chemical shift of some protons versus pH were (pK(a1) visible spectroscopy (pK(a1) visible spectroscopy (pK(a1) < 0.75; pK(a2) = 4.66 +/- 0.10; pK(a3) = 6.76 +/- 0.10). NMR studies have shown that pigment I does not undergo hydration, and the hypothesis of the occurrence of hemiacetal forms in equilibrium was discarded.

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

    Science.gov (United States)

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

    2014-02-18

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

  7. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy

    Science.gov (United States)

    Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2016-01-01

    NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (1H, 13C, and 31P) and two-dimensional (1H-13C and 1H-31P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. 1H, 13C, and 31P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the 1H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative 1H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the 1H-31P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

  8. New methods and applications in solid-state NMR spectroscopy of quadrupolar nuclei.

    Science.gov (United States)

    Ashbrook, Sharon E; Sneddon, Scott

    2014-11-05

    Solid-state nuclear magnetic resonance (NMR) spectroscopy has long been established as offering unique atomic-scale and element-specific insight into the structure, disorder, and dynamics of materials. NMR spectra of quadrupolar nuclei (I > (1)/2) are often perceived as being challenging to acquire and to interpret because of the presence of anisotropic broadening arising from the interaction of the electric field gradient and the nuclear electric quadrupole moment, which broadens the spectral lines, often over several megahertz. Despite the vast amount of information contained in the spectral line shapes, the problems with sensitivity and resolution have, until very recently, limited the application of NMR spectroscopy of quadrupolar nuclei in the solid state. In this Perspective, we provide a brief overview of the quadrupolar interaction, describe some of the basic experimental approaches used for acquiring high-resolution NMR spectra, and discuss the information that these spectra can provide. We then describe some interesting recent examples to showcase some of the more exciting and challenging new applications of NMR spectra of quadrupolar nuclei in the fields of energy materials, microporous materials, Earth sciences, and biomaterials. Finally, we consider the possible directions that this highly informative technique may take in the future.

  9. NMR spectroscopy up to 35.2 T using a series-connected hybrid magnet

    Science.gov (United States)

    Gan, Zhehong; Hung, Ivan; Wang, Xiaoling; Paulino, Joana; Wu, Gang; Litvak, Ilya M.; Gor'kov, Peter L.; Brey, William W.; Lendi, Pietro; Schiano, Jeffrey L.; Bird, Mark D.; Dixon, Iain R.; Toth, Jack; Boebinger, Gregory S.; Cross, Timothy A.

    2017-11-01

    The National High Magnetic Field Laboratory has brought to field a Series-Connected Hybrid magnet for NMR spectroscopy. As a DC powered magnet it can be operated at fields up to 36.1 T. The series connection between a superconducting outsert and a resistive insert dramatically minimizes the high frequency fluctuations of the magnetic field typically observed in purely resistive magnets. Current-density-grading among various resistive coils was used for improved field homogeneity. The 48 mm magnet bore and 42 mm outer diameter of the probes leaves limited space for conventional shims and consequently a combination of resistive and ferromagnetic shims are used. Field maps corrected for field instabilities were obtained and shimming achieved better than 1 ppm homogeneity over a cylindrical volume of 1 cm diameter and height. The magnetic field is regulated within 0.2 ppm using an external 7Li lock sample doped with paramagnetic MnCl2. The improved field homogeneity and field regulation using a modified AVANCE NEO console enables NMR spectroscopy at 1H frequencies of 1.0, 1.2 and 1.5 GHz. NMR at 1.5 GHz reflects a 50% increase in field strength above the highest superconducting magnets currently available. Three NMR probes have been constructed each equipped with an external lock rf coil for field regulation. Initial NMR results obtained from the SCH magnet using these probes illustrate the very exciting potential of ultra-high magnetic fields.

  10. DRAMAtic transforms in magic angle spinning recoupling NMR: The Bessel function pathway.

    Science.gov (United States)

    Goodman, Russell; Hancock, Jason; Siemens, Mark; Jarrell, Harold; Siminovitch, David

    2005-07-01

    In magic angle spinning (MAS) NMR recoupling experiments, the extraction of multiple couplings or a coupling distribution from the observed dephasing signals remains a challenging problem. At least for REDOR experiments, the REDOR transform solves this problem, enabling the simultaneous measurement of multiple dipolar couplings. Focusing on the quadrupolar dephasing observed in QUADRAMA experiments as a representative example, we demonstrate that the same analytical form used for the mathematical description of REDOR dephasing also describes the dephasing observed in a wide variety of MAS NMR recoupling experiments. This fact immediately extends REDOR transform techniques to a much broader suite of recoupling experiments than had previously been realized, including those of DRAMA, MELODRAMA and QUADRAMA. As an illustration, we use the DRAMAtic transform to provide the first inversion of a QUADRAMA dephasing signal to extract the quadrupole coupling distribution. Using a complete elliptic integral of the first kind, we further develop a novel expression for the Pake-spun powder patterns of the corresponding recoupled lineshapes. Our methods and results reinforce the central role that Bessel functions can play in simplifying the integrals that define both the dephasing signals in the time domain, and their Fourier transforms in the frequency domain.

  11. Hydrogen and deuterium NMR of solids by magic-angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Eckman, R.R.

    1982-10-01

    The nuclear magnetic resonance of solids has long been characterized by very large specral broadening which arises from internuclear dipole-dipole coupling or the nuclear electric quadrupole interaction. These couplings can obscure the smaller chemical shift interaction and make that information unavailable. Two important and difficult cases are that of hydrogen and deuterium. The development of cross polarization, heteronuclear radiofrequency decoupling, and coherent averaging of nuclear spin interactions has provided measurement of chemical shift tensors in solids. Recently, double quantum NMR and double quantum decoupling have led to measurement of deuterium and proton chemical shift tensors, respectively. A general problem of these experiments is the overlapping of the tensor powder pattern spectra of magnetically distinct sites which cannot be resolved. In this work, high resolution NMR of hydrogen and deuterium in solids is demonstrated. For both nuclei, the resonances are narrowed to obtain liquid-like isotropic spectra by high frequency rotation of the sample about an axis inclined at the magic angle, ..beta../sub m/ = Arccos (3/sup -1/2/), with respect to the direction of the external magnetic field. For deuterium, the powder spectra were narrowed by over three orders of magnitude by magic angle rotation with precise control of ..beta... A second approach was the observation of deuterium double quantum transitions under magic angle rotation. For hydrogen, magic angle rotation alone could be applied to obtain the isotropic spectrum when H/sub D/ was small. This often occurs naturally when the nuclei are semi-dilute or involved in internal motion. In the general case of large H/sub D/, isotropic spectra were obtained by dilution of /sup 1/H with /sup 2/H combined with magic angle rotation. The resolution obtained represents the practical limit for proton NMR of solids.

  12. Application of HR-MAS NMR spectroscopy for studying chemotype variations of Withania somnifera (L.) Dunal.

    Science.gov (United States)

    Bharti, S K; Bhatia, Anil; Tewari, S K; Sidhu, O P; Roy, Raja

    2011-10-01

    Withania somnifera (L.) Dunal (Solanaceae), commonly known as Ashwagandha, is one of the most valued Indian medicinal plants with a number of pharmaceutical and nutraceutical applications. Metabolic profiling has been performed by HR-MAS NMR spectroscopy on fresh leaf and root tissue specimens from four chemotypes of W. somnifera. The HR-MAS NMR spectroscopy of lyophilized defatted leaf tissue specimens clearly distinguishes resonances of medicinally important secondary metabolites (withaferin A and withanone) and its distinctive quantitative variability among the chemotypes. A total of 41 metabolites were identified from both the leaf and root tissues of the chemotypes. The presence of methanol in leaf and root tissues of W. somnifera was detected by HR-MAS NMR spectroscopy. Multivariate principal component analysis (PCA) on HR-MAS (1) H NMR spectra of leaves revealed clear variations in primary metabolites among the chemotypes. The results of the present study demonstrated an efficient method, which can be utilized for metabolite profiling of primary and secondary metabolites in medicinally important plants. Copyright © 2011 John Wiley & Sons, Ltd.

  13. Monitoring electrochemical reactions in situ using steady-state free precession {sup 13}C NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nunes, Luiza M.S. [Instituto de Química de São Carlos, Universidade de São Paulo, Avenida Trabalhador São-Carlense 400, São Carlos, São Paulo 13560-070 (Brazil); Embrapa Instrumentação, Rua XV de Novembro 1452, São Carlos, São Paulo 13560-970 (Brazil); Moraes, Tiago B. [Embrapa Instrumentação, Rua XV de Novembro 1452, São Carlos, São Paulo 13560-970 (Brazil); Instituto de Física de São Carlos, Universidade de São Paulo, Avenida Trabalhador São-Carlense 400, São Carlos, São Paulo 13566-590 (Brazil); Barbosa, Lucio L. [Departamento de Química, Universidade Federal do Espírito Santo, Avenida Fernando Ferrari 514, Vitória, Espírito Santo 29075-910 (Brazil); Mazo, Luiz H. [Instituto de Química de São Carlos, Universidade de São Paulo, Avenida Trabalhador São-Carlense 400, São Carlos, São Paulo 13560-070 (Brazil); and others

    2014-11-19

    Highlights: • Analysis of electrochemical reaction in situ by 13C NMR spectroscopy was demonstrated. • {sup 13}C NMR signals are obtained in few minutes, using steady-state free precession (SSFP) pulse sequence. • The analysis is performed in standard NMR spectrometer. • KBDM can be an alternative to Fourier Transform to process SSFP signal. - Abstract: All attempts to use in situ{sup 13}C NMR in spectroelectrochemical studies, using static cells and unlabeled substrates, have failed due to the very long average time (several hours). In this paper, we demonstrated that steady-state free precession (SSFP) pulse sequence can enhance signal to noise ratio and reduces the average time of {sup 13}C NMR signals by more than one order of magnitude. The results showed that each {sup 13}C NMR spectrum during the electrochemical reduction of 9-chloroanthracene, in a static cell, can be acquired in eleven minutes. This short averaging time allowed the analysis of the reaction every 30 min during 3 h. The phase and truncation anomalies present in SSFP spectra were minimized using Traff apodization function and Krylov basis diagonalization method (KBDM)

  14. Differential Epitope Mapping by STD NMR Spectroscopy To Reveal the Nature of Protein-Ligand Contacts.

    Science.gov (United States)

    Monaco, Serena; Tailford, Louise E; Juge, Nathalie; Angulo, Jesus

    2017-11-27

    Saturation transfer difference (STD) NMR spectroscopy is extensively used to obtain epitope maps of ligands binding to protein receptors, thereby revealing structural details of the interaction, which is key to direct lead optimization efforts in drug discovery. However, it does not give information about the nature of the amino acids surrounding the ligand in the binding pocket. Herein, we report the development of the novel method differential epitope mapping by STD NMR (DEEP-STD NMR) for identifying the type of protein residues contacting the ligand. The method produces differential epitope maps through 1) differential frequency STD NMR and/or 2) differential solvent (D 2 O/H 2 O) STD NMR experiments. The two approaches provide different complementary information on the binding pocket. We demonstrate that DEEP-STD NMR can be used to readily obtain pharmacophore information on the protein. Furthermore, if the 3D structure of the protein is known, this information also helps in orienting the ligand in the binding pocket. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  15. The effect of antitumor glycosides on glioma cells and tissues as studied by proton HR-MAS NMR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Isabel García-Álvarez

    Full Text Available The effect of the treatment with glycolipid derivatives on the metabolic profile of intact glioma cells and tumor tissues, investigated using proton high resolution magic angle spinning ((1H HR-MAS nuclear magnetic resonance (NMR spectroscopy, is reported here. Two compounds were used, a glycoside and its thioglycoside analogue, both showing anti-proliferative activity on glioma C6 cell cultures; however, only the thioglycoside exhibited antitumor activity in vivo. At the drug concentrations showing anti-proliferative activity in cell culture (20 and 40 µM, significant increases in choline containing metabolites were observed in the (1H NMR spectra of the same intact cells. In vivo experiments in nude mice bearing tumors derived from implanted C6 glioma cells, showed that reduction of tumor volume was associated with significant changes in the metabolic profile of the same intact tumor tissues; and were similar to those observed in cell culture. Specifically, the activity of the compounds is mainly associated with an increase in choline and phosphocholine, in both the cell cultures and tumoral tissues. Taurine, a metabolite that has been considered a biomarker of apoptosis, correlated with the reduction of tumor volume. Thus, the results indicate that the mode of action of the glycoside involves, at least in part, alteration of phospholipid metabolism, resulting in cell death.

  16. Solid-State 13C NMR Spectroscopy Applied to the Study of Carbon Blacks and Carbon Deposits Obtained by Plasma Pyrolysis of Natural Gas

    Directory of Open Access Journals (Sweden)

    Jair C. C. Freitas

    2016-01-01

    Full Text Available Solid-state 13C nuclear magnetic resonance (NMR spectroscopy was used in this work to analyze the physical and chemical properties of plasma blacks and carbon deposits produced by thermal cracking of natural gas using different types of plasma reactors. In a typical configuration with a double-chamber reactor, N2 or Ar was injected as plasma working gas in the first chamber and natural gas was injected in the second chamber, inside the arc column. The solid residue was collected at different points throughout the plasma apparatus and analyzed by 13C solid-state NMR spectroscopy, using either cross polarization (CP or direct polarization (DP, combined with magic angle spinning (MAS. The 13C CP/MAS NMR spectra of a number of plasma blacks produced in the N2 plasma reactor showed two resonance bands, broadly identified as associated with aromatic and aliphatic groups, with indication of the presence of oxygen- and nitrogen-containing groups in the aliphatic region of the spectrum. In contrast to DP experiments, only a small fraction of 13C nuclei in the plasma blacks are effectively cross-polarized from nearby 1H nuclei and are thus observed in spectra recorded with CP. 13C NMR spectra are thus useful to distinguish between different types of carbon species in plasma blacks and allow a selective study of groups spatially close to hydrogen in the material.

  17. Uptake of BSH in M2R melanoma cells monitored by NMR spectroscopy

    International Nuclear Information System (INIS)

    Koudinova, N.; Elhanati, G.; Salomon, Y.; Bendel, P.

    2000-01-01

    The accumulation ratio of BSH, relative to that of boric acid, in M2R mouse melanoma cells, was measured using 11 B NMR of the cell extracts. The cells were incubated in growth medium for up to 24 h, in the presence of 0.8 mM boric acid and 0.25-1.5 mM BSH. The aqueous phase of the cellular extracts was re-suspended for NMR spectroscopy. The relative accumulation ratio of BSH/boric acid determined from 9 separate experiments was 0.45±0.09. (author)

  18. Grape juice quality control by means of ¹H nmr spectroscopy and chemometric analyses

    Directory of Open Access Journals (Sweden)

    Caroline Werner Pereira da Silva Grandizoli

    2014-01-01

    Full Text Available This work shows the application of ¹H NMR spectroscopy and chemometrics for quality control of grape juice. A wide range of quality assurance parameters were assessed by single ¹H NMR experiments acquired directly from juice. The investigation revealed that conditions and time of storage should be revised and indicated on all labels. The sterilization process of homemade grape juices was efficient, making it possible to store them for long periods without additives. Furthermore, chemometric analysis classified the best commercial grape juices to be similar to homemade grape juices, indicating that this approach can be used to determine the authenticity after adulteration.

  19. Grape juice quality control by means of {sup 1}H NMR spectroscopy and chemometric analyses

    Energy Technology Data Exchange (ETDEWEB)

    Grandizoli, Caroline Werner Pereira da Silva; Campos, Francinete Ramos; Simonelli, Fabio; Barison, Andersson, E-mail: andernmr@ufpr.br [Universidade Federal do Paraná (UFPR), Curitiba (Brazil). Departamento de Química

    2014-07-01

    This work shows the application of {sup 1}H NMR spectroscopy and chemometrics for quality control of grape juice. A wide range of quality assurance parameters were assessed by single {sup 1}H NMR experiments acquired directly from juice. The investigation revealed that conditions and time of storage should be revised and indicated on all labels. The sterilization process of homemade grape juices was efficient, making it possible to store them for long periods without additives. Furthermore, chemometric analysis classified the best commercial grape juices to be similar to homemade grape juices, indicating that this approach can be used to determine the authenticity after adulteration. (author)

  20. Determination of water content in olive oil by 31P NMR spectroscopy.

    Science.gov (United States)

    Hatzakis, Emmanuel; Dais, Photis

    2008-03-26

    A method for moisture determination in olive oil using 31P NMR spectroscopy is developed. This method is based on the replacement of the hydrogen atoms of water molecules with the tagging agents 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane and diphenylphosphinic chloride. Both reagents were successful in determining moisture in olive oil. However, only the second reagent provided a clean and instantaneous reaction under mild condition with no side reactions as observed with the first reagent. A study comparison was made to assess the agreement between the present analytical NMR method and the well-established methods of Karl Fischer titration.

  1. 31P NMR spectroscopy of tumors in the evaluation of response to therapy

    International Nuclear Information System (INIS)

    Sijens, P.E.

    1988-01-01

    In this thesis the effects of different kinds of therapy on tumour metabolism were investigated by in vivo 31P NMR spectroscopy. From the first five chapters (laboratory-animal studies) it turns out that after radiotherapy as well as after hyperthermy or chemoterapy changes can be observed in the 31P NMR spectra of tumours. In a number of cases a durable decline occurred in the ratio of the high-energetic adenosinephosphate (ATP) and the low-energeic anorganic phosphate, cuased by the mortification of tumourcells. On the other hand, tumour regression after effective chemotherapy resulted in a growth of the ATP/Pi ratio. In one case a temporary drop occurred which could be related to a temporary decrease in tumour perfusion. In anoter case a temporary drop of the ATP/Pi ratio correlated with resistence against treatment with cis-diaminodichoroplatina. In contrast with the changes in ATP/Pi ratio, the changes, after (chemo)therapy, in tumour pH do not seem to be related with the respons of the tumour. The results of the laboratory-animal experiments indicate that in vivo 31P NMR spectroscopy could be applied in the clinic in order to establish betime the response of tumours on therapy. In ch. 6 initial experiences with clinical NMR spectroscopy of human breast cancer are described. The results indicate that by 31P NMR spectroscopy malignant breast tissues can be discerned from normal breast tissues, following radiotherapy and subsequent tumour regression, in the spectrum of the tumorous region an intense PCr signal developed which appeared to reflect a metabolic change in the tumous itself. 177 refs.; 27 figs.; 6 tabs

  2. 1H magic-angle spinning NMR evolves as a powerful new tool for membrane proteins

    Science.gov (United States)

    Schubeis, Tobias; Le Marchand, Tanguy; Andreas, Loren B.; Pintacuda, Guido

    2018-02-01

    Building on a decade of continuous advances of the community, the recent development of very fast (60 kHz and above) magic-angle spinning (MAS) probes has revolutionised the field of solid-state NMR. This new spinning regime reduces the 1H-1H dipolar couplings, so that direct detection of the larger magnetic moment available from 1H is now possible at high resolution, not only in deuterated molecules but also in fully-protonated substrates. Such capabilities allow rapid "fingerprinting" of samples with a ten-fold reduction of the required sample amounts with respect to conventional approaches, and permit extensive, robust and expeditious assignment of small-to-medium sized proteins (up to ca. 300 residues), and the determination of inter-nuclear proximities, relative orientations of secondary structural elements, protein-cofactor interactions, local and global dynamics. Fast MAS and 1H detection techniques have nowadays been shown to be applicable to membrane-bound systems. This paper reviews the strategies underlying this recent leap forward in sensitivity and resolution, describing its potential for the detailed characterization of membrane proteins.

  3. On the use of ultracentrifugal devices for routine sample preparation in biomolecular magic-angle-spinning NMR.

    Science.gov (United States)

    Mandal, Abhishek; Boatz, Jennifer C; Wheeler, Travis B; van der Wel, Patrick C A

    2017-03-01

    A number of recent advances in the field of magic-angle-spinning (MAS) solid-state NMR have enabled its application to a range of biological systems of ever increasing complexity. To retain biological relevance, these samples are increasingly studied in a hydrated state. At the same time, experimental feasibility requires the sample preparation process to attain a high sample concentration within the final MAS rotor. We discuss these considerations, and how they have led to a number of different approaches to MAS NMR sample preparation. We describe our experience of how custom-made (or commercially available) ultracentrifugal devices can facilitate a simple, fast and reliable sample preparation process. A number of groups have since adopted such tools, in some cases to prepare samples for sedimentation-style MAS NMR experiments. Here we argue for a more widespread adoption of their use for routine MAS NMR sample preparation.

  4. High resolution magic angle spinning NMR applied to the analysis of organic compounds bound to solid supports.

    Science.gov (United States)

    Espinosa, Juan F

    2011-01-01

    In situ structural characterization of organic compounds attached to solid supports can be achieved by high-resolution magic angle spinning NMR (HRMAS NMR), a technique that provides solution-like spectra for resin-bound molecules. This review outlines the principles of the technique, the influence of the solid support on data quality, and NMR experiments that are useful for obtaining valuable information. The review describes, with multiple examples mainly from the last 7 years, how HRMAS NMR has been applied to monitor solid-phase reactions, elucidate reaction products and quantify compound loading on a solid support. Other applications, such as conformational analysis of immobilized compounds and investigation of molecular interactions with compounds in solution, are also discussed.

  5. On the use of ultracentrifugal devices for routine sample preparation in biomolecular magic-angle-spinning NMR

    Energy Technology Data Exchange (ETDEWEB)

    Mandal, Abhishek; Boatz, Jennifer C. [University of Pittsburgh School of Medicine, Department of Structural Biology (United States); Wheeler, Travis B. [University of Pittsburgh School of Medicine, Department of Cell Biology (United States); Wel, Patrick C. A. van der, E-mail: vanderwel@pitt.edu [University of Pittsburgh School of Medicine, Department of Structural Biology (United States)

    2017-03-15

    A number of recent advances in the field of magic-angle-spinning (MAS) solid-state NMR have enabled its application to a range of biological systems of ever increasing complexity. To retain biological relevance, these samples are increasingly studied in a hydrated state. At the same time, experimental feasibility requires the sample preparation process to attain a high sample concentration within the final MAS rotor. We discuss these considerations, and how they have led to a number of different approaches to MAS NMR sample preparation. We describe our experience of how custom-made (or commercially available) ultracentrifugal devices can facilitate a simple, fast and reliable sample preparation process. A number of groups have since adopted such tools, in some cases to prepare samples for sedimentation-style MAS NMR experiments. Here we argue for a more widespread adoption of their use for routine MAS NMR sample preparation.

  6. Quantitative analysis of water heavy by NMR spectroscopy

    International Nuclear Information System (INIS)

    Gomez Gil, V.

    1975-01-01

    Nuclear Magnetic Resonance has been applied to a wide variety of quantitative problems. A typical example has been the determination of isotopic composition. In this paper two different analytical methods for the determination of water in deuterium oxide are described. The first one, employs acetonitril as an internal standard compound and in the second one calibration curve of signal integral curve versus amount of D 2 O is constructed. Both methods give results comparable to those of mass spectrometry of IR spectroscopy. (Author) 5 refs

  7. Sub-picosecond time resolved infrared spectroscopy of high-spin state formation in Fe(II) spin crossover complexes

    DEFF Research Database (Denmark)

    Døssing, Anders Rørbæk; Wolf, Matthias M. N.; Gross, Ruth

    2008-01-01

      The photoinduced low-spin (S = 0) to high-spin (S = 2) transition of the iron(II) spin-crossover systems [Fe(btpa)](PF6)2 and [Fe(b(bdpa))](PF6)2 in solution have been studied for the first time by means of ultrafast transient infrared spectroscopy at room temperature. Negative and positive inf...... absorption cross sections. The simulated infrared difference spectra are dominated by an increase of the absorption cross section upon high-spin state formation in accordance with the experimental infrared spectra.......  The photoinduced low-spin (S = 0) to high-spin (S = 2) transition of the iron(II) spin-crossover systems [Fe(btpa)](PF6)2 and [Fe(b(bdpa))](PF6)2 in solution have been studied for the first time by means of ultrafast transient infrared spectroscopy at room temperature. Negative and positive...... infrared difference bands between 1000 and 1065 cm-1 that appear within the instrumental system response time of 350 fs after excitation at 387 nm display the formation of the vibrationally unrelaxed and hot high-spin 5T2 state. Vibrational relaxation is observed and characterized by the time constants 9...

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

    Science.gov (United States)

    Gopinath, T.; Veglia, Gianluigi

    2015-04-01

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

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

    Science.gov (United States)

    Gopinath, T; Veglia, Gianluigi

    2015-04-01

    Solid-state NMR spectroscopy of proteins is a notoriously low-throughput technique. Relatively low-sensitivity and poor resolution of protein samples require long acquisition times for multidimensional NMR experiments. To speed up data acquisition, we developed a family of experiments called Polarization Optimized Experiments (POE), in which we utilized the orphan spin operators that are discarded in classical multidimensional NMR experiments, recovering them to allow simultaneous acquisition of multiple 2D and 3D experiments, all while using conventional probes with spectrometers equipped with one receiver. POE allow the concatenation of multiple 2D or 3D pulse sequences into a single experiment, thus potentially combining all of the aforementioned advances, boosting the capability of ssNMR spectrometers at least two-fold without the addition of any hardware. In this perspective, we describe the first generation of POE, such as dual acquisition MAS (or DUMAS) methods, and then illustrate the evolution of these experiments into MEIOSIS, a method that enables the simultaneous acquisition of multiple 2D and 3D spectra. Using these new pulse schemes for the solid-state NMR investigation of biopolymers makes it possible to obtain sequential resonance assignments, as well as distance restraints, in about half the experimental time. While designed for acquisition of heteronuclei, these new experiments can be easily implemented for proton detection and coupled with other recent advancements, such as dynamic nuclear polarization (DNP), to improve signal to noise. Finally, we illustrate the application of these methods to microcrystalline protein preparations as well as single and multi-span membrane proteins reconstituted in lipid membranes. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. Simplifying the complex 1H NMR spectra of fluorine-substituted benzamides by spin system filtering and spin-state selection: multiple-quantum-single-quantum correlation.

    Science.gov (United States)

    Baishya, Bikash; Reddy, G N Manjunatha; Prabhu, Uday Ramesh; Row, T N Guru; Suryaprakash, N

    2008-10-23

    The proton NMR spectra of fluorine-substituted benzamides are very complex (Figure 1) due to severe overlap of (1)H resonances from the two aromatic rings, in addition to several short and long-range scalar couplings experienced by each proton. With no detectable scalar couplings between the inter-ring spins, the (1)H NMR spectra can be construed as an overlap of spectra from two independent phenyl rings. In the present study we demonstrate that it is possible to separate the individual spectrum for each aromatic ring by spin system filtering employing the multiple-quantum-single-quantum correlation methodology. Furthermore, the two spin states of fluorine are utilized to simplify the spectrum corresponding to each phenyl ring by the spin-state selection. The demonstrated technique reduces spectral complexity by a factor of 4, in addition to permitting the determination of long-range couplings of less than 0.2 Hz and the relative signs of heteronuclear couplings. The technique also aids the judicious choice of the spin-selective double-quantum-single-quantum J-resolved experiment to determine the long-range homonuclear couplings of smaller magnitudes.

  11. Mapping the variation of the carrot metabolome using 1H NMR spectroscopy and consensus PCA.

    Science.gov (United States)

    Clausen, Morten Rahr; Edelenbos, Merete; Bertram, Hanne Christine

    2014-05-14

    Genetic variation is the most influential factor for carrot (Daucus carota L.) composition. However, difference in metabolite content between carrot varieties has not been described by NMR, although primary metabolites are important for human health and sensory properties. The aim of the present study was to investigate the effect of genotype on carrot metabolite composition using a (1)H NMR-based metabolomics approach. After extraction using aqueous and organic solvents, 25 hydrophilic metabolites, β-carotene, sterols, triacylglycerols, and phospholipids were detected. Multiblock PCA showed that three principal components could be identified for classification of the five carrot varieties using different spectroscopic regions and the results of the two solvent extraction methods as blocks. The varieties were characterized by differences in carbohydrate, amino acid, nucleotide, fatty acid, sterol, and β-carotene contents. (1)H NMR spectroscopy coupled with multiblock data analysis was an efficient and useful tool to map the carrot metabolome and identify genetic differences between varieties.

  12. Orientational ordering studies of fluorinated thermotropic liquid crystals by NMR spectroscopy.

    Science.gov (United States)

    Calucci, Lucia; Geppi, Marco; Urban, Stanislaw

    2014-10-01

    Fluorinated calamitic thermotropic liquid crystals represent an important class of materials for high-tech applications, especially in the field of liquid crystal displays. The investigation of orientational ordering in these systems is fundamental owing to the dependence of their applications on the anisotropic nature of macroscopic optical, dielectric, and visco-elastic properties. NMR spectroscopy is the most powerful technique for studying orientational order in liquid crystalline systems at a molecular level thanks to the possibility of exploiting different anisotropic observables (chemical shift, dipolar couplings, and quadrupolar coupling) and nuclei ((2)H, (13)C, and (19)F). In this paper, the basic theory and NMR experiments useful for the investigation of orientational order on fluorinated calamitic liquid crystals are reported, and a review of the literature published on this subject is given. Finally, orientational order parameters determined by NMR data are discussed in comparison to those obtained by optical and dielectric anisotropy measurements. Copyright © 2014 John Wiley & Sons, Ltd.

  13. Illumination of Nanoliter-NMR Spectroscopy Chips for Real-Time Photochemical Reaction Monitoring.

    Science.gov (United States)

    Gomez, M Victoria; Juan, Alberto; Jiménez-Márquez, Francisco; de la Hoz, Antonio; Velders, Aldrik H

    2018-02-06

    We report the use of a small-volume nuclear-magnetic-resonance (NMR)-spectroscopy device with integrated fiber-optics for the real-time detection of UV-vis-light-assisted chemical reactions. An optical fiber is used to guide the light from LEDs or a laser diode positioned safely outside the magnet toward the 25 nL detection volume and placed right above the microfluidic channel, irradiating the transparent back of the NMR chip. The setup presented here overcomes the limitations of conventional NMR systems for in situ UV-vis illumination, with the microchannel permitting efficient light penetration even in highly concentrated solutions, requiring lower-power light intensities, and enabling high photon flux. The efficacy of the setup is illustrated with two model reactions activated at different wavelengths.

  14. 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

  15. Chemical Shifts of the Carbohydrate Binding Domain of Galectin-3 from Magic Angle Spinning NMR and Hybrid Quantum Mechanics/Molecular Mechanics Calculations.

    Science.gov (United States)

    Kraus, Jodi; Gupta, Rupal; Yehl, Jenna; Lu, Manman; Case, David A; Gronenborn, Angela M; Akke, Mikael; Polenova, Tatyana

    2018-03-22

    Magic angle spinning NMR spectroscopy is uniquely suited to probe the structure and dynamics of insoluble proteins and protein assemblies at atomic resolution, with NMR chemical shifts containing rich information about biomolecular structure. Access to this information, however, is problematic, since accurate quantum mechanical calculation of chemical shifts in proteins remains challenging, particularly for 15 N H . Here we report on isotropic chemical shift predictions for the carbohydrate recognition domain of microcrystalline galectin-3, obtained from using hybrid quantum mechanics/molecular mechanics (QM/MM) calculations, implemented using an automated fragmentation approach, and using very high resolution (0.86 Å lactose-bound and 1.25 Å apo form) X-ray crystal structures. The resolution of the X-ray crystal structure used as an input into the AF-NMR program did not affect the accuracy of the chemical shift calculations to any significant extent. Excellent agreement between experimental and computed shifts is obtained for 13 C α , while larger scatter is observed for 15 N H chemical shifts, which are influenced to a greater extent by electrostatic interactions, hydrogen bonding, and solvation.

  16. Real-time protein NMR spectroscopy and investigation of assisted protein folding.

    Science.gov (United States)

    Kumar, Amit; Balbach, Jochen

    2015-10-01

    During protein-folding reactions toward the native structure, short-lived intermediate states can be populated. Such intermediates expose hydrophobic patches and can self-associate leading to non-productive protein misfolding. A major focus of current research is the characterization of short-lived intermediates and how molecular chaperones enable productive folding. Real-time NMR spectroscopy, together with the development of advanced methods, is reviewed here and the potential these methods have to characterize intermediate states as well as interactions with molecular chaperone proteins at single-residue resolution is highlighted. Various chaperone interactions can guide the protein-folding reaction and thus are important for protein structure formation, stability, and activity of their substrates. Chaperone-assisted protein folding, characterization of intermediates, and their molecular interactions using real-time NMR spectroscopy will be discussed. Additionally, recent advances in NMR methods employed for characterization of high-energy intermediates will be discussed. Real-time NMR combines high resolution with kinetic information of protein reactions, which can be employed not only for protein-folding studies and the characterization of folding intermediates but also to investigate the molecular mechanisms of assisted protein folding. Real-time NMR spectroscopy remains an effective tool to reveal structural details about the interaction between chaperones and transient intermediates. Methodologically, it provides in-depth understanding of how kinetic intermediates and their thermodynamics contribute to the protein-folding reaction. This review summarizes the most recent advances in this field. This article is part of a Special Issue titled Proline-directed Foldases: Cell Signaling Catalysts and Drug Targets. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Study of acute biochemical effects of thallium toxicity in mouse urine by NMR spectroscopy.

    Science.gov (United States)

    Tyagi, Ritu; Rana, Poonam; Khan, Ahmad Raza; Bhatnagar, Deepak; Devi, M Memita; Chaturvedi, Shubhra; Tripathi, Rajendra P; Khushu, Subash

    2011-10-01

    Thallium (Tl) is a toxic heavy metal and its exposure to the human body causes physiological and biochemical changes due to its interference with potassium-dependent biological reactions. A high-resolution (1)H NMR spectroscopy based metabonomic approach has been applied for investigating acute biochemical effects caused by thallium sulfate (Tl(2)SO(4)). Male strain A mice were divided in three groups and received three doses of Tl(2)SO(4) (5, 10 and 20 mg kg(-1) b.w., i.p.). Urine samples collected at 3, 24, 72 and 96 h post-dose time points were analyzed by (1)H NMR spectroscopy. NMR spectral data were processed and analyzed using principal components analysis to represent biochemical variations induced by Tl(2)SO(4). Results showed Tl-exposed mice urine to have distinct metabonomic phenotypes and revealed dose- and time-dependent clustering of treated groups. The metabolic signature of urine analysis from Tl(2)SO(4)-treated animals exhibited an increase in the levels of creatinine, taurine, hippurate and β-hydroxybutyrate along with a decrease in energy metabolites trimethylamine and choline. These findings revealed Tl-induced disturbed gut flora, membrane metabolite, energy and protein metabolism, representing physiological dysfunction of vital organs. The present study indicates the great potential of NMR-based metabonomics in mapping metabolic response for toxicology, which could ultimately lead to identification of potential markers for Tl toxicity. Copyright © 2011 John Wiley & Sons, Ltd.

  18. 14N NMR Spectroscopy Study of Binding Interaction between Sodium Azide and Hydrated Fullerene

    Directory of Open Access Journals (Sweden)

    Tamar Chachibaia

    2017-04-01

    Full Text Available Our study is the first attempt to study the interaction between NaN3 and hydrated fullerenes C60 by means of a non-chemical reaction-based approach. The aim is to study deviations of signals obtained by 14N NMR spectroscopy to detect the binding interaction between sodium azide and hydrated fullerene. We considered 14N NMR spectroscopy as one of the most suitable methods for the characterization of azides to show resonance signals corresponding to the three non-equivalent nitrogen atoms. The results demonstrate that there are changes in the chemical shift positions and line-broadening, which are related to the different molar ratios of NaN3:C60 in the samples.

  19. Metabolic fingerprinting of Tussilago farfara L. using ¹H-NMR spectroscopy and multivariate data analysis.

    Science.gov (United States)

    Zhi, Hai-Juan; Qin, Xue-Mei; Sun, Hai-Feng; Zhang, Li-Zeng; Guo, Xiao-Qing; Li, Zhen-Yu

    2012-01-01

    The flower bud of Tussilago farfara L. is widely used for the treatment of coughs, bronchitis and asthmatic disorders in traditional Chinese medicine. In Europe, the plant has been used as herbal remedies for virtually the same applications, but the leaves are preferred over flowers. To systematically evaluate the chemical profiles of Tusssilago farfara leaves and flowers along with the identification of the polar and non-polar metabolites. Metabolic profiling carried out by means of ¹H-NMR spectroscopy and multivariate data analysis was applied to crude extracts from flowers and leaves. Metabolites were identified directly from the crude extracts through one-dimensional and two-dimensional NMR spectra. A broad range of metabolites were detected without any chromatographic separation. Principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) of ¹H-NMR data provided a clear separation between the samples. The corresponding loadings plot indicated that higher levels of phenylpropanoids, amino acids, organic acids and fatty acids, as well as lower levels of sugars, terpenoids and sterols were present in the leaves, as compared with flowers. For the flowers, more phenylpropanoids were present in fully open flowers, while more sugars and fatty acids were present in flower buds. NMR spectra (one- and two-dimensional) are useful for identifying metabolites, especially for the overlapped signals. The NMR-based metabolomics approach has great potential for chemical comparison study of the metabolome of herbal drugs. Copyright © 2012 John Wiley & Sons, Ltd.

  20. Monitoring the Electrochemical Processes in the Lithium–Air Battery by Solid State NMR Spectroscopy

    Science.gov (United States)

    2013-01-01

    A multi-nuclear solid-state NMR approach is employed to investigate the lithium–air battery, to monitor the evolution of the electrochemical products formed during cycling, and to gain insight into processes affecting capacity fading. While lithium peroxide is identified by 17O solid state NMR (ssNMR) as the predominant product in the first discharge in 1,2-dimethoxyethane (DME) based electrolytes, it reacts with the carbon cathode surface to form carbonate during the charging process. 13C ssNMR provides evidence for carbonate formation on the surface of the carbon cathode, the carbonate being removed at high charging voltages in the first cycle, but accumulating in later cycles. Small amounts of lithium hydroxide and formate are also detected in discharged cathodes and while the hydroxide formation is reversible, the formate persists and accumulates in the cathode upon further cycling. The results indicate that the rechargeability of the battery is limited by both the electrolyte and the carbon cathode stability. The utility of ssNMR spectroscopy in directly detecting product formation and decomposition within the battery is demonstrated, a necessary step in the assessment of new electrolytes, catalysts, and cathode materials for the development of a viable lithium–oxygen battery. PMID:24489976

  1. Monitoring the Electrochemical Processes in the Lithium-Air Battery by Solid State NMR Spectroscopy.

    Science.gov (United States)

    Leskes, Michal; Moore, Amy J; Goward, Gillian R; Grey, Clare P

    2013-12-27

    A multi-nuclear solid-state NMR approach is employed to investigate the lithium-air battery, to monitor the evolution of the electrochemical products formed during cycling, and to gain insight into processes affecting capacity fading. While lithium peroxide is identified by 17 O solid state NMR (ssNMR) as the predominant product in the first discharge in 1,2-dimethoxyethane (DME) based electrolytes, it reacts with the carbon cathode surface to form carbonate during the charging process. 13 C ssNMR provides evidence for carbonate formation on the surface of the carbon cathode, the carbonate being removed at high charging voltages in the first cycle, but accumulating in later cycles. Small amounts of lithium hydroxide and formate are also detected in discharged cathodes and while the hydroxide formation is reversible, the formate persists and accumulates in the cathode upon further cycling. The results indicate that the rechargeability of the battery is limited by both the electrolyte and the carbon cathode stability. The utility of ssNMR spectroscopy in directly detecting product formation and decomposition within the battery is demonstrated, a necessary step in the assessment of new electrolytes, catalysts, and cathode materials for the development of a viable lithium-oxygen battery.

  2. Protolytic properties of polyamine wasp toxin analogues studied by 13C NMR spectroscopy

    DEFF Research Database (Denmark)

    Strømgaard, Kristian; Piazzi, Lorna; Olsen, Christian A

    2006-01-01

    Acid-base properties of the natural polyamine wasp toxin PhTX-433 (1) and seven synthetic analogues [PhTX-343 (2), PhTX-334 (3), PhTX-443 (4), PhTX-434 (5), PhTX-344 (6), PhTX-444 (7), and PhTX-333 (8)], each having four protolytic sites, were characterized by 13C NMR spectroscopy. Nonlinear, mul...

  3. Evidence for a dipolar-coupled AM system in carnosine in human calf muscle from in vivo 1H NMR spectroscopy

    Science.gov (United States)

    Schröder, Leif; Bachert, Peter

    2003-10-01

    Spin systems with residual dipolar couplings such as creatine, taurine, and lactate in skeletal muscle tissue exhibit first-order spectra in in vivo 1H NMR spectroscopy at 1.5 T because the coupled protons are represented by (nearly) symmetrized eigenfunctions. The imidazole ring protons (H2, H4) of carnosine are suspected to form also a coupled system. The ring's stiffness could enable a connectivity between these anisochronous protons with the consequence of second-order spectra at low field strength. Our purpose was to study whether this deviation from the Paschen-Back condition can be used to detect the H2-H4 coupling in localized 1D 1H NMR spectra obtained at 1.5 T (64 MHz) from the human calf in a conventional whole-body scanner. As for the hydrogen hyperfine interaction, a Breit-Rabi equation was derived to describe the transition from Zeeman to Paschen-Back regime for two dipolar-coupled protons. The ratio of the measurable coupling strength ( Sk) and the difference in resonance frequencies of the coupled spins (Δ ω) induces quantum-state mixing of various degree upon definition of an appropriate eigenbase of the coupled spin system. The corresponding Clebsch-Gordan coefficients manifest in characteristic energy corrections in the Breit-Rabi formula. These additional terms were used to define an asymmetry parameter of the line positions as a function of Sk and Δ ω. The observed frequency shifts of the resonances were found to be consistent with this parameter within the accuracy achievable in in vivo NMR spectroscopy. Thus it was possible to identify the origin of satellite peaks of H2, H4 and to describe this so far not investigated type of residual dipolar coupling in vivo.

  4. Analysis of Hydroperoxides in solid Polyethylene by NMR and EPR Spectroscopy

    International Nuclear Information System (INIS)

    Assink, Roger A.; Celina, Mathias C.; Dunbar, Timothy D.; Alam, Todd M.; Clough, Roger Lee; Gillen, Kenneth T.

    2000-01-01

    The authors have shown that the hydroperoxide species in γ-irradiated 13 C-polyethylene can be directly observed by 13 C MAS NMR spectroscopy. The experiment was performed without the need for special sample preparation such as chemical derivatization or dissolution. Annealing experiments were employed to study the thermal decomposition of the hydroperoxide species and to measure an activation energy of 98 kJ/mol. EPR spectroscopy suggests that residual polyenyl and alkylperoxy radicals are predominantly trapped in interracial or crystalline regions, while the peroxy radicals observed after UV-photolysis of hydroperoxides are in amorphous regions

  5. 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.

  6. The 'Nuts and Bolts' of 13C NMR Spectroscopy at Elevated-Pressures and -Temperatures for Monitoring In Situ CO2 Conversion to Metal Carbonates

    Science.gov (United States)

    Moore, J. K.; Surface, J. A.; Skemer, P. A.; Conradi, M. S.; Hayes, S. E.

    2013-12-01

    We will present details of newly-constructed specialized NMR designed to conduct in situ elevated-pressure, elevated-temperature 13C NMR studies on unmixed slurries of minerals in the presence of CO2 or other gases. This static probe is capable of achieving 300 bar, 300C conditions, and it is designed to spectroscopically examine 13C signals in mixtures of solids, liquids, gases, and supercritical fluids. Ultimately, our aim is to monitor CO2 uptake in both ultramafic rocks and in more porous geological materials to understand the mechanisms of chemisorption as a function of temperature, pressure and pH. We will give details of the hardware setup, and we will show a variety of static in situ NMR, as well as ex situ 'magic-angle spinning' NMR to show the analyses that are possible of minerals in pure form and in mixtures. In addition, specific NMR pulse sequences, techniques, and modeling will be described in detail. In this in situ NMR probe, we are able to simulate processes at geologically relevant fluid pressures and temperatures, monitoring the kinetics of CO2 conversion to carbonates. The in situ NMR experiments consist of heterogeneous mixtures of rock, salty brine solution, and moderate pressure CO2 gas at elevated temperatures. The purpose of studying these reactions is to determine conditions that affect the efficacy of carbonate formation in various targeted geological reservoirs (i.e., peroditite, or others). Via 13C NMR, we have spectroscopically characterized and quantified the conversion of CO2 to magnesium carbonate and calcium carbonate minerals, including metastable intermediates (such as hydromagnesite, or dypingite in the case of magnesium carbonate species, or vaterite in the case of calcium carbonate species). Such species are distinguishable from a combination of the 13C isotropic chemical shift, the static 13C lineshape, and changes in spin-lattice (T1) relaxation times. We will demonstrate that NMR can be used for quantitative

  7. Nuclear spin: Fifty years of ups and downs

    Energy Technology Data Exchange (ETDEWEB)

    Pines, A. [Lawrence Berkeley National Lab., CA (United States)

    1996-12-31

    Rumors of its demise notwithstanding, nuclear magnetic resonance (NMR) continues to flourish fifty years after our birth. The lecture will be a reminiscence about moments of excitation, coherence and relaxation in the history of NMR which produced, among other developments, spin echoes and time reversal, Fourier transform and multidimensional spectroscopy, magnetic resonance imaging, and high resolution solid state NMR. Applications of modern NMR spectroscopy cut across the boundaries of physics, chemistry, materials, biology and medicine.

  8. Hydrogen cluster/network in tobermorite as studied by multiple-quantum spin counting {sup 1}H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Mogami, Yuuki [Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan); Yamazaki, Satoru; Matsuno, Shinya [Analysis and Simulation Center, Asahi Kasei Corporation, Fuji, Shizuoka 416-8501 (Japan); Matsui, Kunio [Products and Marketing Development Dept., Asahi Kasei Construction Materials Corporation, Sakai-machi, Ibaraki 306-0493 (Japan); Noda, Yasuto [Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan); Takegoshi, K., E-mail: takeyan@kuchem.kyoto-u.ac.jp [Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan)

    2014-12-15

    Proton multiple-quantum (MQ) spin-counting experiment has been employed to study arrangement of hydrogen atoms in 9 Å/11 Å natural/synthetic tobermorites. Even though all tobermorite samples give similar characterless, broad static-powder {sup 1}H NMR spectra, their MQ spin-counting spectra are markedly different; higher quanta in 11 Å tobermorite do not grow with the MQ excitation time, while those in 9 Å one do. A statistical analysis of the MQ results recently proposed [26] is applied to show that hydrogens align in 9 Å tobermorite one dimensionally, while in 11 Å tobermorite they exist as a cluster of 5–8 hydrogen atoms.

  9. Biological response in various compartments of the rat lens after in vivo exposure to UVR-B analyzed by HR-MAS 1H NMR spectroscopy.

    Science.gov (United States)

    Tessem, May-Britt; Bathen, Tone F; Löfgren, Stefan; Saether, Oddbjørn; Mody, Vino; Meyer, Linda; Dong, Xiuqin; Söderberg, Per G; Midelfart, Anna

    2006-12-01

    The purpose of the present study was to investigate metabolic changes in different compartments of the rat lens (anterior, nuclear, posterior, and equatorial) after exposure to an acute double threshold dose of ultraviolet-B radiation (UVR-B) by using high-resolution magic angle spinning (HR-MAS) (1)H nuclear magnetic resonance (NMR) spectroscopy and pattern recognition (PR) METHODS: methods. One eye in each of 28 6-week-old female albino Sprague-Dawley rats was exposed to in vivo 7.5 kJ/m2 UVR-B for 15 minutes. The contralateral eye was left unexposed. One week after irradiation, all rats were killed, and both lenses were isolated. Each lens was cored by a trephine, and the cylinder was sliced into three portions (anterior, nuclear, and posterior). The lens material that remained after the coring process was analyzed as the equatorial region. Analysis of lens metabolism was performed by HR-MAS 1H NMR spectroscopy (14.1 T; Avance DRX600; Bruker BioSpin GmbH, Rheinstetten, Germany), and the metabolic profiles were statistically analyzed by the PR method of principal component analysis (PCA). Metabolic differences were detected among the compartments in the lens, both in samples from the contralateral nonexposed lenses and in samples from lenses exposed to in vivo UVR-B. In the rat lens, exposure to UVR-B caused changes in GSH, phosphocholine, myo-inositol, succinate, formate, and adenosine triphosphate (ATP)/adenosine diphosphate (ADP) and in levels of the amino acids phenylalanine, taurine, hypo-taurine, tyrosine, alanine, valine, isoleucine, and glutamate, that varied among lens compartments. HR-MAS 1H NMR spectroscopy, combined with PR methods (PCA), is effective for analysis of separate parts of the intact rat lens. To understand the biochemistry of the lens, it is important to divide the lens into sections, representing functionally and anatomically distinct compartments.

  10. Identification and quantitation of xenobiotics by 1H NMR spectroscopy in poisoning cases.

    Science.gov (United States)

    Imbenotte, M; Azaroual, N; Cartigny, B; Vermeersch, G; Lhermitte, M

    2003-04-23

    In order to analyse a wide range of xenobiotics and their metabolites present in biological fluids, NMR spectroscopy can be used. A large variety of xenobiotics (therapeutic agents, pesticides, solvents, alcohols) can be characterized and quantitated directly, without sample preparation. NMR investigations were applied to acute poisoning cases, involving drugs such as salicylates and valproic acid (VPA). In a salicylate poisoning case, the three major metabolites of acetylsalicylic acid have been detected in crude urine, and rapid identification of lysine revealed the origin of the intoxication, namely lysine acetylsalicylate (Aspegic). Valproic acid as its glucuronide was identified in urine samples from two poisoned patients. 1H NMR was also used to identify and quantitate paraquat (Gramoxone) in urine owing to its two aromatic signals at 8.49 and 9.02 ppm, in two acutely poisoned patients (183 and 93 mg/l). An intentional poisoning case with tetrahydrofuran (THF) was also investigated. Serum and urine samples were collected. THF was characterized by its resonances at 1.90 and 3.76 ppm, and quantified at 813 and 850 mg/l in the two biological fluids, respectively. Moreover, two other compounds were detected: lactate and gamma-hydroxybutyric acid (GHB). 1H NMR spectroscopic analysis of serum samples from three poisoned patients revealed methanol in one case and ethylene glycol in the two others. Moreover, in the same spectrum, the corresponding metabolites formate and glycolate were found. Compared with the reference chromatographic or spectrophotometric methods, requiring time-consuming extraction and/or derivatization steps, NMR spectroscopy allows the determination of many exogenous and endogenous compounds, without any pre-selection of the analytes.

  11. Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

    Energy Technology Data Exchange (ETDEWEB)

    Ok, Salim; Hoyt, David W.; Andersen, Amity; Sheets, Julie; Welch, Susan A.; Cole, David R.; Mueller, Karl T.; Washton, Nancy M.

    2017-01-18

    Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nano-porous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) were observed with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed non-porous, 12 nm particle size silica and a mesoporous silica with 200 nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. For pure methane, no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2 bar, 32.6 bar, 56.4 bar, 65.1 bar, 112.7 bar, and 130.3 bar). However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.

  12. Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

    International Nuclear Information System (INIS)

    Ok, Salim; Hoyt, David W.; Andersen, Amity; Sheets, Julie; Welch, Susan A.

    2017-01-01

    Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nanoporous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, we observed changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) with 13 C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed nonporous, 12 nm particle size silica and a mesoporous silica with 200 nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. There was no significant thermal effects were found for the observed 13 C chemical shifts at all pressures studied here (28.2, 32.6, 56.4, 65.1, 112.7, and 130.3 bar) for pure methane. However, the 13 C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13 C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD, and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.

  13. Absolute Quantification of Water in Microporous Solids with1H Magic Angle Spinning NMR and Standard Addition.

    Science.gov (United States)

    Houlleberghs, Maarten; Hoffmann, Andreas; Dom, Dirk; Kirschhock, Christine E A; Taulelle, Francis; Martens, Johan A; Breynaert, Eric

    2017-07-05

    Zeolites are microporous materials driving industrial scale adsorption, ion exchange, and catalytic processes. Their water content dramatically impacts their properties, but its quantification with Karl Fisher titration or thermal gravimetric analysis is problematic. When standard addition of water is combined with 1 H magic angle spinning (MAS) NMR detection, absolute quantification of water in microporous materials becomes possible. The method was demonstrated on five different, commercially available zeolites.

  14. Relativistic Spin-Orbit Heavy Atom on the Light Atom NMR Chemical Shifts: General Trends Across the Periodic Table Explained.

    Science.gov (United States)

    Vícha, Jan; Komorovsky, Stanislav; Repisky, Michal; Marek, Radek; Straka, Michal

    2018-04-20

    The importance of relativistic effects on the NMR parameters in heavy-atom (HA) compounds, particularly the SO-HALA (Spin-Orbit Heavy Atom on the Light Atom) effect on NMR chemical shifts, has been known for about 40 years. Yet, a general correlation between the electronic-structure and SO-HALA effect have been missing. By analyzing 1H NMR chemical shifts of the 6th-period hydrides (Cs-At) we discovered general electronic-structure principles and mechanisms that dictate the size and sign of the SO-HALA NMR chemical shifts. In brief, partially occupied HA valence shells induce relativistic shielding at the light atom (LA) nuclei, while empty HA valence shells induce relativistic deshielding. In particular, the LA nucleus is relativistically shielded in 5d2-5d8 and 6p4 HA hydrides and deshielded in 4f0, 5d0, 6s0, 6p0 HA hydrides. This general and intuitive concept explains periodic trends in the 1H NMR chemical shifts along the 6th-period hydrides (Cs-At) studied in this work. We present substantial evidence that the introduced principles have a general validity across the periodic table and can be extended to non-hydride LAs. The decades-old question why compounds with occupied frontier π molecular orbitals (MOs) cause SO-HALA shielding at the LA nuclei, while the frontier σ MOs cause deshielding is answered. We further derive connection between the SO-HALA NMR chemical shifts and Spin-Orbit-induced Electron Deformation Density (SO-EDD), a property, which can be obtained easily from differential electron densities and can be represented graphically. SO-EDD provides an intuitive understanding of the SO-HALA effect in terms of the depletion/concentration of the electron density at LA nuclei caused by spin-orbit coupling due to HA in the presence of magnetic field. Using an analogy between SO-EDD concept and arguments from classic NMR theory, the complex question of the SO-HALA NMR chemical shifts becomes easily understandable for a wide chemical audience.

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

    Science.gov (United States)

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

    2015-04-01

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

  16. NMR-based approach to the analysis of radiopharmaceuticals: radiochemical purity, specific activity, and radioactive concentration values by proton and tritium NMR spectroscopy.

    Science.gov (United States)

    Schenk, David J; Dormer, Peter G; Hesk, David; Pollack, Scott R; Lavey, Carolee Flader

    2015-06-15

    Compounds containing tritium are widely used across the drug discovery and development landscape. These materials are widely utilized because they can be efficiently synthesized and produced at high specific activity. Results from internally calibrated (3)H and (1)H nuclear magnetic resonance (NMR) spectroscopy suggests that at least in some cases, this calibrated approach could supplement or potentially replace radio-high-performance liquid chromatography for radiochemical purity, dilution and scintillation counting for the measurement of radioactivity per volume, and liquid chromatography/mass spectrometry analysis for the determination of specific activity. In summary, the NMR-derived values agreed with those from the standard approaches to within 1% to 9% for solution count and specific activity. Additionally, the NMR-derived values for radiochemical purity deviated by less than 5%. A benefit of this method is that these values may be calculated at the same time that (3)H NMR analysis provides the location and distribution of tritium atoms within the molecule. Presented and discussed here is the application of this method, advantages and disadvantages of the approach, and a rationale for utilizing internally calibrated (1)H and (3)H NMR spectroscopy for specific activity, radioactive concentration, and radiochemical purity whenever acquiring (3)H NMR for tritium location. Copyright © 2015 John Wiley & Sons, Ltd.

  17. Stereochemistry of 16a-Hydroxyfriedelin and 3-Oxo-16-methylfriedel-16-ene Established by 2D NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Vagner Fernandes Knupp

    2009-02-01

    Full Text Available Friedelin (1, 3b-friedelinol (2, 28-hydroxyfriedelin (3, 16a-hydroxyfriedelin (4, 30-hydroxyfriedelin (5 and 16a,28-dihydroxyfriedelin (6 were isolated through fractionation of the hexane extract obtained from branches of Salacia elliptica. After a week in CDCl3 solution, 16a-hydroxyfriedelin (4 reacted turning into 3-oxo-16-methylfriedel-16-ene (7. This is the first report of a dehydration followed by a Nametkin rearrangement of a pentacyclic triterpene in CDCl3 solution occurring in the NMR tube. These seven pentacyclic triterpenes was identified through NMR spectroscopy and the stereochemistry of compound 4 and 7 was established by 2D NMR (NOESY spectroscopy and mass spectrometry (GC-MS. It is also the first time that all the 13C-NMR and 2D NMR spectral data are reported for compounds 4 and 7.

  18. Structural study of α-amino-acid crystals by 1H CRAMPS NMR spectroscopy

    Science.gov (United States)

    Kimura, Hideaki; Nakamura, Kaori; Eguchi, Akiko; Sugisawa, Hisashi; Deguchi, Kenzo; Ebisawa, Kazuyoshi; Suzuki, Ei-ichiro; Shoji, Akira

    1998-06-01

    1H CRAMPS (combined rotation and multiple pulse spectroscopy) NMR was applied to structural analysis of polymorphic forms of α-amino acid crystals in order to test the power of 1H CRAMPS NMR compared with the 13C and 15N NMR methods. We have studied two different stages of α-amino acid crystals: α-glycine and γ-glycine, and A-histidine and B-histidine. As a result, it was found that the α-methylene proton (H α) signal of α-glycine splits into two peaks (4.4 and 3.4 ppm), but that of γ-glycine gives a singlet peak (3.3 ppm), which was reasonably explained by the 1H electrostatic potential charge calculation for this glycine system. Furthermore, it was found that the 1H chemical shift difference between the H 2 and H 5 peaks from the imidazole ring of A-histidine (0.4 ppm) could easily be distinguished from that of B-histidine (0.9 ppm). Thus, the 1H chemical shifts of α-amino acids are very sensitive to a slight difference in magnetic surroundings of protons as well as to differences of the hydrogen bond network. Therefore, the 1H CRAMPS NMR spectra are very useful for the structural analysis of α-amino acid crystals.

  19. Study of radiation induced changes of phosphorus metabolism in mice by (31)P NMR spectroscopy.

    Science.gov (United States)

    Sersa, Igor; Kranjc, Simona; Sersa, Gregor; Nemec-Svete, Alenka; Lozar, Bojan; Sepe, Ana; Vidmar, Jernej; Sentjurc, Marjeta

    2010-09-01

    The aim of this study was to examine whether (31)P NMR can efficiently detect X-ray radiation induced changes of energy metabolism in mice. Exposure to ionizing radiation causes changes in energy supply that are associated with the tissue damage because of oxidative stress and uncoupled oxidative phosphorylation. This has as a consequence decreased phosphocreatine to adenosine triphosphate ratio (Pcr/ATP) as well as increased creatine kinase (CK) and liver enzymes (transaminases AST and ALT) levels in serum. In this study, experimental mice that received 7 Gy of X-ray radiation and a control group were studied by (31)P NMR spectroscopy and biochemically by measuring CK and liver enzyme levels in plasma. Mice (irradiated and control) were measured at regular time intervals for the next three weeks after the exposure to radiation. A significant change in the Pcr/ATP ratio, determined from corresponding peaks of (31)P NMR spectra, was observed in the 7 Gy group 2 days or more after the irradiation, while no significant change in the Pcr/ATP ratio, was observed in the control group. This result was supported by parallel measurements of CK levels that were highly increased immediately after the irradiation which correlates with the observed decrease of the Pcr/ATP ratio and with it associated drop of muscle energy supply. The (31)P NMR measurements of the Pcr/ATP ratio can in principle serve as an instantaneous and noninvasive index for assessment of the received dose of irradiation.

  20. Efficient spin transitions in inelastic electron tunneling spectroscopy.

    Science.gov (United States)

    Lorente, Nicolás; Gauyacq, Jean-Pierre

    2009-10-23

    The excitation of the spin degrees of freedom of an adsorbed atom by tunneling electrons is computed using strong coupling theory. Recent measurements [Heinrich, Science 306, 466 (2004)] reveal that electron currents in a magnetic system efficiently excite its magnetic moments. Our theory shows that the incoming electron spin strongly couples with that of the adsorbate so that memory of the initial spin state is lost, leading to large excitation efficiencies. First-principles transmissions are evaluated in quantitative agreement with the experiment.

  1. Spin noise spectroscopy beyond thermal equilibrium and linear response.

    Science.gov (United States)

    Glasenapp, P; Sinitsyn, N A; Yang, Luyi; Rickel, D G; Roy, D; Greilich, A; Bayer, M; Crooker, S A

    2014-10-10

    Per the fluctuation-dissipation theorem, the information obtained from spin fluctuation studies in thermal equilibrium is necessarily constrained by the system's linear response functions. However, by including weak radio frequency magnetic fields, we demonstrate that intrinsic and random spin fluctuations even in strictly unpolarized ensembles can reveal underlying patterns of correlation and coupling beyond linear response, and can be used to study nonequilibrium and even multiphoton coherent spin phenomena. We demonstrate this capability in a classical vapor of (41)K alkali atoms, where spin fluctuations alone directly reveal Rabi splittings, the formation of Mollow triplets and Autler-Townes doublets, ac Zeeman shifts, and even nonlinear multiphoton coherences.

  2. Mg/Al ordering in layered double hydroxides revealed by multinuclear NMR spectroscopy.

    Science.gov (United States)

    Sideris, Paul J; Nielsen, Ulla Gro; Gan, Zhehong; Grey, Clare P

    2008-07-04

    The anion-exchange ability of layered double hydroxides (LDHs) has been exploited to create materials for use in catalysis, drug delivery, and environmental remediation. The specific cation arrangements in the hydroxide layers of hydrotalcite-like LDHs, of general formula Mg2+(1-x)Al3+(x)OH2(Anion(n-)(x/n)).yH2O, have, however, remained elusive, and their elucidation could enhance the functional optimization of these materials. We applied rapid (60 kilohertz) magic angle spinning (MAS) to obtain high-resolution hydrogen-1 nuclear magnetic resonance (1H NMR) spectra and characterize the magnesium and aluminum distribution. These data, in combination with 1H-27Al double-resonance and 25Mg triple-quantum MAS NMR data, show that the cations are fully ordered for magnesium:aluminum ratios of 2:1 and that at lower aluminum content, a nonrandom distribution of cations persists, with no Al3+-Al3+ close contacts. The application of rapid MAS NMR methods to investigate proton distributions in a wide range of materials is readily envisaged.

  3. Solid-state NMR analysis of membrane proteins and protein aggregates by proton detected spectroscopy

    International Nuclear Information System (INIS)

    Zhou, Donghua H.; Nieuwkoop, Andrew J.; Berthold, Deborah A.; Comellas, Gemma; Sperling, Lindsay J.; Tang, Ming; Shah, Gautam J.; Brea, Elliott J.; Lemkau, Luisel R.; Rienstra, Chad M.

    2012-01-01

    Solid-state NMR has emerged as an important tool for structural biology and chemistry, capable of solving atomic-resolution structures for proteins in membrane-bound and aggregated states. Proton detection methods have been recently realized under fast magic-angle spinning conditions, providing large sensitivity enhancements for efficient examination of uniformly labeled proteins. The first and often most challenging step of protein structure determination by NMR is the site-specific resonance assignment. Here we demonstrate resonance assignments based on high-sensitivity proton-detected three-dimensional experiments for samples of different physical states, including a fully-protonated small protein (GB1, 6 kDa), a deuterated microcrystalline protein (DsbA, 21 kDa), a membrane protein (DsbB, 20 kDa) prepared in a lipid environment, and the extended core of a fibrillar protein (α-synuclein, 14 kDa). In our implementation of these experiments, including CONH, CO(CA)NH, CANH, CA(CO)NH, CBCANH, and CBCA(CO)NH, dipolar-based polarization transfer methods have been chosen for optimal efficiency for relatively high protonation levels (full protonation or 100 % amide proton), fast magic-angle spinning conditions (40 kHz) and moderate proton decoupling power levels. Each H–N pair correlates exclusively to either intra- or inter-residue carbons, but not both, to maximize spectral resolution. Experiment time can be reduced by at least a factor of 10 by using proton detection in comparison to carbon detection. These high-sensitivity experiments are especially important for membrane proteins, which often have rather low expression yield. Proton-detection based experiments are expected to play an important role in accelerating protein structure elucidation by solid-state NMR with the improved sensitivity and resolution.

  4. Uncovering the triggers for GPCR activation using solid-state NMR spectroscopy

    Science.gov (United States)

    Kimata, Naoki; Reeves, Philip J.; Smith, Steven O.

    2015-04-01

    G protein-coupled receptors (GPCRs) span cell membranes with seven transmembrane helices and respond to a diverse array of extracellular signals. Crystal structures of GPCRs have provided key insights into the architecture of these receptors and the role of conserved residues. However, the question of how ligand binding induces the conformational changes that are essential for activation remains largely unanswered. Since the extracellular sequences and structures of GPCRs are not conserved between receptor subfamilies, it is likely that the initial molecular triggers for activation vary depending on the specific type of ligand and receptor. In this article, we describe NMR studies on the rhodopsin subfamily of GPCRs and propose a mechanism for how retinal isomerization switches the receptor to the active conformation. These results suggest a general approach for determining the triggers for activation in other GPCR subfamilies using NMR spectroscopy.

  5. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva

    2016-08-15

    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  6. Conformational problem of alkanes in liquid crystals by NMR spectroscopy: a mini-review.

    Science.gov (United States)

    Weber, Adrian C J; Chen, Daniel H J

    2014-10-01

    Recent discoveries of the role of alkane flexibility in determining liquid-crystal behaviour are surveyed. With the impetus for understanding the alkane conformational problem established, recent model dependent (1)H NMR work on the topic will be reviewed where progress is made but the need to circumvent models eventually becomes evident. A closer look at the rigid basic units of alkanes will provide the way forward where it is shown that the orientational ordering and anisotropic potentials of these molecules dissolved in liquid crystals scale with each other. Once this relationship is established, a series of works using anisotropic and isotropic (1)H NMR spectroscopy to study alkane conformational statistics will be covered, wherein the influence of the gas, isotropic condensed and anisotropic condensed phases will be described. Copyright © 2014 John Wiley & Sons, Ltd.

  7. Remeasuring HEWL pKa values by NMR spectroscopy 

    DEFF Research Database (Denmark)

    Webb, Helen; Tynan-Connolly, Barbara Mary; Lee, Gregory M

    2011-01-01

    protonated carbons and protons in this protein. We extracted pK(a) values from the resulting titration curves using standard fitting methods, and compared these values to each other, and with those measured previously by ¹H NMR (Bartik et al., Biophys J 1994;66:1180–1184). This analysis gives insights......Site-specific pK(a) values measured by NMR spectroscopy provide essential information on protein electrostatics, the pH-dependence of protein structure, dynamics and function, and constitute an important benchmark for protein pK(a) calculation algorithms. Titration curves can be measured...... field effects, and conformational changes. We have re-measured titration curves for all carboxylates and His 15 in Hen Egg White Lysozyme (HEWL) by recording the pH-dependent chemical shifts of all backbone amide nitrogens and protons, Asp/Glu side chain protons and carboxyl carbons, and imidazole...

  8. Monitoring of the insecticide trichlorfon by phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy

    International Nuclear Information System (INIS)

    Talebpour, Zahra; Ghassempour, Alireza; Zendehzaban, Mehdi; Bijanzadeh, Hamid Reza; Mirjalili, Mohammad Hossein

    2006-01-01

    Trichlorfon is an organophosphorus insecticide, which is extensively being used for protection of fruit crops. Trichlorfon is a thermal labile compound, which cannot be easily determined by gas chromatography (GC) and has no suitable group for sensitive detection by high performance liquid chromatography (HPLC). In this study, a 31 P nuclear magnetic resonance ( 31 P NMR) has been described for monitoring of trichlorfon without any separation step. The quantitative works of 31 P NMR spectroscopy has been performed in the presence of an internal standard (hexamethylphosphoramide). Limit of detection (LOD) for this method has been found to be 55 mg L -1 , without any sample preparation, and the linear working range was 150-5500 mg L -1 . Relative standard deviation (R.S.D.%) of the method for three replicates within and between days was obtained ≤9%. The average recovery efficiency was approximately 99-112%. This method was applied for monitoring trichlorfon in a commercial insecticide sample and tomato sample

  9. An instrument control and data analysis program for NMR imaging and spectroscopy

    International Nuclear Information System (INIS)

    Roos, M.S.; Mushlin, R.A.; Veklerov, E.; Port, J.D.; Ladd, C.; Harrison, C.G.

    1988-01-01

    We describe a software environment created to support real-time instrument control and signal acquisition as well as array-processor based signal and image processing in up to five dimensions. The environment is configured for NMR imaging and in vivo spectroscopy. It is designed to provide flexible tools for implementing novel NMR experiments in the research laboratory. Data acquisition and processing operations are programmed in macros which are loaded in assembled from to minimize instruction overhead. Data arrays are dynamically allocated for efficient use of memory and can be mapped directly into disk files. The command set includes primitives for real-time control of data acquisition, scalar arithmetic, string manipulation, branching, a file system and vector operations carried out by an array processor. 6 figs

  10. Coherent evolution of parahydrogen induced polarisation using laser pump, NMR probe spectroscopy: Theoretical framework and experimental observation.

    Science.gov (United States)

    Halse, Meghan E; Procacci, Barbara; Henshaw, Sarah-Louise; Perutz, Robin N; Duckett, Simon B

    2017-05-01

    We recently reported a pump-probe method that uses a single laser pulse to introduce parahydrogen (p-H 2 ) into a metal dihydride complex and then follows the time-evolution of the p-H 2 -derived nuclear spin states by NMR. We present here a theoretical framework to describe the oscillatory behaviour of the resultant hyperpolarised NMR signals using a product operator formalism. We consider the cases where the p-H 2 -derived protons form part of an AX, AXY, AXYZ or AA'XX' spin system in the product molecule. We use this framework to predict the patterns for 2D pump-probe NMR spectra, where the indirect dimension represents the evolution during the pump-probe delay and the positions of the cross-peaks depend on the difference in chemical shift of the p-H 2 -derived protons and the difference in their couplings to other nuclei. The evolution of the NMR signals of the p-H 2 -derived protons, as well as the transfer of hyperpolarisation to other NMR-active nuclei in the product, is described. The theoretical framework is tested experimentally for a set of ruthenium dihydride complexes representing the different spin systems. Theoretical predictions and experimental results agree to within experimental error for all features of the hyperpolarised 1 H and 31 P pump-probe NMR spectra. Thus we establish the laser pump, NMR probe approach as a robust way to directly observe and quantitatively analyse the coherent evolution of p-H 2 -derived spin order over micro-to-millisecond timescales. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  11. Coherent evolution of parahydrogen induced polarisation using laser pump, NMR probe spectroscopy: Theoretical framework and experimental observation

    Science.gov (United States)

    Halse, Meghan E.; Procacci, Barbara; Henshaw, Sarah-Louise; Perutz, Robin N.; Duckett, Simon B.

    2017-05-01

    We recently reported a pump-probe method that uses a single laser pulse to introduce parahydrogen (p-H2) into a metal dihydride complex and then follows the time-evolution of the p-H2-derived nuclear spin states by NMR. We present here a theoretical framework to describe the oscillatory behaviour of the resultant hyperpolarised NMR signals using a product operator formalism. We consider the cases where the p-H2-derived protons form part of an AX, AXY, AXYZ or AA‧XX‧ spin system in the product molecule. We use this framework to predict the patterns for 2D pump-probe NMR spectra, where the indirect dimension represents the evolution during the pump-probe delay and the positions of the cross-peaks depend on the difference in chemical shift of the p-H2-derived protons and the difference in their couplings to other nuclei. The evolution of the NMR signals of the p-H2-derived protons, as well as the transfer of hyperpolarisation to other NMR-active nuclei in the product, is described. The theoretical framework is tested experimentally for a set of ruthenium dihydride complexes representing the different spin systems. Theoretical predictions and experimental results agree to within experimental error for all features of the hyperpolarised 1H and 31P pump-probe NMR spectra. Thus we establish the laser pump, NMR probe approach as a robust way to directly observe and quantitatively analyse the coherent evolution of p-H2-derived spin order over micro-to-millisecond timescales.

  12. Spin crossover studies in cationic complexes of iron by using Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Vadera, S.R.; Kumar, N.

    1990-01-01

    The spin transition in two new cationic complexes of iron, i.e. iron bipyridine formate, [Fe(bipy) 3 ](HCOO) 2 .5(HCOOH) and iron bipyridine tetrafluoro borate, [Fe(bipy) 3 ](BF 4 ) 2 .2H 2 O were studied by Moessbauer spectroscopy. From quadrupole splitting values, it was established that at different temperatures both complexes show the coexistence of both high spin state and low spin state at 300 K, while complete transformation to low spin state occurs at 77 K. Both compounds were prepared by electrochemical technique. (author) 12 refs.; 1 fig.; 1 tab

  13. Arrangement and mobility of water in vermiculite hydrates followed by 1H NMR spectroscopy.

    Science.gov (United States)

    Sanz, J; Herrero, C P; Serratosa, J M

    2006-04-20

    The arrangement of water molecules in one- and two-layer hydrates of high-charged vermiculites, saturated with alkaline (Li(+), Na(+)) and alkali-earth (Mg(2+), Ca(2+), Ba(2+)) cations, has been analyzed with (1)H NMR spectroscopy. Two different orientations for water molecules have been found, depending on the hydration state and the sites occupied by interlayer cations. As the amount of water increases, hydrogen bond interactions between water molecules increase at expenses of water-silicate interactions. This interaction favors water mobility in vermiculites. A comparison of the temperature dependence of relaxation times T(1) and T(2) for one and two-layer hydrates of Na-vermiculite shows that the rotations of water molecules around C(2)-axes and that of cation hydration shells around the c-axis is favored in the two-layer hydrate. In both hydrates, the anisotropic diffusion of water takes place at room temperature, preserving the orientation of water molecules relative to the silicate layers. Information obtained by NMR spectroscopy is compatible with that deduced by infrared spectroscopy and with structural studies carried out with X-ray and neutron diffraction techniques on single-crystals of vermiculite.

  14. Importance of triples contributions to NMR spin-spin coupling constants computed at the CC3 and CCSDT levels

    DEFF Research Database (Denmark)

    Faber, Rasmus; Sauer, Stephan P. A.; Gauss, Jürgen

    2017-01-01

    that the most important contributions arising from connected triple excitations in the coupled cluster expansion are accounted for at the CC3 level. Thus we believe that the CC3 method will become the standard approach for calculation of reference values of nuclear spin-spin coupling constants....

  15. Characterization of Silicon Nanocrystal Surfaces by Multidimensional Solid-State NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hanrahan, Michael P. [Department; US DOE Ames Laboratory, Ames, Iowa 50011, United States; Fought, Ellie L. [Department; Windus, Theresa L. [Department; Wheeler, Lance M. [Chemistry; Anderson, Nicholas C. [Chemistry; Neale, Nathan R. [Chemistry; Rossini, Aaron J. [Department; US DOE Ames Laboratory, Ames, Iowa 50011, United States

    2017-11-17

    The chemical and photophysical properties of silicon nanocrystals (Si NCs) are strongly dependent on the chemical composition and structure of their surfaces. Here we use fast magic angle spinning (MAS) and proton detection to enable the rapid acquisition of dipolar and scalar 2D 1H-29Si heteronuclear correlation (HETCOR) solid-state NMR spectra and reveal a molecular picture of hydride-terminated and alkyl-functionalized surfaces of Si NCs produced in a nonthermal plasma. 2D 1H-29Si HETCOR and dipolar 2D 1H-1H multiple-quantum correlation spectra illustrate that resonances from surface mono-, di-, and trihydride groups cannot be resolved, contrary to previous literature assignments. Instead the 2D NMR spectra illustrate that there is large distribution of 1H and 29Si chemical shifts for the surface hydride species in both the as-synthesized and functionalized Si NCs. However, proton-detected 1H-29Si refocused INEPT experiments can be used to unambiguously differentiate NMR signals from the different surface hydrides. Varying the 29Si evolution time in refocused INEPT experiments and fitting the oscillation of the NMR signals allows for the relative populations of the different surface hydrides to be estimated. This analysis confirms that monohydride species are the predominant surface species on the as-synthesized Si NCs. A reduction in the populations of the di- and trihydrides is observed upon functionalization with alkyl groups, consistent with our previous hypothesis that the trihydride, or silyl (*SiH3), group is primarily responsible for initiating surface functionalization reactions. Density functional theory (DFT) calculations were used to obtain quantum chemical structural models of the Si NC surface and reproduce the observed 1H and 29Si chemical shifts. The approaches outlined here will be useful to obtain a more detailed picture of surface structures for Si NCs and other hydride-passivated nanomaterials.

  16. NMR spin relaxation in proteins: The patterns of motion that dissipate power to the bath

    Science.gov (United States)

    Shapiro, Yury E.; Meirovitch, Eva

    2014-04-01

    We developed in recent years the two-body coupled-rotator slowly relaxing local structure (SRLS) approach for the analysis of NMR relaxation in proteins. The two bodies/rotators are the protein (diffusion tensor D1) and the spin-bearing probe, e.g., the 15N-1H bond (diffusion tensor, D2), coupled by a local potential (u). A Smoluchowski equation is solved to yield the generic time correlation functions (TCFs), which are sums of weighted exponentials (eigenmodes). By Fourier transformation one obtains the generic spectral density functions (SDFs) which underlie the experimental relaxation parameters. The typical paradigm is to characterize structural dynamics in terms of the best-fit values of D1, D2, and u. Additional approaches we pursued employ the SRLS TCFs, SDFs, or eigenmodes as descriptors. In this study we develop yet another perspective. We consider the SDF as function of the angular velocity associated with the fluctuating fields underlying NMR relaxation. A parameter called j-fraction, which represents the relative contribution of eigenmode, i, to a given value of the SDF function at a specific frequency, ω, is defined. j-fraction profiles of the dominant eigenmodes are derived for 0 ≤ ω ≤ 1012 rad/s. They reveal which patterns of motion actuate power dissipation at given ω-values, what are their rates, and what is their relative contribution. Simulations are carried out to determine the effect of timescale separation, D1/D2, axial potential strength, and local diffusion axiality. For D1/D2 ≤ 0.01 and strong local potential of 15 kBT, power is dissipated by global diffusion, renormalized (by the strong potential) local diffusion, and probe diffusion on the surface of a cone (to be called cone diffusion). For D1/D2 = 0.1, power is dissipated by mixed eigenmodes largely of a global-diffusion-type or cone-diffusion-type, and a nearly bare renormalized-local-diffusion eigenmode. For D1/D2 > 0.1, most eigenmodes are of a mixed type. The analysis is

  17. Internal dynamics in helical molecules studied by X-ray diffraction, NMR spectroscopy and DFT calculations

    Czech Academy of Sciences Publication Activity Database

    Dračínský, Martin; Storch, Jan; Církva, Vladimír; Císařová, I.; Sýkora, Jan

    2017-01-01

    Roč. 19, č. 4 (2017), s. 2900-2907 ISSN 1463-9076 R&D Projects: GA ČR GA15-11223S; GA ČR GA15-12719S Institutional support: RVO:61388963 ; RVO:67985858 Keywords : helicene * NMR spectroscopy * DFT calculations Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry; Physical chemistry (UCHP-M) Impact factor: 4.123, year: 2016 http://pubs.rsc.org/en/content/articlehtml/2013/cp/c6cp07552e

  18. Probing the structural details of xylan degradation by real-time NMR spectroscopy

    DEFF Research Database (Denmark)

    Petersen, Bent O.; Lok, Finn; Meier, Sebastian

    2014-01-01

    fraction of cereal cell wall polysaccharides consists of arabinoxylans. Arabinoxylan and its degradation products are therefore present in a variety of agro-industrial residues and products. Here, we undertook to track the structural details of wheat arabinoxylan degradation with high resolution NMR...... spectroscopy. More than 15 carbohydrate residues were distinguished in the substrate and more than 20 residues in partially degraded samples without any sample cleanup. The resolution of a plethora of structural motifs in situ permits the readout of persisting structures in degradation processes...

  19. NMR spectroscopy and atomic force microscopy characterization of hybrid organic – inorganic coatings

    Czech Academy of Sciences Publication Activity Database

    Brus, Jiří; Špírková, Milena

    2005-01-01

    Roč. 220, č. 1 (2005), s. 155-164 ISSN 1022-1360. [Discussion Conference Spectroscopy of Partially Ordered Macromolecular Systems /22./. Prague, 21.07.2003-24.07.2003] R&D Projects: GA ČR GA203/01/0735; GA AV ČR IAA4050008 Institutional research plan: CEZ:AV0Z40500505 Keywords : atomic force microscopy * coatings and films * solid-state NMR Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.913, year: 2005

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

    Science.gov (United States)

    Wachter-Jurcsak, Nanette; Zamani, Hossein

    1999-05-01

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

  1. Rapid Determination of Total Thujone in Absinthe Using 1H NMR Spectroscopy

    OpenAIRE

    Yulia B. Monakhova; Thomas Kuballa; Dirk W. Lachenmeier

    2011-01-01

    1H NMR spectroscopy is utilized to quantify total thujone (sum of alpha- and beta-isomers) in absinthe. For sample preparation, a simple dilution with buffer is required. Thujone produces a distinct peak of the CH2 group in the cyclopentanone moiety in the 2.13–2.11 ppm range. No overlap with other typical constituents such as anethole or fenchone occurs. The detection limit of 0.3 mg/L is adequate to control the EU maximum limit. The relative standard deviation was 6%, and linearity was obse...

  2. Structural Investigations of Portland Cement Components, Hydration, and Effects of Admixtures by Solid-State NMR Spectroscopy

    DEFF Research Database (Denmark)

    Skibsted, Jørgen Bengaard; Andersen, Morten D.; Jakobsen, Hans Jørgen

    2006-01-01

    been investigated in detail by 29Si and 27Al MAS NMR where the combination of the results for these spin-nuclei provides important information on the degree of Al-incorporation in the C-S-H structure and of the average chain lengths of tetrahedral SiO4 and AlO4 units. This presentation will illustrate...

  3. Dichlorobis(5-methyl-2-(phenylazopyridine ruthenium(II complex: characterization and NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    Kanidtha Hansongnern

    2005-12-01

    Full Text Available The new azoimine functionalized ligand, 5-methyl-2-(phenylazopyridine (5mazpy was synthesized. It reacted with RuCl3.3H2O in ethanolic solution to give the isomeric [Ru(5mazpy2Cl2] complexes. One of the isomers was characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, UV-Visible absorption spectroscopy, and cyclic voltammetry. Results from infrared spectroscopy show that the N=N stretching mode in the complex appeared at a lower frequency than that in the free ligand. The formulation of complex was comfirmed by elemental analysis. The 1H and 13C NMR spectra of complex exhibited two sets of ligand peaks, this indicated that both 5mazpy ligands were in different environments. Therefore, the [Ru(5mazpy2Cl2] complex has no C2-symmetry. Results from UV-Visible absorption spectroscopy show that the complex exhibited the t2(Ru → π*(5mazpy MLCT transitions in the visible region. Redox studies showed the Ru(III/Ru(II couple at +0.62 V and two azo reductions couple at -1.17 V and -1.51 V versus ferrocene couple.

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

    CERN Document Server

    Vosegaard, T; Nielsen, N C

    2002-01-01

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

  5. Effect of spatial spin modulation on relaxation and NMR frequencies of sup 5 sup 7 Fe nuclei in ferroelectric antiferromagnetic BiFeO sub 3

    CERN Document Server

    Zalessky, A V; Zvezdin, A K; Gippius, A A; Morozova, E N; Khozeev, D F; Bush, A S; Pokatilov, V S

    2002-01-01

    The NMR spectra on the iron nuclei in the BiFeO sub 3 antiferromagnetic sample enriched by the sup 5 sup 7 Fe (95.43%) with the spatially-modulated magnetic structure are studied. It is established that the cycloid-type spin modulation in the BiFeO sub 3 produces spatial modulation of the nuclear spin-spin relaxation velocity and leads to the spectral nonuniform widening of the NMR local line. It is determined also that the local magnetic moments of the iron ions on various cycloid sections differently depend on temperature which testifies to different character of the spin waves excitation. The analogy of the experimental results with the NMR regularities in the Bloch wall is discussed

  6. Possible quadrupolar nematic phase in the frustrated spin chain LiCuSbO4: An NMR investigation

    Science.gov (United States)

    Bosiočić, M.; Bert, F.; Dutton, S. E.; Cava, R. J.; Baker, P. J.; Požek, M.; Mendels, P.

    2017-12-01

    The frustrated one-dimensional quantum magnet LiCuSbO4 is a rare realization of the J1-J2 spin chain model with an easily accessible saturation field, formerly estimated at 12 T. Exotic multipolar nematic phases were theoretically predicted in such compounds just below the saturation field, but without unambiguous experimental observation so far. In this paper we present extensive experimental research on the compound in a wide temperature (30 mK to 300 K) and field (0-13.3 T) range by muon spin rotation (μ SR ), 7Li nuclear magnetic resonance (NMR), and magnetic susceptibility (SQUID). μ SR experiments in zero magnetic field demonstrate the absence of long-range 3D ordering down to 30 mK. Together with former heat capacity data [Dutton et al., Phys. Rev. Lett. 108, 187206 (2012), 10.1103/PhysRevLett.108.187206], magnetic susceptibility measurements suggest a short-range-correlated vector chiral phase in the field range 0-4 T. At the intermediate-field values (5-12 T), the system enters a 3D-ordered spin density wave phase with 0.75 μB per copper site at lowest temperatures (125 mK), estimated by NMR. At still higher field, the magnetization is found to be saturated above 13 T where the spin lattice T1-1 relaxation reveals a spin gap estimated at 3.2(2) K. We narrow down the possibility of observing a multipolar nematic phase to the range 12.5-13 T.

  7. Spin inelastic electron tunneling spectroscopy on local spin adsorbed on surface.

    Science.gov (United States)

    Fransson, J

    2009-06-01

    The recent experimental conductance measurements taken on magnetic impurities on metallic surfaces, using scanning tunneling microscopy technique and suggesting occurrence of inelastic scattering processes, are theoretically addressed. We argue that the observed conductance signatures are caused by transitions between the spin states that have opened due to, for example, exchange coupling between the local spins and the tunneling electrons, and are directly interpretable in terms of inelastic transitions energies. Feasible measurements using spin-polarized scanning tunneling microscopy that would enable new information about the excitation spectrum of the local spins are discussed.

  8. Mobility of TOAC spin-labelled peptides binding to the Src SH3 domain studied by paramagnetic NMR

    International Nuclear Information System (INIS)

    Lindfors, Hanna E.; Koning, Peter E. de; Wouter Drijfhout, Jan; Venezia, Brigida; Ubbink, Marcellus

    2008-01-01

    Paramagnetic relaxation enhancement provides a tool for studying the dynamics as well as the structure of macromolecular complexes. The application of side-chain coupled spin-labels is limited by the mobility of the free radical. The cyclic, rigid amino acid spin-label TOAC (2,2,6,6-Tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid), which can be incorporated straightforwardly by peptide synthesis, provides an attractive alternative. In this study, TOAC was incorporated into a peptide derived from focal adhesion kinase (FAK), and the interaction of the peptide with the Src homology 3 (SH3) domain of Src kinase was studied, using paramagnetic NMR. Placing TOAC within the binding motif of the peptide has a considerable effect on the peptide-protein binding, lowering the affinity substantially. When the TOAC is positioned just outside the binding motif, the binding constant remains nearly unaffected. Although the SH3 domain binds weakly and transiently to proline-rich peptides from FAK, the interaction is not very dynamic and the relative position of the spin-label to the protein is well-defined. It is concluded that TOAC can be used to generate reliable paramagnetic NMR restraints

  9. Mobility of TOAC spin-labelled peptides binding to the Src SH3 domain studied by paramagnetic NMR

    Energy Technology Data Exchange (ETDEWEB)

    Lindfors, Hanna E. [Leiden University, Leiden Institute of Chemistry, Gorlaeus Laboratories (Netherlands); Koning, Peter E. de; Wouter Drijfhout, Jan [Leiden University Medical Centre, Department of Immunohematology and Blood Transfusion (Netherlands); Venezia, Brigida; Ubbink, Marcellus [Leiden University, Leiden Institute of Chemistry, Gorlaeus Laboratories (Netherlands)], E-mail: m.ubbink@chem.leidenuniv.nl

    2008-07-15

    Paramagnetic relaxation enhancement provides a tool for studying the dynamics as well as the structure of macromolecular complexes. The application of side-chain coupled spin-labels is limited by the mobility of the free radical. The cyclic, rigid amino acid spin-label TOAC (2,2,6,6-Tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid), which can be incorporated straightforwardly by peptide synthesis, provides an attractive alternative. In this study, TOAC was incorporated into a peptide derived from focal adhesion kinase (FAK), and the interaction of the peptide with the Src homology 3 (SH3) domain of Src kinase was studied, using paramagnetic NMR. Placing TOAC within the binding motif of the peptide has a considerable effect on the peptide-protein binding, lowering the affinity substantially. When the TOAC is positioned just outside the binding motif, the binding constant remains nearly unaffected. Although the SH3 domain binds weakly and transiently to proline-rich peptides from FAK, the interaction is not very dynamic and the relative position of the spin-label to the protein is well-defined. It is concluded that TOAC can be used to generate reliable paramagnetic NMR restraints.

  10. Biological effects and physical safety aspects of NMR imaging and in vivo spectroscopy

    International Nuclear Information System (INIS)

    Tenforde, T.S.; Budinger, T.F.

    1985-08-01

    An assessment is made of the biological effects and physical hazards of static and time-varying fields associated with the NMR devices that are being used for clinical imaging and in vivo spectroscopy. A summary is given of the current state of knowledge concerning the mechanisms of interaction and the bioeffects of these fields. Additional topics that are discussed include: (1) physical effects on pacemakers and metallic implants such as aneurysm clips, (2) human health studies related to the effects of exposure to nonionizing electromagnetic radiation, and (3) extant guidelines for limiting exposure of patients and medical personnel to the fields produced by NMR devices. On the basis of information available at the present time, it is concluded that the fields associated with the current generation of NMR devices do not pose a significant health risk in themselves. However, rigorous guidelines must be followed to avoid the physical interaction of these fields with metallic implants and medical electronic devices. 476 refs., 5 figs., 2 tabs

  11. Analysis of trivalent cation complexation to functionalized mesoporous silica using solid-state NMR spectroscopy.

    Science.gov (United States)

    Shusterman, Jennifer; Mason, Harris; Bruchet, Anthony; Zavarin, Mavrik; Kersting, Annie B; Nitsche, Heino

    2014-11-28

    Functionalized mesoporous silica has applications in separations science, catalysis, and sensors. In this work, we studied the fundamental interactions of trivalent cations with functionalized mesoporous silica. We contacted trivalent cations of varying ionic radii with N-[5-(trimethoxysilyl)-2-aza-1-oxopentyl]caprolactam functionalized mesoporous silica with the aim of probing the binding mechanism of the metal to the surface of the solid. We studied the functionalized silica using solid-state nuclear magnetic resonance (NMR) spectroscopy before and after contact with the metals of interest. We collected NMR spectra of the various metals, as well as of (29)Si and (13)C to probe the silica substrate and the ligand properties, respectively. The NMR spectra indicate that the metals bind to the functionalized silica via two mechanisms. Aluminum sorbed to both the silica and the ligand, but with different coordination for each. Scandium also sorbed to both the silica and the ligand, and unlike the aluminum, had the same coordination number. Additionally, the functionalized silica was susceptible to acid hydrolysis and two primary mechanisms of degradation were observed: detachment from the silica surface and opening of the seven-membered ring in the ligand. Opening of the seven-membered ring may be beneficial in that it decreases steric hindrance of the molecule for binding.

  12. Investigation of Oxidative Degradation in Polymers Using (17)O NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Alam, Todd M.; Celina, Mathew; Assink, Roger A.; Clough, Roger L.; Gillen, Kenneth T.; Wheeler David R.

    1999-07-20

    The thermal oxidation of pentacontane (C{sub 50}H{sub 102}), and of the homopolymer polyisoprene, has been investigated using {sup 17}O NMR spectroscopy. By performing the oxidation using {sup 17}O labeled O{sub 2} gas, it is possible to easily identify degradation products, even at relatively low concentrations. It is demonstrated that details of the degradation mechanism can be obtained from analysis of the {sup 17}O NMR spectra as a function of total oxidation. Pentacontane reveals the widest variety of reaction products, and exhibits changes in the relative product distributions with increasing O{sub 2} consumption. At low levels of oxygen incorporation, peroxides are the major oxidation product, while at later stages of degradation these species are replaced by increasing concentrations of ketones, alcohols, carboxylic acids and esters. Analyzing the product distribution can help in identification of the different free-radical decomposition pathways of hydroperoxides, including recombination, proton abstraction and chain scission, as well as secondary reactions. The {sup 17}O NMR spectra of thermally oxidized polyisoprene reveal fewer degradation functionalities, but exhibit an increased complexity in the type of observed degradation species due to structural features such as unsaturation and methyl branching. Alcohols and ethers formed from hydrogen abstraction and free radical termination.

  13. Biological effects and physical safety aspects of NMR imaging and in vivo spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tenforde, T.S.; Budinger, T.F.

    1985-08-01

    An assessment is made of the biological effects and physical hazards of static and time-varying fields associated with the NMR devices that are being used for clinical imaging and in vivo spectroscopy. A summary is given of the current state of knowledge concerning the mechanisms of interaction and the bioeffects of these fields. Additional topics that are discussed include: (1) physical effects on pacemakers and metallic implants such as aneurysm clips, (2) human health studies related to the effects of exposure to nonionizing electromagnetic radiation, and (3) extant guidelines for limiting exposure of patients and medical personnel to the fields produced by NMR devices. On the basis of information available at the present time, it is concluded that the fields associated with the current generation of NMR devices do not pose a significant health risk in themselves. However, rigorous guidelines must be followed to avoid the physical interaction of these fields with metallic implants and medical electronic devices. 476 refs., 5 figs., 2 tabs.

  14. Detection of Apoptosis and Necrosis in Normal Human Lung Cells Using 1H NMR Spectroscopy

    Science.gov (United States)

    Shih, Chwen-Ming; Ko, Wun-Chang; Yang, Liang-Yo; Lin, Chien-Ju; Wu, Jui-Sheng; Lo, Tsui-Yun; Wang, Shwu-Huey; Chen, Chien-Tsu

    2005-05-01

    This study aimed to detect apoptosis and necrosis in MRC-5, a normal human lung cell line, by using noninvasive proton nuclear magnetic resonance (1H NMR). Live MRC-5 cells were processed first for 1H NMR spectroscopy; subsequently their types and the percentage of cell death were assessed on a flow cytometer. Cadmium (Cd) and mercury (Hg) induced apoptosis and necrosis in MRC-5 cells, respectively, as revealed by phosphatidylserine externalization on a flow cytometer. The spectral intensity ratio of methylene (CH2) resonance (at 1.3 ppm) to methyl (CH3) resonance (at 0.9 ppm) was directly proportional to the percentage of apoptosis and strongly and positively correlated with PI staining after Cd treatment (r2 = 0.9868, P In contrast, this ratio only increased slightly within 2-h Hg treatment, and longer Hg exposure failed to produce further increase. Following 2-h Hg exposure, the spectral intensity of choline resonance (at 3.2 ppm) was abolished, but this phenomenon was absent in Cd-induced apoptosis. These findings together demonstrate that 1H NMR is a novel tool with a quantitative potential to distinguish apoptosis from necrosis as early as the onset of cell death in normal human lung cells.

  15. Bis(pentamethylcyclopentadienyl)ytterbium: An investigation of weak interactions in solution using multinuclear NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, David Joel [Univ. of California, Berkeley, CA (United States)

    1995-07-01

    NMR spectroscopy is ideal for studying weak interactions (formation enthalpy ≤20 kcal/mol) in solution. The metallocene bis(pentamethylcyclopentadienyl)ytterbium, Cp*2Yb, is ideal for this purpose. cis-P2PtH2complexes (P = phosphine) were used to produce slow-exchange Cp*2YbL adducts for NMR study. Reversible formation of (P2PtH)2 complexes from cis-P2PtH2 complexes were also studied, followed by interactions of Cp*2Yb with phosphines, R3PX complexes. A NMR study was done on the interactions of Cp*2Yb with H2, CH4, Xe, CO, silanes, stannanes, C6H6, and toluene.

  16. Rapid Determination of Total Thujone in Absinthe Using 1H NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yulia B. Monakhova

    2011-01-01

    Full Text Available 1H NMR spectroscopy is utilized to quantify total thujone (sum of α- and β-isomers in absinthe. For sample preparation, a simple dilution with buffer is required. Thujone produces a distinct peak of the CH2 group in the cyclopentanone moiety in the 2.13–2.11 ppm range. No overlap with other typical constituents such as anethole or fenchone occurs. The detection limit of 0.3 mg/L is adequate to control the EU maximum limit. The relative standard deviation was 6%, and linearity was observed from 1 to 100 mg/L. Applicability was proven by analysis of 69 authentic absinthes. The correlation between NMR and our previous method consisting of liquid-liquid extraction followed by GC/MS was significant (P<0.0001,R=0.93. The simple and cheap NMR method can be used for rapid screening of absinthes for total thujone content while chromatographic techniques are recommended for more specific (α- and β-thujone isomers analysis if required.

  17. An experimental validation of a Bayesian model for quantification in NMR spectroscopy

    Science.gov (United States)

    Matviychuk, Yevgen; von Harbou, Erik; Holland, Daniel J.

    2017-12-01

    The traditional peak integration method for quantitative analysis in nuclear magnetic resonance (NMR) spectroscopy is inherently limited by its ability to resolve overlapping peaks and is susceptible to noise. The alternative model-based approaches not only extend quantification capabilities to these challenging examples but also provide a means for automation of the entire process of NMR data analysis. In this paper, we present a general model for an NMR signal that, in a principled way, takes into account the effects of chemical shifts, relaxation, lineshape imperfections, phasing, and baseline distortions. We test the model using both simulations and experiments, concentrating on simple spectra with well-resolved peaks where we expect conventional analysis to be effective. Our results of quantifying mixture compositions compare favorably with the established methods. At high SNR (> 40dB), all approaches usually achieve for these test systems an absolute accuracy of at least 0.01mol /mol for the concentrations of all species. Our model-based approach is successful even for SNR < 20dB ; it achieves 0.05 - 0.1mol /mol accuracy in cases where precise phasing is practically impossible due to high levels of noise in the data.

  18. Selectively dispersed isotope labeling for protein structure determination by magic angle spinning NMR

    Energy Technology Data Exchange (ETDEWEB)

    Eddy, Matthew T. [Massachusetts Institute of Technology, Department of Chemistry (United States); Belenky, Marina [Brandeis University, Department of Chemistry (United States); Sivertsen, Astrid C. [Massachusetts Institute of Technology, Francis Bitter Magnet Laboratory (United States); Griffin, Robert G. [Massachusetts Institute of Technology, Department of Chemistry (United States); Herzfeld, Judith, E-mail: herzfeld@brandeis.edu [Brandeis University, Department of Chemistry (United States)

    2013-10-15

    The power of nuclear magnetic resonance spectroscopy derives from its site-specific access to chemical, structural and dynamic information. However, the corresponding multiplicity of interactions can be difficult to tease apart. Complimentary approaches involve spectral editing on the one hand and selective isotope substitution on the other. Here we present a new 'redox' approach to the latter: acetate is chosen as the sole carbon source for the extreme oxidation numbers of its two carbons. Consistent with conventional anabolic pathways for the amino acids, [1-{sup 13}C] acetate does not label {alpha} carbons, labels other aliphatic carbons and the aromatic carbons very selectively, and labels the carboxyl carbons heavily. The benefits of this labeling scheme are exemplified by magic angle spinning spectra of microcrystalline immunoglobulin binding protein G (GB1): the elimination of most J-couplings and one- and two-bond dipolar couplings provides narrow signals and long-range, intra- and inter-residue, recoupling essential for distance constraints. Inverse redox labeling, from [2-{sup 13}C] acetate, is also expected to be useful: although it retains one-bond couplings in the sidechains, the removal of CA-CO coupling in the backbone should improve the resolution of NCACX spectra.

  19. Studies on the MxiH protein in T3SS needles using DNP-enhanced ssNMR spectroscopy.

    Science.gov (United States)

    Fricke, Pascal; Demers, Jean-Philippe; Becker, Stefan; Lange, Adam

    2014-01-13

    Bacterial T3SS needles formed by the protein MxiH are studied using DNP-enhanced ssNMR spectroscopy at 14.1 T (600 MHz). This technique provides spectra of good resolution, allowing us to draw conclusions about the protein dynamics. With the obtained signal enhancement, samples of limited quantity now get within reach of ssNMR studies. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Confirming the 3D Solution Structure of a Short Double-Stranded DNA Sequence Using NMR Spectroscopy

    Science.gov (United States)

    Ruhayel, Rasha A.; Berners-Price, Susan J.

    2010-01-01

    2D [superscript 1]H NOESY NMR spectroscopy is routinely used to give information on the closeness of hydrogen atoms through space. This work is based on a 2D [superscript 1]H NOESY NMR spectrum of a 12 base-pair DNA duplex. This 6-h laboratory workshop aims to provide advanced-level chemistry students with a basic, yet solid, understanding of how…

  1. Secondary structure determination of human. beta. -endorphin by /sup 1/H NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lichtarge, O.; Jardetzky, O.; Li, C.H.

    1987-09-08

    The /sup 1/H NMR spectra of human ..beta..-endorphin indicate that the peptide exists in random-coil form in aqueous solution but becomes helical in mixed solvent. Thermal denaturation NMR experiments show that in water there is no transition between 24 and 75/sup 0/C, while a slow noncooperative thermal unfolding is observed in a 60% methanol-40% water mixed solvent in the same temperature range. These findings are consistent with circular dichroism studies by other workers concluding that ..beta..-endorphin is a random coil in water but that it forms 50% ..cap alpha..-helix or more in mixed solvents. The peptide in the mixed water-methanol solvent was further studied by correlated spectroscopy (COSY) and nuclear Overhauser effect spectroscopy (NOESY) experiments. These allow a complete set of assignments to be made and establish two distinct stretches over which the solvent induces formation of ..cap alpha..-helices: the first occurs between Tyr-1 and Thr-12 and the second between Leu-14 and extending to Lys-28. There is evidence that the latter is capped by a turn occurring between Lys-28 and Glu-31. These helices form at the enkephalin receptor binding site, which is at the amino terminus, and at the morphine receptor binding site, located at the carboxyl terminus. The findings suggest that these two receptors may specifically recognize ..cap alpha..-helices.

  2. Structural analysis of the exopolysaccharide produced by Streptococcus thermophilus ST1 solely by NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Saewen, Elin [Arrhenius Laboratory, Stockholm University, Department of Organic Chemistry (Sweden); Huttunen, Eine; Zhang Xue [University of Helsinki, Department of Food Technology (Finland); Yang Zhennai [Northeast Agricultural Research Center of China, Center of Agro-food Technology (China); Widmalm, Goeran, E-mail: gw@organ.su.s [Arrhenius Laboratory, Stockholm University, Department of Organic Chemistry (Sweden)

    2010-06-15

    The use of lactic acid bacteria in fermentation of milk results in favorable physical and rheological properties due to in situ exopolysaccharide (EPS) production. The EPS from S. thermophilus ST1 produces highly viscous aqueous solutions and its structure has been investigated by NMR spectroscopy. Notably, all aspects of the elucidation of its primary structure including component analysis and absolute configuration of the constituent monosaccharides were carried out by NMR spectroscopy. An array of techniques was utilized including, inter alia, PANSY and NOESY-HSQC TILT experiments. The EPS is composed of hexasaccharide repeating units with the following structure: {yields} 3)[{alpha}-d-Glcp-(1 {yields} 4)]-{beta}-d-Galp-(1 {yields} 4)-{beta}-d-Glcp-(1 {yields} 4)[{beta}-d-Galf-(1 {yields} 6)]-{beta}-d-Glcp-(1 {yields} 6)-{beta}-d-Glcp-(1 {sup {yields}}, in which the residues in square brackets are terminal groups substituting backbone sugar residues that consequently are branch-points in the repeating unit of the polymer. Thus, the EPS consists of a backbone of four sugar residues with two terminal sugar residues making up two side-chains of the repeating unit. The molecular mass of the polymer was determined using translational diffusion experiments which resulted in M{sub w} = 62 kDa, corresponding to 64 repeating units in the EPS.

  3. Characterization of the ground state dynamics of proteorhodopsin by NMR and optical spectroscopies

    International Nuclear Information System (INIS)

    Stehle, Jochen; Scholz, Frank; Löhr, Frank; Reckel, Sina; Roos, Christian; Blum, Michaela; Braun, Markus; Glaubitz, Clemens; Dötsch, Volker; Wachtveitl, Josef; Schwalbe, Harald

    2012-01-01

    We characterized the dynamics of proteorhodopsin (PR), solubilized in diC7PC, a detergent micelle, by liquid-state NMR spectroscopy at T = 323 K. Insights into the dynamics of PR at different time scales could be obtained and dynamic hot spots could be identified at distinct, functionally relevant regions of the protein, including the BC loop, the EF loop, the N-terminal part of helix F and the C-terminal part of helix G. We further characterize the dependence of the photocycle on different detergents (n-Dodecyl β-D-maltoside DDM; 1,2-diheptanoyl-sn-glycero-3-phosphocholine diC7PC) by ultrafast time-resolved UV/VIS spectroscopy. While the photocycle intermediates of PR in diC7PC and DDM exhibit highly similar spectral characteristics, significant changes in the population of these intermediates are observed. In-situ NMR experiments have been applied to characterize structural changes during the photocycle. Light-induced chemical shift changes detected during the photocycle in diC7PC are very small, in line with the changes in the population of intermediates in the photocycle of proteorhodopsin in diC7PC, where the late O-intermediate populated in DDM is missing and the population is shifted towards an equilibrium of intermediates states (M, N, O) without accumulation of a single populated intermediate.

  4. Structural analysis of the exopolysaccharide produced by Streptococcus thermophilus ST1 solely by NMR spectroscopy

    International Nuclear Information System (INIS)

    Saewen, Elin; Huttunen, Eine; Zhang Xue; Yang Zhennai; Widmalm, Goeran

    2010-01-01

    The use of lactic acid bacteria in fermentation of milk results in favorable physical and rheological properties due to in situ exopolysaccharide (EPS) production. The EPS from S. thermophilus ST1 produces highly viscous aqueous solutions and its structure has been investigated by NMR spectroscopy. Notably, all aspects of the elucidation of its primary structure including component analysis and absolute configuration of the constituent monosaccharides were carried out by NMR spectroscopy. An array of techniques was utilized including, inter alia, PANSY and NOESY-HSQC TILT experiments. The EPS is composed of hexasaccharide repeating units with the following structure: → 3)[α-d-Glcp-(1 → 4)]-β-d-Galp-(1 → 4)-β-d-Glcp-(1 → 4)[β-d-Galf-(1 → 6)]-β-d-Glcp-(1 → 6)-β-d-Glcp-(1 → , in which the residues in square brackets are terminal groups substituting backbone sugar residues that consequently are branch-points in the repeating unit of the polymer. Thus, the EPS consists of a backbone of four sugar residues with two terminal sugar residues making up two side-chains of the repeating unit. The molecular mass of the polymer was determined using translational diffusion experiments which resulted in M w = 62 kDa, corresponding to 64 repeating units in the EPS.

  5. Potential of NMR spectroscopy for the study of human amniotic fluid.

    Science.gov (United States)

    Graça, Gonçalo; Duarte, Iola F; Goodfellow, Brian J; Barros, António S; Carreira, Isabel M; Couceiro, Ana Bela; Spraul, Manfred; Gil, Ana M

    2007-11-01

    1D and 2D 800 MHz high-resolution nuclear magnetic resonance spectroscopy of human amniotic fluid (HAF) enabled the identification of approximately 50 metabolites. In addition, liquid chromatography-NMR and diffusion ordered spectroscopy (DOSY) allowed signal overlap to be reduced and the characterization of higher molecular weight (Mw) components, respectively. Indeed, the DOSY spectrum of a Mw >10 kDa HAF fraction enabled three protein families, differing in average Mw, to be detected and may therefore be of potential value in the study of disorder-related variations in HAF protein profiles. The effects of freeze-drying, storage at -20 or -70 degrees C, and freeze-thawing cycles on HAF compositional stability were investigated, as well as stability at room temperature (to account for overnight data acquisition runs). These data are the basis for establishing statistically validated correlations between HAF NMR data and any physiological disorders of the fetus/mother. Freeze-drying caused signal loss for urea, ethanol, and compounds resonating at 2.22 and 1.17 ppm. Storage at -70 degrees C or lower is recommended since only minor compositional changes were observed, affecting mainly acetate and pyruvate. Freeze-thaw cycles did not cause significant compositional changes, and room-temperature stability studies indicated a 4-5 h maximum period of handling/acquisition time to ensure HAF stability.

  6. Hydration of some urine components measured by H-NMR spectroscopy

    International Nuclear Information System (INIS)

    Nakaya, Shigeyuki; Tanaka, Yasuo; Yoshioka, Yoshichika; Yoshida, Yuki; Yasuda, Naoki

    1989-01-01

    High resolution H-NMR spectroscopy was used to estimate the degree of hydration of some of the human urine components (NaCl, KCl, urea) in aqueous solutions. The NMR relaxation time of water proton was measured with graded concentrations of each components up to the limit of its water solubility (0.1-5M for NaCl, 0.1-4M for KCl, 0.1-10M for urea) and used as a parameter of hydration. To standardize the experimental conditions all tested urine components were dissolved in 90% pure water/10% heavy water mixture, and placed in sample tubes in a volume of 0.2 ml (in the case of 5 mm diameter tube) or 5 ml (in the case of 20 mm diameter tube). Fourier-transferred spectra obtained with above urine components showed a single peak of water proton at 4.72±0.01 ppm. The NMR relaxation times (T 1 , T 2 ) of this peak were measured by the inversion recovery (T 1 ) and CPMG (Carr-Purcell-Meiboom-Gill) method (T 2 ). The hydration number (h mol/mol) was then calculated according to the Zimmerman's formula. At their highest concentrations, hydration numbers for urea, KCl and NaCl were 3, 5, and 6 when calculated from T 1 and 3, 5, and 7 when calculated from T 2 respectively. These results are in agreement with previous data obtained using various physicochemical methods (e.g. electromotive force, thermodynamics), but not with those reported in other NMR studies. (author)

  7. pKa determination by ¹H NMR spectroscopy - an old methodology revisited.

    Science.gov (United States)

    Bezençon, Jacqueline; Wittwer, Matthias B; Cutting, Brian; Smieško, Martin; Wagner, Bjoern; Kansy, Manfred; Ernst, Beat

    2014-05-01

    pKa values of acids and protonated bases have an essential impact on organic synthesis, medicinal chemistry, and material and food sciences. In drug discovery and development, they are of utmost importance for the prediction of pharmacokinetic and pharmacodynamic properties. To date, various methods for the determination of pKa values are available, including UV-spectroscopic, potentiometric, and capillary electrophoretic techniques. An additional option is provided by nuclear magnetic resonance (NMR) spectroscopy. The underlying principle is the alteration of chemical shifts of NMR-active nuclei (e.g., (13)C and (1)H) depending on the protonation state of adjacent acidic or basic sites. When these chemical shifts are plotted against the pH, the inflection point of the resulting sigmoidal curve defines the pKa value. Although pKa determinations by (1)H NMR spectroscopy are reported for numerous cases, the potential of this approach is not yet fully evaluated. We therefore revisited this method with a diverse set of test compounds covering a broad range of pKa values (pKa 0.9-13.8) and made a comparison with four commonly used approaches. The methodology revealed excellent correlations (R(2)=0.99 and 0.97) with electropotentiometric and UV spectroscopic methods. Moreover, the comparison with in silico results (Epik and Marvin) also showed high correlations (R(2)=0.92 and 0.94), further confirming the reliability and utility of this approach. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Single-Crystalline cooperite (PtS): Crystal-Chemical characterization, ESR spectroscopy, and {sup 195}Pt NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rozhdestvina, V. I., E-mail: veronika@ascnet.ru; Ivanov, A. V.; Zaremba, M. A. [Far East Division, Russian Academy of Sciences, Institute of Geology and Nature Management (Russian Federation); Antsutkin, O. N.; Forsling, W. [Lulea University of Technology (Sweden)

    2008-05-15

    Single-crystalline cooperite (PtS) with a nearly stoichiometric composition was characterized in detail by X-ray diffraction, electron-probe X-ray microanalysis, and high-resolution scanning electron microscopy. For the first time it was demonstrated that {sup 195}Pt static and MAS NMR spectroscopy can be used for studying natural platinum minerals. The {sup 195}Pt chemical-shift tensor of cooperite was found to be consistent with the axial symmetry and is characterized by the following principal values: {delta}{sub xx} = -5920 ppm, {delta}{sub yy} = -3734 ppm, {delta}{sub zz} = +4023 ppm, and {delta}{sub iso} = -1850 ppm. According to the ESR data, the samples of cooperite contain copper(II), which is adsorbed on the surface during the layer-by-layer crystal growth and is not involved in the crystal lattice.

  9. Muon spin spectroscopy of ferrocene: characterization of muoniated ferrocenyl radicals.

    Science.gov (United States)

    McKenzie, Iain

    2014-06-14

    Radicals formed by the reaction of muonium (Mu), a light isotope of hydrogen, with ferrocene and ferrocene-d10 have been studied with the avoided level crossing muon spin resonance (ALC-μSR) and longitudinal field muon spin relaxation (LF-μSR) techniques between 10 and 100 K. A single type of radical was observed in each compound and the muon hyperfine coupling constants (hfcc) and the muon spin relaxation rates were measured as a function of temperature. A previous report concerning the observation of Mu adducts of ferrocene (U. A. Jayasooriya et al. Chem. - Eur. J., 2007, 13, 2266-2276) appears to be incorrect. DFT calculations were performed to aid in the assignment of the ALC-μSR spectra. A tentative assignment is that the observed radicals were formed by Mu addition to the exterior of the cyclopentadienyl rings and that the structures are distorted due to interactions with neighbouring molecules. The temperature dependence of the muon hfcc can be explained assuming the population of two levels with different muon hfccs separated by 1.4 ± 0.1 kJ mol(-1). The temperature dependence of the width and amplitude of the Δ1 resonance and the muon spin relaxation rate suggests that the electron spin relaxation rate increase with temperature, but the relaxation mechanism is unknown.

  10. Radio frequency scanning tunneling spectroscopy for single-molecule spin resonance.

    Science.gov (United States)

    Müllegger, Stefan; Tebi, Stefano; Das, Amal K; Schöfberger, Wolfgang; Faschinger, Felix; Koch, Reinhold

    2014-09-26

    We probe nuclear and electron spins in a single molecule even beyond the electromagnetic dipole selection rules, at readily accessible magnetic fields (few mT) and temperatures (5 K) by resonant radio-frequency current from a scanning tunneling microscope. We achieve subnanometer spatial resolution combined with single-spin sensitivity, representing a 10 orders of magnitude improvement compared to existing magnetic resonance techniques. We demonstrate the successful resonant spectroscopy of the complete manifold of nuclear and electronic magnetic transitions of up to ΔI(z)=±3 and ΔJ(z)=±12 of single quantum spins in a single molecule. Our method of resonant radio-frequency scanning tunneling spectroscopy offers, atom-by-atom, unprecedented analytical power and spin control with an impact on diverse fields of nanoscience and nanotechnology.

  11. Spin-echo based diagonal peak suppression in solid-state MAS NMR homonuclear chemical shift correlation spectra

    Science.gov (United States)

    Wang, Kaiyu; Zhang, Zhiyong; Ding, Xiaoyan; Tian, Fang; Huang, Yuqing; Chen, Zhong; Fu, Riqiang

    2018-02-01

    The feasibility of using the spin-echo based diagonal peak suppression method in solid-state MAS NMR homonuclear chemical shift correlation experiments is demonstrated. A complete phase cycling is designed in such a way that in the indirect dimension only the spin diffused signals are evolved, while all signals not involved in polarization transfer are refocused for cancellation. A data processing procedure is further introduced to reconstruct this acquired spectrum into a conventional two-dimensional homonuclear chemical shift correlation spectrum. A uniformly 13C, 15N labeled Fmoc-valine sample and the transmembrane domain of a human protein, LR11 (sorLA), in native Escherichia coli membranes have been used to illustrate the capability of the proposed method in comparison with standard 13C-13C chemical shift correlation experiments.

  12. Chemically Methylated and Reduced Pectins: Preparation and Characterisation by 1H-NMR Spectroscopy, Enzymatic Degradation and Gelling Properties

    DEFF Research Database (Denmark)

    Rosenbohm, Christoph; Lundt, Inge; Christensen, T.M.I.E.

    2003-01-01

    with lower DM. A simple method for determination of DM by 1H-NMR spectroscopy is presented. New modified pectins have been prepared by treatment of pectins having different DM’s with NaBH4 to reduce selectively the methyl esters to primary alcohols in the presence of free acids. The degree of reduction (DR......) and the DM of the remaining carboxylic acids could likewise be determined by 1H-NMR spectroscopy. The new reduced pectins can be tolerated by the pectin degrading enzymes polygalacturonase PGI and PGII as well as by pectin lyase, all from Aspergillus niger, but the enzymes exhibit lower specific activities...

  13. Uses of 1H NMR and 13C NMR spectroscopy in studies of phenylenedioxydiacetamides complexation with the cations of calcium and potassium in solution

    International Nuclear Information System (INIS)

    Lin, W.Q.; Souza, M.C.B.V. de; Alt, H.G.

    1988-01-01

    The complexation abilities and the coordination sites of 12 derivatives using infrared, 1 HNMR and 13 C NMR spectroscopy are analyzed. The spectroscopic results indicate that only the 1,2-phenylenedioxydiacetamides are suitable ligands; the 1,3 derivatives did not react. These ionophors 1-8 represent fourdentale chelating ligands where all four oxygen atmos are involved in bonds to the metal. Independent from its charge one cations is coordinate by two ionophors. (M.J.C.) [pt

  14. Photoexcited Muon Spin Spectroscopy: A New Method for Measuring Excess Carrier Lifetime in Bulk Silicon.

    Science.gov (United States)

    Yokoyama, K; Lord, J S; Miao, J; Murahari, P; Drew, A J

    2017-12-01

    We have measured excess carrier lifetime in silicon using photoexcited muon spin spectroscopy. Positive muons implanted deep in a wafer can interact with the optically injected excess carriers and directly probe the bulk carrier lifetime while minimizing the effect from surface recombination. The method is based on the relaxation rate of muon spin asymmetry, which depends on the excess carrier density. The underlying microscopic mechanism has been understood by simulating the four-state muonium model in Si under illumination. We apply the technique to different injection levels and temperatures, and demonstrate its ability for injection- and temperature-dependent lifetime spectroscopy.

  15. NMR spin relaxation in proteins: The patterns of motion that dissipate power to the bath

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, Yury E., E-mail: eva.meirovitch@biu.ac.il, E-mail: yuryeshapiro@gmail.com; Meirovitch, Eva, E-mail: eva.meirovitch@biu.ac.il, E-mail: yuryeshapiro@gmail.com [The Mina and Everard Goodman Faculty of Life Sciences, Bar-Ilan University, Ramat-Gan 52900-02 (Israel)

    2014-04-21

    We developed in recent years the two-body coupled-rotator slowly relaxing local structure (SRLS) approach for the analysis of NMR relaxation in proteins. The two bodies/rotators are the protein (diffusion tensor D{sub 1}) and the spin-bearing probe, e.g., the {sup 15}N−{sup 1}H bond (diffusion tensor, D{sub 2}), coupled by a local potential (u). A Smoluchowski equation is solved to yield the generic time correlation functions (TCFs), which are sums of weighted exponentials (eigenmodes). By Fourier transformation one obtains the generic spectral density functions (SDFs) which underlie the experimental relaxation parameters. The typical paradigm is to characterize structural dynamics in terms of the best-fit values of D{sub 1}, D{sub 2}, and u. Additional approaches we pursued employ the SRLS TCFs, SDFs, or eigenmodes as descriptors. In this study we develop yet another perspective. We consider the SDF as function of the angular velocity associated with the fluctuating fields underlying NMR relaxation. A parameter called j-fraction, which represents the relative contribution of eigenmode, i, to a given value of the SDF function at a specific frequency, ω, is defined. j-fraction profiles of the dominant eigenmodes are derived for 0 ≤ ω ≤ 10{sup 12} rad/s. They reveal which patterns of motion actuate power dissipation at given ω-values, what are their rates, and what is their relative contribution. Simulations are carried out to determine the effect of timescale separation, D{sub 1}/D{sub 2}, axial potential strength, and local diffusion axiality. For D{sub 1}/D{sub 2} ≤ 0.01 and strong local potential of 15 k{sub B}T, power is dissipated by global diffusion, renormalized (by the strong potential) local diffusion, and probe diffusion on the surface of a cone (to be called cone diffusion). For D{sub 1}/D{sub 2} = 0.1, power is dissipated by mixed eigenmodes largely of a global-diffusion-type or cone-diffusion-type, and a nearly bare renormalized

  16. Muon spin rotation and other microscopic probes of spin-glass dynamics

    International Nuclear Information System (INIS)

    MacLaughlin, D.E.

    1980-01-01

    A number of different microscopic probe techniques have been employed to investigate the onset of the spin-glass state in dilute magnetic alloys. Among these are Moessbauer-effect spectroscopy, neutron scattering, ESR of the impurity spins, host NMR and, most recently, muon spin rotation and depolarization. Spin probes yield information on the microscopic static and dynamic behavior of the impurity spins, and give insight into both the spin freezing process and the nature of low-lying excitations in the ordered state. Microscopic probe experiments in spin glasses are surveyed, and the unique advantages of muon studies are emphasized

  17. Structure, magnetization, and NMR studies of the spin-glass compound (LixV1-x)3BO5 ( x≈0.40 and 0.33)

    Science.gov (United States)

    Zong, X.; Niazi, A.; Borsa, F.; Ma, X.; Johnston, D. C.

    2007-08-01

    Structural and magnetic properties of (LixV1-x)3BO5 powders (x=0.33) and single crystals (x=0.40) were studied by x-ray diffraction, magnetization, and NMR measurements. Both powder and single crystal x-ray diffraction data are consistent with the previously reported structure of the system. Magnetization measurements show an overall antiferromagnetic interaction among vanadium spins and reveal a transition into a spin glass state at a sample and magnetic field dependent temperature below ˜10K . The high temperature (T>20K) susceptibility is analyzed using a linear spin trimer model suggested in the literature but such a model is found to be insufficient to explain the data. Li7 and B11 NMR studies indicate an inhomogeneous dynamics close to the zero-field spin-glass transition temperature. The distribution of electronic spin relaxation times is derived using a recently proposed method and the broad temperature-dependent distribution obtained gives a consistent description of the NMR results. The temperature dependence of the distribution indicates a strong slowing down of the local moment spin dynamics as the system cools toward the zero-field spin-glass transition temperature even in the presence of a strong applied magnetic field up to 4.7T .

  18. Effective Floquet Hamiltonian for spin I = 1 in magic angle spinning ...

    Indian Academy of Sciences (India)

    WINTEC

    Floquet Hamiltonians; contact transformations in NMR; Spin-1 MAS NMR; effective Ham- iltonians. 1. Introduction. Solid state nuclear magnetic resonance spectroscopy is an important technique to study structures, dyna- mics and electric charge distribution around nuclei in solids. It is also more difficult to perform and ana-.

  19. Structural Elucidation of Metabolites of Synthetic Cannabinoid UR-144 by Cunninghamella elegans Using Nuclear Magnetic Resonance (NMR) Spectroscopy.

    Science.gov (United States)

    Watanabe, Shimpei; Kuzhiumparambil, Unnikrishnan; Fu, Shanlin

    2018-03-08

    The number of new psychoactive substances keeps on rising despite the controlling efforts by law enforcement. Although metabolism of the newly emerging drugs is continuously studied to keep up with the new additions, the exact structures of the metabolites are often not identified due to the insufficient sample quantities for techniques such as nuclear magnetic resonance (NMR) spectroscopy. The aim of the study was to characterise several metabolites of the synthetic cannabinoid (1-pentyl-1H-indol-3-yl) (2,2,3,3-tetramethylcyclopropyl) methanone (UR-144) by NMR spectroscopy after the incubation with the fungus Cunninghamella elegans. UR-144 was incubated with C. elegans for 72 h, and the resulting metabolites were chromatographically separated. Six fractions were collected and analysed by NMR spectroscopy. UR-144 was also incubated with human liver microsomes (HLM), and the liquid chromatography-high resolution mass spectrometry analysis was performed on the HLM metabolites with the characterised fungal metabolites as reference standards. Ten metabolites were characterised by NMR analysis including dihydroxy metabolites, carboxy and hydroxy metabolites, a hydroxy and ketone metabolite, and a carboxy and ketone metabolite. Of these metabolites, dihydroxy metabolite, carboxy and hydroxy metabolites, and a hydroxy and ketone metabolite were identified in HLM incubation. The results indicate that the fungus is capable of producing human-relevant metabolites including the exact isomers. The capacity of the fungus C. elegans to allow for NMR structural characterisation by enabling production of large amounts of metabolites makes it an ideal model to complement metabolism studies.

  20. Multiphoton electronic-spin generation and transmission spectroscopy in n-type GaAs

    Energy Technology Data Exchange (ETDEWEB)

    Idrish Miah, M., E-mail: m.miah@griffith.edu.a [Department of Physics, University of Chittagong, Chittagong 4331 (Bangladesh)

    2011-01-17

    Multiphoton electronic-spin generation in semiconductors was investigated using differential transmission spectroscopy. The generation of the electronic spins in the semiconductor samples were achieved by multiphoton pumping with circularly polarized light beam and was probed by the spin-resolved transmission of the samples. The electronic spin-polarization of conduction band was estimated and was found to depend on the delay of the probe beam, temperature as well as on the multiphoton pumping energy. The temperature dependence showed a decrease of the spin-polarization with increasing temperature. The electronic spin-polarization was found to depolarize rapidly for multiphoton pumping energy larger than the energy gap of the split-off band to the conduction band. The results were compared with those obtained in one-photon pumping, which shows that an enhancement of the electronic spin-polarization was achieved in multiphoton pumping. The findings resulting from this investigation might have potential applications in opto-spintronics, where the generation of highly polarized electronic spins is required.

  1. Multiphoton electronic-spin generation and transmission spectroscopy in n-type GaAs

    International Nuclear Information System (INIS)

    Idrish Miah, M.

    2011-01-01

    Multiphoton electronic-spin generation in semiconductors was investigated using differential transmission spectroscopy. The generation of the electronic spins in the semiconductor samples were achieved by multiphoton pumping with circularly polarized light beam and was probed by the spin-resolved transmission of the samples. The electronic spin-polarization of conduction band was estimated and was found to depend on the delay of the probe beam, temperature as well as on the multiphoton pumping energy. The temperature dependence showed a decrease of the spin-polarization with increasing temperature. The electronic spin-polarization was found to depolarize rapidly for multiphoton pumping energy larger than the energy gap of the split-off band to the conduction band. The results were compared with those obtained in one-photon pumping, which shows that an enhancement of the electronic spin-polarization was achieved in multiphoton pumping. The findings resulting from this investigation might have potential applications in opto-spintronics, where the generation of highly polarized electronic spins is required.

  2. Localized proton NMR spectroscopy using stimulated echoes: applications to human skeletal muscle in vivo.

    Science.gov (United States)

    Bruhn, H; Frahm, J; Gyngell, M L; Merboldt, K D; Hänicke, W; Sauter, R

    1991-01-01

    Localized proton NMR spectroscopy using stimulated echoes (STEAM) has been used to study metabolites in different proximal skeletal muscles of normal volunteers at rest. Single scan water-suppressed proton NMR spectra obtained at 1.5 and 2.0 T (Siemens Magnetom) from a 64-ml volume-of-interest (VOI) yield resonances due to triglycerides, phosphocreatine plus a minor contribution from creatine, and betaines comprising carnitine and choline-containing compounds. The observation of the pH-dependent resonances of carnosine required multiple acquisitions and echo times as short as 20 ms. T1 and T2 relaxation times of muscle metabolites were obtained by varying the repetition time and echo time of the STEAM sequence, respectively. Although rather long T2 values such as 180 ms for (phospho-) creatine correspond to natural resonance linewidths of only 2 Hz, the observed linewidths of typically 10-12 Hz are entirely determined by the short T2 relaxation times (25-30 ms) of the water protons used for shimming. The spectroscopic results from 24 muscle studies on 17 young male volunteers show remarkable intra- and interindividual differences in the absolute signal intensities of mobile lipids. Further metabolic variations were observed for the relative concentrations of betaines (by a factor of 2) and carnosine (by a factor of 3) when total creatine is assumed to be constant.

  3. In vivo 31P-NMR spectroscopy of chronically stimulated canine skeletal muscle

    International Nuclear Information System (INIS)

    Clark, B.J. III; McCully, A.K.; Subramanian, H.V.; Hammond, R.L.; Salmons, S.; Chance, B.; Stephenson, L.W.

    1988-01-01

    Chronic stimulation converts skeletal muscle of mixed fiber type to a uniform muscle made up of type I, fatigue-resistant fibers. Here, the bioenergetic correlates of fatigue resistance in conditioned canine latissimus dorsi are assessed with in vivo phosphorus-31 nuclear magnetic resonance ( 31 P-NMR) spectroscopy. After chronic electrical stimulation, five dogs underwent 31 P-NMR spectroscopic and isometric tension measurements on conditioned and contralateral control muscle during stimulation for 200, 300, 500, and 800 ms of an 1,100-ms duty cycle. With stimulation, phosphocreatine (PCr) fell proportional to the degree of stimulation in both conditioned and control muscle but fell significantly less in conditioned muscle at all the least intense stimulation period (200 ms). Isometric tension, expressed as a tension time index per gram muscle, was significantly greater in the conditioned muscle at the two longest stimulation periods. The overall small change in PCr and the lack of a plateau in tension observed in the conditioned muscle are similar to that seen in cardiac muscle during increased energy demand. This study indicates that the conditioned muscle's markedly enhanced resistance to fatigue is in part the result of its increased capacity for oxidative phosphorylation

  4. Impurity profiling of carbocisteine by HPLC-CAD, qNMR and UV/vis spectroscopy.

    Science.gov (United States)

    Wahl, Oliver; Holzgrabe, Ulrike

    2014-07-01

    For the impurity profiling of the mucolytic and anti-inflammatory drug carbocisteine a high performance liquid chromatographic (HPLC) method using corona charged aerosol detection (CAD) was developed and fully validated following the ICH guideline Q2(R1). The response was linear (R²>0.995) over a small concentration range (0.05-0.25 or 0.10-0.60% respectively) and a detection limit of at least 0.03% was registered. The separation was achieved on a mixed mode column combining hydrophobic C18 and strong cation exchange retention mechanisms using a mass spectrometer compatible volatile mobile phase consisting of trifluoroacetic acid 10 mM and acetonitrile 12% (V/V). Impurities, not assessable by HPLC-CAD such as the volatile chloroacetic acid and the unstable cysteine, were determined by quantitative NMR (qNMR) with maleic acid as internal standard and UV/vis spectroscopy after reaction with Ellman's reagent, respectively. Six batches of three different manufacturers were tested by means of those methods. The purity varied from below 99.0 to higher than 99.8 per cent. The major impurities of all batches were the starting material cystine and N,S-dicarboxymethylcysteine being a synthesis by-product. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Assessment of metabolic phenotypic variability in children’s urine using 1H NMR spectroscopy

    Science.gov (United States)

    Maitre, Léa; Lau, Chung-Ho E.; Vizcaino, Esther; Robinson, Oliver; Casas, Maribel; Siskos, Alexandros P.; Want, Elizabeth J.; Athersuch, Toby; Slama, Remy; Vrijheid, Martine; Keun, Hector C.; Coen, Muireann

    2017-04-01

    The application of metabolic phenotyping in clinical and epidemiological studies is limited by a poor understanding of inter-individual, intra-individual and temporal variability in metabolic phenotypes. Using 1H NMR spectroscopy we characterised short-term variability in urinary metabolites measured from 20 children aged 8-9 years old. Daily spot morning, night-time and pooled (50:50 morning and night-time) urine samples across six days (18 samples per child) were analysed, and 44 metabolites quantified. Intraclass correlation coefficients (ICC) and mixed effect models were applied to assess the reproducibility and biological variance of metabolic phenotypes. Excellent analytical reproducibility and precision was demonstrated for the 1H NMR spectroscopic platform (median CV 7.2%). Pooled samples captured the best inter-individual variability with an ICC of 0.40 (median). Trimethylamine, N-acetyl neuraminic acid, 3-hydroxyisobutyrate, 3-hydroxybutyrate/3-aminoisobutyrate, tyrosine, valine and 3-hydroxyisovalerate exhibited the highest stability with over 50% of variance specific to the child. The pooled sample was shown to capture the most inter-individual variance in the metabolic phenotype, which is of importance for molecular epidemiology study design. A substantial proportion of the variation in the urinary metabolome of children is specific to the individual, underlining the potential of such data to inform clinical and exposome studies conducted early in life.

  6. Metabolic characterization of Withania somnifera from different regions of India using NMR spectroscopy.

    Science.gov (United States)

    Namdeo, Ajay G; Sharma, Ajay; Yadav, Kavita N; Gawande, Rupali; Mahadik, Kakasaheb R; Lopez-Gresa, Maria Pilar; Kim, Hye Kyong; Choi, Young Hae; Verpoorte, Robert

    2011-11-01

    Withania somnifera (L.) Dun. (Solanaceae), known as Indian ginseng, is one of the most popular medicinal plants in India. Considering the importance and common use of this plant, it is necessary to investigate its holistic metabolite profile. However, with existing analytical methods which are based on TLC and HPLC‑UV (or MS), it is difficult to obtain information of the whole range of compounds appropriately. In this study, the metabolic characterization of Withania somnifera leaves, stems, and roots collected in six different regions in India was performed using ¹H NMR spectroscopy followed by principal component analysis (PCA) and hierarchical clustering analysis (HCA). Of the parts of Withania somnifera analyzed in this study, the leaf was found to have the widest range of metabolites, including amino acids, flavonoids, lipids, organic acids, phenylpropanoids, and sugars, as well as the main secondary metabolites of the plant, withanolides. The ¹H NMR spectra revealed the presence of two groups of withanolides: 4-OH and 5,6-epoxy withanolides (withaferin A-like steroids) and 5- OH and 6,7-epoxy withanolides (withanolides Alike steroids). The ratio of these two withanolides was found to be a key discriminating feature of Withania somnifera leaf samples from different origins. © Georg Thieme Verlag KG Stuttgart · New York.

  7. Determination of rate constants of N-alkylation of primary amines by 1H NMR spectroscopy.

    Science.gov (United States)

    Li, Chenghong

    2013-09-05

    Macromolecules containing N-diazeniumdiolates of secondary amines are proposed scaffolds for controlled nitrogen oxide (NO) release medical applications. Preparation of these compounds often involves converting primary amine groups to secondary amine groups through N-alkylation. However, N-alkylation results in not only secondary amines but tertiary amines as well. Only N-diazeniumdiolates of secondary amines are suitable for controlled NO release; therefore, the yield of secondary amines is crucial to the total NO load of the carrier. In this paper, (1)H NMR spectroscopy was used to estimate the rate constants for formation of secondary amine (k1) and tertiary amine (k2) for alkylation reagents such as propylene oxide (PO), methyl acrylate (MA), and acrylonitrile (ACN). At room temperature, the ratio of k2/k1 for the three reactions was found to be around 0.50, 0.026, and 0.0072.

  8. Spatial selectivity of the surface coils used in-vivo in NMR spectroscopy

    International Nuclear Information System (INIS)

    Laval, M.; Decorps, M.; Chaillout, J.J.; Confort, S.

    1984-05-01

    Surface coils are being to be of current use in ''in vivo'' NMR spectroscopy. This kind of resonator yields indeed a very good signal to noise ratio when applied to the examination of limited and superficial regions of large organs. But to allow the biological analysis of detected signals, knowledge of the spatial response is necessary. Radiofrequency isofield surfaces, associated with sensitivity curve computed along the coil axis, give a good idea of analysed volume by surface coils. On the other hand, saturation sequence previously applied to excitation pulse is suggested to make the spatial response of surface coil independant of T 1 relaxation time constant of different chemical species within the sample. A short survey on chemical shift imaging either with surface coils or with uniform radiofrequency field resonator is presented in conclusion [fr

  9. Preparation, characterization, and NMR spectroscopy of encapsulated proteins dissolved in low viscosity fluids

    International Nuclear Information System (INIS)

    Babu, Charles R.; Flynn, Peter F.; Wand, A. Joshua

    2003-01-01

    Encapsulating a protein in a reverse micelle and dissolving it in a low-viscosity solvent can lower the rotational correlation time of a protein and thereby provides a novel strategy for studying proteins in a variety of contexts. The preparation of the sample is a key element in this approach and is guided by a number of competing parameters. Here we examine the applicability of several strategies for the preparation and characterization of encapsulated proteins dissolved in low viscosity fluids that are suitable for high performance NMR spectroscopy. Ubiquitin is used as a model system to explore various issues such as the homogeneity of the encapsulation, characterization of the hydrodynamic performance of reverse micelles containing protein molecules, and the effective pH of the water environment of the reverse micelle

  10. Simultaneous 31P NMR spectroscopy and EMG in exercising and recovering human skeletal muscle: technical aspects

    DEFF Research Database (Denmark)

    Vestergaard-Poulsen, P; Thomsen, C; Sinkjaer, T

    1994-01-01

    The bioenergetics of human skeletal muscle can be studied by 31P NMR spectroscopy (31P-MRS) and by surface electromyography (SEMG). Simultaneous 31P-MRS and SEMG permit accurate and noninvasive studies of the correlation between metabolic and electrical changes in exercising and recovering human...... skeletal muscle, a relationship that is still poorly understood. This study describes the optimization of skeletal muscle 31P-MRS in a whole-body magnet, involving surface coil design, utilization of adiabatic radio frequency pulses and advanced time-domain fitting, to the technical design of SEMG....... A nonmagnetic ergometer was used for ankle dorsiflexions that activated only the anterior tibial muscle as verified by post exercise imaging. The coil design and the adiabatic sech/tanh pulse improved sensitivity by 45% and 56% respectively, compared with standard techniques. Simultaneous electromyographic...

  11. Structures of glycans bound to receptors from saturation transfer difference (STD) NMR spectroscopy: quantitative analysis by using CORCEMA-ST.

    Science.gov (United States)

    Enríquez-Navas, Pedro M; Guzzi, Cinzia; Muñoz-García, Juan C; Nieto, Pedro M; Angulo, Jesús

    2015-01-01

    Glycan-receptor interactions are of fundamental relevance for a large number of biological processes, and their kinetics properties (medium/weak binding affinities) make them appropriated to be studied by ligand observed NMR techniques, among which saturation transfer difference (STD) NMR spectroscopy has been shown to be a very robust and powerful approach. The quantitative analysis of the results from a STD NMR study of a glycan-receptor interaction is essential to be able to translate the resulting spectral intensities into a 3D molecular model of the complex. This chapter describes how to carry out such a quantitative analysis by means of the Complete Relaxation and Conformational Exchange Matrix Approach for STD NMR (CORCEMA-ST), in general terms, and an example of a previous work on an antibody-glycan interaction is also shown.

  12. Predicting Fuel Ignition Quality Using 1H NMR Spectroscopy and Multiple Linear Regression

    KAUST Repository

    Abdul Jameel, Abdul Gani

    2016-09-14

    An improved model for the prediction of ignition quality of hydrocarbon fuels has been developed using 1H nuclear magnetic resonance (NMR) spectroscopy and multiple linear regression (MLR) modeling. Cetane number (CN) and derived cetane number (DCN) of 71 pure hydrocarbons and 54 hydrocarbon blends were utilized as a data set to study the relationship between ignition quality and molecular structure. CN and DCN are functional equivalents and collectively referred to as D/CN, herein. The effect of molecular weight and weight percent of structural parameters such as paraffinic CH3 groups, paraffinic CH2 groups, paraffinic CH groups, olefinic CH–CH2 groups, naphthenic CH–CH2 groups, and aromatic C–CH groups on D/CN was studied. A particular emphasis on the effect of branching (i.e., methyl substitution) on the D/CN was studied, and a new parameter denoted as the branching index (BI) was introduced to quantify this effect. A new formula was developed to calculate the BI of hydrocarbon fuels using 1H NMR spectroscopy. Multiple linear regression (MLR) modeling was used to develop an empirical relationship between D/CN and the eight structural parameters. This was then used to predict the DCN of many hydrocarbon fuels. The developed model has a high correlation coefficient (R2 = 0.97) and was validated with experimentally measured DCN of twenty-two real fuel mixtures (e.g., gasolines and diesels) and fifty-nine blends of known composition, and the predicted values matched well with the experimental data.

  13. Novel solution conformation of DNA observed in d(GAATTCGAATTC) by two-dimensional NMR spectroscopy

    International Nuclear Information System (INIS)

    Chary, K.V.R.; Hosur, R.V.; Govil, G.; Zu-kun, T.; Miles, H.T.

    1987-01-01

    Resonance assignments of nonexchangeable base and sugar protons of the self-complementary dodecanucleotide d(GAATTCGAATTC) have been obtained by using the two-dimensional Fourier transform NMR methods correlated spectroscopy and nuclear Overhauser effect spectroscopy. Conformational details about the sugar pucker, the glycosidic dihedral angle, and the overall secondary structure of the molecule has been derived from the relative intensities of cross peaks in the two-dimensional NMR spectra in aqueous solution. It is observed that d(GAATTCGAATTC) assumes a novel double-helical structure. The solution conformations of the two complementary strands are identical, unlike those observed in a related sequence in the solid state. Most of the five-membered sugar rings adopt an unusual O1'-endo geometry. All the glycosidic dihedral angles are in the anti domain. The AATT segments A2-T5 and A8-T11 show better stacking compared to the rest of the molecule. These features fit into a right-handed DNA model for the above two segments, with the sugar geometries different from the conventional ones. There are important structural variations in the central TCG portion, which is known to show preferences for DNase I activity, and between G1-A2 and G7-A8, which are cleavage points in the EcoRI recognition sequence. The sugar puckers for G1 and G7 are significantly different from the rest of the molecule. Further, in the three segments mentioned above, the sugar phosphate geometry is such that the distances between protons on adjacent nucleotides are much larger than those expected for a right-handed DNA. The authors suggest that such crevices in the DNA structure may act as hot points in initiation of protein recognition

  14. Syntheses, crystal structures, NMR spectroscopy, and vibrational spectroscopy of Sr(PO{sub 3}F).H{sub 2}O and Sr(PO{sub 3}F)

    Energy Technology Data Exchange (ETDEWEB)

    Jantz, Stephan G.; Hoeppe, Henning A. [Lehrstuhl fuer Festkoerperchemie, Institut fuer Physik, Universitaet Augsburg (Germany); Wuellen, Leo van; Fischer, Andreas [Lehrstuhl fuer Chemische Physik und Materialwissenschaften, Institut fuer Physik, Universitaet Augsburg (Germany); Libowitzky, Eugen [Institute for Mineralogy and Crystallography, Faculty of Geosciences, Geography and Astronomy, University of Vienna (Austria); Baran, Enrique J. [Centro de Quimica Inorganica (CEQUINOR/CONICET, UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata (Argentina); Weil, Matthias [Institute for Chemical Technologies and Analytics, Division Structural Chemistry, Vienna University of Technology (Austria)

    2016-03-15

    Single crystals of Sr(PO{sub 3}F).H{sub 2}O {P2_1/c, Z = 4, a = 7.4844(2) Aa, b = 7.0793(2) Aa, c = 8.4265(2) Aa, β = 108.696(1) , V = 422.91(2) Aa"3, 2391 F_o"2, 70 parameters, R_1[F"2 > 2σ(F"2)] = 0.036; wR_2(F"2 all) = 0.049, S = 1.054} were grown from an aqueous solution by a metathesis reaction. The structure comprises [SrO{sub 8}] polyhedra and PO{sub 3}F tetrahedra that form a layered arrangement parallel to (100). The topotactic dehydration of this phase proceeds between 80 and 140 C to afford Sr(PO{sub 3}F). The monazite-type crystal structure of Sr(PO{sub 3}F) was elucidated from the X-ray powder data by simulated annealing [P2{sub 1}/c, Z = 4, a = 6.71689(9) Aa, b = 7.11774(11) Aa, c = 8.66997(13) Aa, β = 128.0063(7) , V = 326.605(8) Aa{sup 3}, R{sub p} = 0.010, R{sub wp} = 0.015, R{sub F} = 0.030]. During dehydration, the structure of Sr(PO{sub 3}F) .H{sub 2}O collapses along [100] from a layered arrangement into a framework structure, accompanied by a change of the coordination number of the Sr{sup 2+} ions from eight to nine. The magic-angle spinning (MAS) NMR and vibrational spectroscopy data of both phases are discussed. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Using an Interactive Web-Based Learning NMR Spectroscopy as a Means to Improve Problem Solving Skills for Undergraduates

    International Nuclear Information System (INIS)

    Supasorn, Saksri; Vibuljun, Sunantha; Panijpan, Bhinyo; Rajviroongit, Shuleewan

    2005-10-01

    An Interactive Web-Based Learning NMR Spectroscopy course is developed to improve and facilitate student ' s learning as well as achievement of learning objectives in the concepts of multiplicity, chemical shift, and problem solving. This web-based learning course is emphasized on NMR problem solving, therefore, the concepts of multiplicity and chemical shift, basic concepts for practice problem solving, are also emphasized. Most of animations and pictures in this web-based learning are new created and simplified to explain processes and principles in NMR spectroscopy. With meaningful animations and pictures, simplified English language used, step-by-step problem solving, and interactive test, it can be self-learning web site and best on the student ' s convenience

  16. NATURAL CYCLOPENTANOID CYANOHYDRIN GLYCOSIDES .13. STRUCTURE DETERMINATION OF NATURAL EPOXYCYCLOPENTANES BY X-RAY CRYSTALLOGRAPHY AND NMR-SPECTROSCOPY

    DEFF Research Database (Denmark)

    Olafsdottir, E. S.; Sorensen, A. M.; Cornett, Claus

    1991-01-01

    nonannellated cyclopentane derivatives. The new glucosides were shown, by NMR spectroscopy (including NOE measurements), X-ray crystallography, and enzymatic hydrolysis to the corresponding cyanohydrins, to be (1R,2R,3R,4R)- and (1S,2S,3S,4S)-1-(beta-D-glucopyranosyloxy)-2,3-epoxy-4-hydroxycyclopenta ne-1...

  17. Interaction of epothilone B (patupilone) with microtubules as detected by two-dimensional solid-state NMR spectroscopy

    NARCIS (Netherlands)

    Kumar, A.; Heise, H.; Blommers, M. J. J.; Krastel, P.; Schmitt, E.; Petersen, F.; Jeganathan, S.; Mandelkow, E. -M; Carlomagno, T.; Griesinger, C.; Baldus, M.

    2010-01-01

    Solid evidence: Induction of the polymerization of β-tubulin dimers into microtubules by epothilones, such as patupilone, by an as yet unknown mechanism leads to the apoptosis of cancer cells. Solid-state NMR spectroscopy of patupilone bound to microtubules has now enabled the identification of

  18. Relative stability of protein structures determined by X-ray crystallography or NMR spectroscopy : A molecular dynamics simulation study

    NARCIS (Netherlands)

    Fan, H; Mark, AE

    2003-01-01

    The relative stability of protein structures determined by either X-ray crystallography or nuclear magnetic resonance (NMR) spectroscopy has been investigated by using molecular dynamics simulation techniques. Published structures of 34 proteins containing between 50 and 100 residues have been

  19. Analysis of local molecular motions of aromatic sidechains in proteins by 2D and 3D fast MAS NMR spectroscopy and quantum mechanical calculations

    Czech Academy of Sciences Publication Activity Database

    Paluch, P.; Pawlak, T.; Jeziorna, A.; Trébosc, J.; Hou, G.; Vega, A. J.; Amoureux, J. P.; Dračínský, Martin; Polenova, T.; Potrzebowski, M. J.

    2015-01-01

    Roč. 17, č. 43 (2015), s. 28789-28801 ISSN 1463-9076 R&D Projects: GA ČR GA15-11223S Institutional support: RVO:61388963 Keywords : solid-state NMR * angle spinning NMR * NMR Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.449, year: 2015 http://pubs.rsc.org/en/content/articlepdf/2015/cp/c5cp04475h

  20. Tunneling Spectroscopy Study of Spin-Polarized Quasiparticle Injection Effects in Cuparate/Manganite Heterostructures

    Science.gov (United States)

    Wei, J. Y. T.; Yeh, N. C.; Vasquez, R. P.

    1998-01-01

    Scanning tunneling spectroscopy was performed at 4.2K on epitaxial thin-film heterostructures comprising YBa2Cu3O7 and La0.7Ca0.3MnO3, to study the microscopic effects of spin-polarized quasiparticle injection from the half-metallic ferromagnetic manganite on the high-Tc cuprate superconductor.

  1. Elucidation of meso- and microporosity in soil components with 129-Xe NMR spectroscopy of adsorbed xenon

    Science.gov (United States)

    Filimonova, Svetlana; Nossov, Andrey; Knicker, Heike; Kögel-Knabner, Ingrid

    2010-05-01

    Soil meso- and micropores (2-50 nm and bio-macromolecules. Natural soil particle size fractions were obtained from a non-allophanic Andosol and from Arenosol, i.e. soils containing charred residues and also characterised by a high content of Al oxides (case of the Andosol). DOM sorption on the studied Al oxides occurred inhomogeneously as it was inferred from the existence of the "empty" pores and the pores coated with OM. The latter were evidenced by the different Xe adsorption enthalpies estimated from the temperature dependences of the chemical shift. The increased sensitivity of the HP 129-Xe NMR allowed us detecting micropores in the charcoals, where the N2 adsorption method underestimated porosity due to the restricted diffusion of N2 at 77 K. The observed differences between the HP and TP 129-Xe patterns were explained by the slow diffusion of xenon within an interconnected but highly constricted pore system of the charcoals. The estimated width of those constricted pore openings was of the order of one or two diameters of the Xe atom. Similar "bottle neck" effects may also exist in the natural soil particle size fractions, as it was inferred from the increased pore access for Xe adsorption performed at elevated pressures (2-4 bar). The unusually large 129-Xe shifts (up to 170 ppm) detected for the for the H2O2-treated clay fractions of the Andosol (Bw horizon) coincided with their large specific surface areas(up to 220 m2/g) and were attributed to the pores formed by agglomerates of the nano-sized Al - humus complexes with contribution from the charred residues. Micropores found in the Arenosol fractions were attributed to the charred residues. Briefly, 129-Xe NMR spectroscopy shows its potential for studying soil meso- and micropores due to: i) higher sensitivity for probing micropores within polymeric organic structures, e.g. charcoals, as compared to the N2 adsorption; ii) possibility to use elevated pressures of the adsorbate for increasing the pore

  2. TG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oil

    KAUST Repository

    Elbaz, Ayman M.

    2015-11-12

    There is an increasing interest in the comprehensive study of heavy fuel oil (HFO) due to its growing use in furnaces, boilers, marines, and recently in gas turbines. In this work, the thermal combustion characteristics and chemical composition of HFO were investigated using a range of techniques. Thermogravimetric analysis (TGA) was conducted to study the nonisothermal HFO combustion behavior. Chemical characterization of HFO was accomplished using various standard methods in addition to direct infusion atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (APCI-FTICR MS), high resolution 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear multiple bond correlation (HMBC) spectroscopy. By analyzing thermogravimetry and differential thermogravimetry (TG/DTG) results, three different reaction regions were identified in the combustion of HFO with air, specifically, low temperature oxidation region (LTO), fuel deposition (FD), and high temperature oxidation (HTO) region. At the high end of the LTO region, a mass transfer resistance (skin effect) was evident. Kinetic analysis in LTO and HTO regions was conducted using two different kinetic models to calculate the apparent activation energy. In both models, HTO activation energies are higher than those for LTO. The FT-ICR MS technique resolved thousands of aromatic and sulfur containing compounds in the HFO sample and provided compositional details for individual molecules of three major class species. The major classes of compounds included species with one sulfur atom (S1), with two sulfur atoms (S2), and purely hydrocarbons (HC). The DBE (double bond equivalent) abundance plots established for S1 and HC provided additional information on their distributions in the HFO sample. The 1H NMR and 13C NMR results revealed that nearly 59% of the 1H nuclei were distributed as paraffinic CH2 and 5% were in aromatic groups. Nearly 21% of 13C nuclei were

  3. Unusual spin frozen state in a frustrated pyrochlore system NaCaCo{sub 2}F{sub 7} as observed by NMR

    Energy Technology Data Exchange (ETDEWEB)

    Sarkar, R.; Brueckner, F.; Klauss, H.H. [IFP, TU Dresden (Germany); Krizan, J.W.; Cava, R.J. [Department of Chemistry, Princeton University, Princeton, NJ (United States)

    2016-07-01

    We present {sup 23}Na -and {sup 19}F NMR results on the magnetically frustrated pyrochlore NaCaCo{sub 2}F{sub 7} with a frustration index of f = θ{sub CW}/T{sub f} ∝ 56. Recent neutron scattering experiments proposed XY like antiferromagnetic spin clusters at low energies in NaCaCo{sub 2}F{sub 7}. {sup 23}Na NMR -spectra reveal the presence of two magnetically non equivalent Na sites in conjunction with the local Co{sup 2+} spin structure. Below 3.6 K both the {sup 23}Na -and {sup 19}F spectra broaden due to the formation of static spin correlations. A huge reduction of the {sup 19}F -and {sup 23}Na NMR signal intensity hints at a quasi-static field distribution in NaCaCo{sub 2}F{sub 7} in this regime. The {sup 19}F spin-lattice relaxation rate {sup 19}(1/T{sub 1}) exhibits a peak at around 2.9 K, at the same temperature range where ac and dc susceptibility data show a broad maximum. The character of the spin fluctuation appears to be isotropic. The overall temperature dependence of {sup 19}(1/T{sub 1}) can be described by the BPP theory considering a fluctuating hyperfine field with an autocorrelation function. The correlation time of the autocorrelation function exhibits an activation behavior further indicating the spin-frozen state. While the present NMR studies suggest the spin frozen state at low temperatures, μSR investigations however reveal the presence of so called persistent spin dynamics down to 20 mK implying an exotic ground state in NaCaCo{sub 2}F{sub 7}.

  4. Determination of the 14N quadrupole coupling constant of nitroxide spin probes by W-band ELDOR-detected NMR

    Science.gov (United States)

    Florent, Marc; Kaminker, Ilia; Nagarajan, Vijayasarathi; Goldfarb, Daniella

    2011-06-01

    Nitroxide spin probe electron paramagnetic resonance (EPR) has proven to be a very successful method to probe local polarity and solvent hydrogen bonding properties at the molecular level. The g xx and the 14N hyperfine A zz principal values are the EPR parameters of the nitroxide spin probe that are sensitive to these properties and are therefore monitored experimentally. Recently, the 14N quadrupole interaction of nitroxides has been shown to be also highly sensitive to polarity and H-bonding (A. Savitsky et al., J. Phys. Chem. B 112 (2008) 9079). High-field electron spin echo envelope modulation (ESEEM) was used successfully to determine the P xx and P yy principal components of the 14N quadrupole tensor. The P zz value was calculated from the traceless character of the quadrupole tensor. We introduce here high-field (W-band, 95 GHz, 3.5 T) electron-electron double resonance (ELDOR)-detected NMR as a method to obtain the 14N P zz value directly, together with A zz. This is complemented by W-band hyperfine sublevel correlation (HYSCORE) measurements carried out along the g xx direction to determine the principal P xx and P yy components. Through measurements of TEMPOL dissolved in solvents of different polarities, we show that A zz increases, while | P zz| decreases with polarity, as predicted by Savitsky et al.

  5. Introduction to Spin Label Electron Paramagnetic Resonance Spectroscopy of Proteins

    Science.gov (United States)

    Melanson, Michelle; Sood, Abha; Torok, Fanni; Torok, Marianna

    2013-01-01

    An undergraduate laboratory exercise is described to demonstrate the biochemical applications of electron paramagnetic resonance (EPR) spectroscopy. The beta93 cysteine residue of hemoglobin is labeled by the covalent binding of 3-maleimido-proxyl (5-MSL) and 2,2,5,5-tetramethyl-1-oxyl-3-methyl methanethiosulfonate (MTSL), respectively. The excess…

  6. Spin polarization of (Ga,Mn)As measured by Andreev spectroscopy: the role of spin-active scattering

    Czech Academy of Sciences Publication Activity Database

    Piano, S.; Grein, R.; Mellor, C.J.; Výborný, Karel; Campion, R.; Wang, M.; Eschrig, M.; Gallagher, B. L.

    2011-01-01

    Roč. 83, č. 8 (2011), 081305/1-081305/4 ISSN 1098-0121 R&D Projects: GA AV ČR KJB100100802; GA MŠk(CZ) 7E08087 EU Projects: European Commission(XE) 214499 - NAMASTE; European Commission(XE) 237375 - SemiSpinNano Grant - others:AV ČR(CZ) AP0801 Program:Akademická prémie - Praemium Academiae Institutional research plan: CEZ:AV0Z10100521 Keywords : Andreev spectroscopy * magnetic semiconductors Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.691, year: 2011

  7. Magic angle spinning NMR reveals sequence-dependent structural plasticity, dynamics, and the spacer peptide 1 conformation in HIV-1 capsid protein assemblies.

    Science.gov (United States)

    Han, Yun; Hou, Guangjin; Suiter, Christopher L; Ahn, Jinwoo; Byeon, In-Ja L; Lipton, Andrew S; Burton, Sarah; Hung, Ivan; Gor'kov, Peter L; Gan, Zhehong; Brey, William; Rice, David; Gronenborn, Angela M; Polenova, Tatyana

    2013-11-27

    A key stage in HIV-1 maturation toward an infectious virion requires sequential proteolytic cleavage of the Gag polyprotein leading to the formation of a conical capsid core that encloses the viral RNA genome and a small complement of proteins. The final step of this process involves severing the SP1 peptide from the CA-SP1 maturation intermediate, which triggers the condensation of the CA protein into the capsid shell. The details of the overall mechanism, including the conformation of the SP1 peptide in CA-SP1, are still under intense debate. In this report, we examine tubular assemblies of CA and the CA-SP1 maturation intermediate using magic angle spinning (MAS) NMR spectroscopy. At magnetic fields of 19.9 T and above, outstanding quality 2D and 3D MAS NMR spectra were obtained for tubular CA and CA-SP1 assemblies, permitting resonance assignments for subsequent detailed structural characterization. Dipolar- and scalar-based correlation experiments unequivocally indicate that SP1 peptide is in a random coil conformation and mobile in the assembled CA-SP1. Analysis of two CA protein sequence variants reveals that, unexpectedly, the conformations of the SP1 tail, the functionally important CypA loop, and the loop preceding helix 8 are modulated by residue variations at distal sites. These findings provide support for the role of SP1 as a trigger of the disassembly of the immature CA capsid for its subsequent de novo reassembly into mature cores and establish the importance of sequence-dependent conformational plasticity in CA assembly.

  8. Two-dimensional NMR spectroscopy: correlated, homonuclear-correlated, and nuclear Overhauser spectroscopy. January 1975-December 1988 (Citations from the INSPEC: Information Services for the Physics and Engineering Communities data base). Report for January 1975-December 1988

    International Nuclear Information System (INIS)

    1988-12-01

    This bibliography contains citations concerning the enhanced analytical techniques of two-dimensional nuclear magnetic resonance (2-D NMR). Applications to specific molecules, biomolecules, and compounds as well as comparisons of three 2-D NMR techniques: correlated spectroscopy (COSY), nuclear Overhauser (NOSEY), and homonuclear-correlated spectroscopy (HOMCOR). (Contains 190 citations fully indexed and including a title list.)

  9. NMR-MRI, μSR and Mössbauer Spectroscopies in Molecular Magnets

    CERN Document Server

    Carretta, Pietro

    2007-01-01

    The discovery of molecular nanomagnets showing novel quantum effects, as the quantum tunneling of the magnetization, has brought to a renewed interest for the study of molecular magnetism and multifunctional molecular material. These materials have recently triggered an intense research activity in view of their possible applicabilities as, for example, as nanosized information storage units and as magnetic nanoparticles for bio-medicine. Several fundamental aspects of the microscopic static and dynamic properties of these molecular materials have been obtained by means of spectroscopies using local probes, as nuclei and muons. In this book an extensive overview on the results obtained during the last decade and on recent achievements in the study of molecular magnets by means of Nuclear Magnetic Resonance, Muon Spin Rotation, Magnetic Resonance Imaging and Mossbauer techniques is presented. The aim is to introduce the reader to these techniques and to give a general background on their application to molecul...

  10. High-dose dosimetry using electron spin resonance (ESR) spectroscopy

    International Nuclear Information System (INIS)

    Kojima, Takuji; Tanaka, Ryuichi

    1992-01-01

    An electron spin resonance (ESR) dosimeter capable of measuring large doses of radiation in radiotherapy and radiation processing is outlined. In particular, an alanine/ESR dosimeter is discussed, focusing on the development of elements, the development of the ESR dosimetric system, the application of alanine/ESR dosimeter, and basic researches. Rod elements for gamma radiation and x radiation and film elements for electron beams are described in detail. The following recent applications of the alanine/ESR dosimeter are introduced: using as a transfer dosimeter, applying to various types of radiation, diagnosing the deterioration of radiological materials and equipments, and applying to ESR imaging. The future subjects to be solved in the alanine/ESR dosimetric system are referred to as follows: (1) improvement of highly accurate elements suitable for the measurement of various types of radiation, (2) establishment of sensitive calibration method of the ESR equipment itself, and (3) calibration and standardization of radiation doses. (K.N.) 65 refs

  11. Dynamic membrane interactions of antibacterial and antifungal biomolecules, and amyloid peptides, revealed by solid-state NMR spectroscopy.

    Science.gov (United States)

    Naito, Akira; Matsumori, Nobuaki; Ramamoorthy, Ayyalusamy

    2018-02-01

    A variety of biomolecules acting on the cell membrane folds into a biologically active structure in the membrane environment. It is, therefore, important to determine the structures and dynamics of such biomolecules in a membrane environment. While several biophysical techniques are used to obtain low-resolution information, solid-state NMR spectroscopy is one of the most powerful means for determining the structure and dynamics of membrane bound biomolecules such as antibacterial biomolecules and amyloidogenic proteins; unlike X-ray crystallography and solution NMR spectroscopy, applications of solid-state NMR spectroscopy are not limited by non-crystalline, non-soluble nature or molecular size of membrane-associated biomolecules. This review article focuses on the applications of solid-state NMR techniques to study a few selected antibacterial and amyloid peptides. Solid-state NMR studies revealing the membrane inserted bent α-helical structure associated with the hemolytic activity of bee venom melittin and the chemical shift oscillation analysis used to determine the transmembrane structure (with α-helix and 3 10 -helix in the N- and C-termini, respectively) of antibiotic peptide alamethicin are discussed in detail. Oligomerization of an amyloidogenic islet amyloid polypeptide (IAPP, or also known as amylin) resulting from its aggregation in a membrane environment, molecular interactions of the antifungal natural product amphotericin B with ergosterol in lipid bilayers, and the mechanism of lipid raft formation by sphingomyelin studied using solid state NMR methods are also discussed in this review article. This article is part of a Special Issue entitled "Biophysical Exploration of Dynamical Ordering of Biomolecular Systems" edited by Dr. Koichi Kato. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. NMR relaxation in spin ice at low temperature due to diffusing emergent monopoles

    Science.gov (United States)

    Henley, Christopher L.

    2013-03-01

    At low temperatures, spin dynamics in ideal spin ice is due mainly to dilute, thermally excited magnetic ``monopole'' excitations. I consider how these will affect the longitudinal (T1) and dephasing (T2) relaxation functions of a nuclear spin in the spin-ice pyrochlore Dy2Ti2O4. Up to the time scale for nearby monopoles to be rearranged, a stretched-exponential form of the relaxation functions is expected, due to averaging over nuclei that have different local environments. ror the dephasing (T2) relaxation, the power of time in the stretched exponential is 3/2 in the case of diffusing monopoles, but 1/2 in the case of fixed, fluctuating magnetic impurities. The flip rate and density of fluctuating spins (whatever their nature) can be extracted from the measured relaxation times T1 and T2, and from known parameters. However, the actual experimental relaxation measured by Kitagawa and Takigawa becomes temperature independent in the very low T limit, and the T2 has a power t 1 / 2 in the exponential, neither of which can be explained by monopoles. I suggest the very low T behavior could be due to magnetic impurities on the (normally nonmagnetic) Ti sites. Supported by NSF grant DMR-1005466.

  13. Multinuclear solid-state high-resolution and C-13 -{Al-27} double-resonance magic-angle spinning NMR studies on aluminum alkoxides

    NARCIS (Netherlands)

    Abraham, A.; Prins, R.; Bokhoven, J.A. van; Eck, E.R.H. van; Kentgens, A.P.M.

    2006-01-01

    A combination of Al-27 magic-angle spinning (MAS)/multiple quantum (MQ)-MAS, C-13-H-1 CPMAS, and C-13-{Al-27} transfer of population in double-resonance (TRAPDOR) nuclear magnetic resonance (NMR) were used for the structural elucidation of the aluminum alkoxides aluminum ethoxide, aluminum

  14. Dynamic domains of amyloid fibrils can be site-specifically assigned with proton detected 3D NMR spectroscopy

    International Nuclear Information System (INIS)

    Falk, Alexander S.; Siemer, Ansgar B.

    2016-01-01

    Several amyloid fibrils have cores framed by highly dynamic, intrinsically disordered, domains that can play important roles for function and toxicity. To study these domains in detail using solid-state NMR spectroscopy, site-specific resonance assignments are required. Although the rapid dynamics of these domains lead to considerable averaging of orientation-dependent NMR interactions and thereby line-narrowing, the proton linewidths observed in these samples is far larger than what is regularly observed in solution. Here, we show that it is nevertheless possible to record 3D HNCO, HNCA, and HNcoCA spectra on these intrinsically disordered domains and to obtain site-specific assignments.

  15. Styrylpyrylium Salts: 1H and 13C NMR High-Resolution Spectroscopy (1D and 2D

    Directory of Open Access Journals (Sweden)

    Jean Claude W. Ouédraogo

    2010-01-01

    Full Text Available 1H and 13C NMR high-resolution spectroscopy (1D and 2D (1H, 1H-COSY, HSQC, HMBC for four styrylpyrylium perchlorates were carried out and signal attributions are reported. Chemical shifts observed on 13C NMR spectra for the styrylpyrylium salts were compared with net atomic charge for carbon obtained by AM1 semiempirical calculations. The position of the styryl group present low effect on chemical shifts for carbon atoms, while the presence of methyl group led to the unshielding of the substituted carbon.

  16. Dynamic domains of amyloid fibrils can be site-specifically assigned with proton detected 3D NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Falk, Alexander S.; Siemer, Ansgar B., E-mail: asiemer@usc.edu [Keck School of Medicine of USC, Department of Biochemistry and Molecular Medicine, Zilkha Neurogenetic Institute (United States)

    2016-11-15

    Several amyloid fibrils have cores framed by highly dynamic, intrinsically disordered, domains that can play important roles for function and toxicity. To study these domains in detail using solid-state NMR spectroscopy, site-specific resonance assignments are required. Although the rapid dynamics of these domains lead to considerable averaging of orientation-dependent NMR interactions and thereby line-narrowing, the proton linewidths observed in these samples is far larger than what is regularly observed in solution. Here, we show that it is nevertheless possible to record 3D HNCO, HNCA, and HNcoCA spectra on these intrinsically disordered domains and to obtain site-specific assignments.

  17. {beta}-Lactam antibiotics epitope mapping with STD NMR spectroscopy: a study of drug-human serum albumin interaction

    Energy Technology Data Exchange (ETDEWEB)

    Milagre, Cintia D. F.; Cabeca, Luis F.; Almeida, Wanda P.; Marsaioli, Anita J., E-mail: cmilagre@rc.unesp.br [Institute of Chemistry, University of Campinas (UNICAMP), SP (Brazil)

    2012-03-15

    Molecular recognition events are key issues in many biological processes. STD NMR (saturation transfer difference nuclear magnetic resonance spectroscopy) is one of the techniques used to understand such biological interactions. Herein, we have investigated the interactions of four {beta}-lactam antibiotics belonging to two classes (cephalosporins and penicillins) with human serum albumin (HSA) by {sup 1}H STD NMR revealing that the interaction between the aromatic moiety and HSA is responsible for the binding efficiency. Thus, the structural differences from the five to six-membered thio ring in penicillins and cephalosporins do not seem to influence antibiotic albumin interactions. (author)

  18. Analysis of Polycyclic Aromatic Hydrocarbon (PAH Mixtures Using Diffusion-Ordered NMR Spectroscopy and Adsorption by Powdered Activated Carbon and Biochar

    Directory of Open Access Journals (Sweden)

    Dong An

    2018-03-01

    Full Text Available Analysis of polycyclic aromatic hydrocarbons (PAHs in air and water sources is a key part of environmental chemistry research, since most PAHs are well known to be associated with negative health impacts on humans. This study explores an approach for analyzing PAH mixtures with advanced nuclear magnetic resonance (NMR spectroscopic techniques including high-resolution one-dimensional (1D NMR spectroscopy and diffusion-ordered NMR spectroscopy (DOSY NMR. With this method, different kinds of PAHs can be detected and differentiated from a mixture with high resolution. The adsorption process of PAH mixtures by PAC and biochar was studied to understand the mechanism and assess the method.

  19. NMR water-proton spin-lattice relaxation time of human red blood cells and red blood cell suspensions

    International Nuclear Information System (INIS)

    Sullivan, S.G.; Rosenthal, J.S.; Winston, A.; Stern, A.

    1988-01-01

    NMR water-proton spin-lattice relaxation times were studied as probes of water structure in human red blood cells and red blood cell suspensions. Normal saline had a relaxation time of about 3000 ms while packed red blood cells had a relaxation time of about 500 ms. The relaxation time of a red blood cell suspension at 50% hematocrit was about 750 ms showing that surface charges and polar groups of the red cell membrane effectively structure extracellular water. Incubation of red cells in hypotonic saline increases relaxation time whereas hypertonic saline decreases relaxation time. Relaxation times varied independently of mean corpuscular volume and mean corpuscular hemoglobin concentration in a sample population. Studies with lysates and resealed membrane ghosts show that hemoglobin is very effective in lowering water-proton relaxation time whereas resealed membrane ghosts in the absence of hemoglobin are less effective than intact red cells. 9 refs.; 3 figs.; 1 table

  20. The dynamic complex of cytochrome c6 and cytochrome f studied with paramagnetic NMR spectroscopy.

    Science.gov (United States)

    Díaz-Moreno, Irene; Hulsker, Rinske; Skubak, Pavol; Foerster, Johannes M; Cavazzini, Davide; Finiguerra, Michelina G; Díaz-Quintana, Antonio; Moreno-Beltrán, Blas; Rossi, Gian-Luigi; Ullmann, G Matthias; Pannu, Navraj S; De la Rosa, Miguel A; Ubbink, Marcellus

    2014-08-01

    The rapid transfer of electrons in the photosynthetic redox chain is achieved by the formation of short-lived complexes of cytochrome b6f with the electron transfer proteins plastocyanin and cytochrome c6. A balance must exist between fast intermolecular electron transfer and rapid dissociation, which requires the formation of a complex that has limited specificity. The interaction of the soluble fragment of cytochrome f and cytochrome c6 from the cyanobacterium Nostoc sp. PCC 7119 was studied using NMR spectroscopy and X-ray diffraction. The crystal structures of wild type, M58H and M58C cytochrome c6 were determined. The M58C variant is an excellent low potential mimic of the wild type protein and was used in chemical shift perturbation and paramagnetic relaxation NMR experiments to characterize the complex with cytochrome f. The interaction is highly dynamic and can be described as a pure encounter complex, with no dominant stereospecific complex. Ensemble docking calculations and Monte-Carlo simulations suggest a model in which charge-charge interactions pre-orient cytochrome c6 with its haem edge toward cytochrome f to form an ensemble of orientations with extensive contacts between the hydrophobic patches on both cytochromes, bringing the two haem groups sufficiently close to allow for rapid electron transfer. This model of complex formation allows for a gradual increase and decrease of the hydrophobic interactions during association and dissociation, thus avoiding a high transition state barrier that would slow down the dissociation process. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Survival of Acetate in Biodegraded Stream Water DOM: New Insights Based on NMR Spectroscopy

    Science.gov (United States)

    Whitty, S.; Waggoner, D. C.; Bowen, J. C.; Cory, R. M.; Kaplan, L.; Hatcher, P.

    2017-12-01

    DOM is a complex chemical mixture of high- (HMW) and low-molecular-weight (LMW) organic molecules that serve as the primary energy sources for heterotrophic bacteria in freshwater environments. However, there are still large uncertainties on the composition of DOM that is labile and thus rapidly metabolized. The current thinking is that labile DOM is primarily composed of monosaccharides, amino acids, and other LMW organic acids such as formic, acetic, or propionic among others, although some humic substances also are biologically labile. To test the contribution of LMW organic acids to the labile fraction of DOM, freshwater samples were collected from five streams within the Rio Tempisquito watershed in Costa Rica and subjected to differing degrees of biodegradation using a series of plug-flow bioreactors with residence times ranging from 0.5-150 min. Varying the residence times of bioreactors allows for separation and identification of labile from less labile to more recalcitrant DOM. The stream water fed into the bioreactors had DOC concentrations that ranged from 0.7-1.2 ppm C and the GF/F-filtered stream water as well as the bioreactor effluents were analyzed directly without pre-treatment using proton nuclear magnetic resonance spectroscopy (1H NMR). Small molecules dominated the 1H NMR spectra with the greatest changes, as a function of bioreactor residence time, in the carbohydrate, terminal methyl, and long-chain methylene structures. In contrast, acetate remained relatively constant after 150 min of bioreactor residence time, thus raising the question of why this inherently labile volatile fatty acid was not consumed by stream microbes colonizing bioreactors that otherwise metabolized approximately 35% of the total dissolved organic carbon present in the stream water. We suggest that acetate may resist biodegradation because it is complexed strongly with inorganic cations.

  2. Characterization of plant-derived carbon and phosphorus in lakes by sequential fractionation and NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shasha [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhu, Yuanrong, E-mail: zhuyuanrong07@mails.ucas.ac.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Wu, Fengchang, E-mail: wufengchang@vip.skleg.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Meng, Wei [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Zhongqi [USDA-ARS Southern Regional Research Center, 1100 Robert E Lee Blvd, New Orleans, LA 70124 (United States); Giesy, John P. [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Biomedical and Veterinary Biosciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)

    2016-10-01

    Although debris from aquatic macrophytes is one of the most important endogenous sources of organic matter (OM) and nutrients in lakes, its biogeochemical cycling and contribution to internal load of nutrients in eutrophic lakes are still poorly understood. In this study, sequential fractionation by H{sub 2}O, 0.1 M NaOH and 1.0 M HCl, combined with {sup 13}C and {sup 31}P NMR spectroscopy, was developed and used to characterize organic carbon (C) and phosphorus (P) in six aquatic plants collected from Tai Lake (Ch: Taihu), China. Organic matter, determined by total organic carbon (TOC), was unequally distributed in H{sub 2}O (21.2%), NaOH (29.9%), HCl (3.5%) and residual (45.3%) fractions. For P in debris of aquatic plants, 53.3% was extracted by H{sub 2}O, 31.9% by NaOH, and 11% by HCl, with 3.8% in residual fractions. Predominant OM components extracted by H{sub 2}O and NaOH were carbohydrates, proteins and aliphatic acids. Inorganic P (P{sub i}) was the primary form of P in H{sub 2}O fractions, whereas organic P (P{sub o}) was the primary form of P in NaOH fractions. The subsequent HCl fractions extracted fewer species of C and P. Some non-extractable carbohydrates, aromatics and metal phytate compounds remained in residual fractions. Based on sequential extraction and NMR analysis, it was proposed that those forms of C (54.7% of TOC) and P (96.2% of TP) in H{sub 2}O, NaOH and HCl fractions are potentially released to overlying water as labile components, while those in residues are stable and likely preserved in sediments of lakes. These results will be helpful in understanding internal loading of nutrients from debris of aquatic macrophytes and their recycling in lakes. - Highlights: • Sequential fractionation combined with NMR analysis was applied on aquatic plants. • Labile and stable C and P forms in aquatic plants were characterized. • 54.7% of OM and 96.2% of P in aquatic plants are potentially available. • 45.3% of OM and 3.8% of P in aquatic

  3. A robust heteronuclear dipolar recoupling method comparable to TEDOR for proteins in magic-angle spinning solid-state NMR

    Science.gov (United States)

    Zhang, Zhengfeng; Li, Jianping; Chen, Yanke; Xie, Huayong; Yang, Jun

    2017-12-01

    In this letter, we propose a robust heteronuclear dipolar recoupling method for proteins in magic-angle spinning (MAS) solid-state NMR. This method is as simple, robust and efficient as the well-known TEDOR in the aspect of magnetization transfer between 15N and 13C. Deriving from our recent band-selective dual back-to-back pulses (DBP) (Zhang et al., 2016), this method uses new phase-cycling schemes to realize broadband DBP (Bro-DBP). For broadband 15N-13C magnetization transfer (simultaneous 15N → 13C‧ and 15N → 13Cα), Bro-DBP has almost the same 15N → 13Cα efficiency while offers 30-40% enhancement on 15N → 13C‧ transfer, compared to TEDOR. Besides, Bro-DBP can also be used as a carbonyl (13C‧)-selected method, whose 15N → 13C‧ efficiency is up to 1.7 times that of TEDOR and is also higher than that of band-selective DBP. The performance of Bro-DBP is demonstrated on the N-formyl-[U-13C,15N]-Met-Leu-Phe-OH (fMLF) peptide and the U-13C, 15N labeled β1 immunoglobulin binding domain of protein G (GB1) microcrystalline protein. Since Bro-DBP is as robust, simple and efficient as TEDOR, we believe it is very useful for protein studies in MAS solid-state NMR.

  4. Spectroscopy of high-spin states of 206Po

    International Nuclear Information System (INIS)

    Baxter, A.M.; Byrne, A.P.; Dracoulis, G.D.; Bark, R.A.; Riess, F.; Stuchbery, A.E.; Kruse, M.C.; Poletti, A.R.

    1990-05-01

    The yrast and near-yrast energy levels of 206 Po have been investigated to over 9 MeV excitation and up to spins with J=24. The measure-ments consisted of γ-γ coincidence data, internal-conversion-electron spectra, time spectra of γ-rays relative to a pulsed beam, excitation functions and γ-ray angular distributions. Two new isomers, with lifetime in the one-nonasecond range,were found. The observed structure is compared with the predictions of empirical shell-model calculations in which 206 Po is regarded as a 208 Pb core with two valence protons and four valence neutron holes. The agreement is generaly satisfactory for the observed odd-parity levels and for even parity levels with J > 12; those with J = 6 to 12 are better accounted for by weak coupling of two valence protons to a 204 Pb core in its 0 + 1, 2 + 1 and 4 + 1 states. 33 refs., 7 tabs., 12 figs

  5. Multiple Quantum Coherences (MQ) NMR and Entanglement Dynamics in the Mixed-Three-Spin XXX Heisenberg Model with Single-Ion Anisotropy

    Science.gov (United States)

    Hamid, Arian Zad

    2016-12-01

    We analytically investigate Multiple Quantum (MQ) NMR dynamics in a mixed-three-spin (1/2,1,1/2) system with XXX Heisenberg model at the front of an external homogeneous magnetic field B. A single-ion anisotropy property ζ is considered for the spin-1. The intensities dependence of MQ NMR coherences on their orders (zeroth and second orders) for two pairs of spins (1,1/2) and (1/2,1/2) of the favorite tripartite system are obtained. It is also investigated dynamics of the pairwise quantum entanglement for the bipartite (sub)systems (1,1/2) and (1/2,1/2) permanently coupled by, respectively, coupling constants J}1 and J}2, by means of concurrence and fidelity. Then, some straightforward comparisons are done between these quantities and the intensities of MQ NMR coherences and ultimately some interesting results are reported. We also show that the time evolution of MQ coherences based on the reduced density matrix of the pair spins (1,1/2) is closely connected with the dynamics of the pairwise entanglement. Finally, we prove that one can introduce MQ coherence of the zeroth order corresponds to the pair spins (1,1/2) as an entanglement witness at some special time intervals.

  6. 'In vivo' and high resolution spectroscopy in solids by NMR: an instrument for transgenic plants study

    International Nuclear Information System (INIS)

    Colnago, L.A.; Herrmann, P.S.P.; Bernardes Filho, R.

    1995-01-01

    This work has developed a study on transgenic plants using two different techniques of nuclear magnetic resonance, in vivo NMR and high resolution NMR. In order to understand the gene mutations and characterize the plants constituents, NMR spectral data were analysed and discussed, then the results were presented

  7. Theory of spin inelastic tunneling spectroscopy for superconductor-superconductor and superconductor-metal junctions

    Science.gov (United States)

    Berggren, P.; Fransson, J.

    2015-05-01

    We address the tunneling conductance and spin inelastic tunneling spectroscopy of localized paramagnetic moments in a superconducting environment, pertaining to recent measurements on Fe-octaethylporphyrin-chloride using superconducting scanning tunneling microscopy. We demonstrate that the Cooper pair correlations in the tip and substrate generate a finite uniaxial anisotropy field acting on the local spin moment, and we argue that this field may be a source for the observed changes in the conductance spectrum for decreasing distance between the scanning tunneling tip and the local magnetic moment. We make a side-by-side comparison between the superconductor-superconductor junction and normal-metal-superconductor junction, and find qualitative agreement between the two setups while quantitative differences become explicit. When simulating the effects of electron pumping, we obtain additional peaks in the conductance spectrum that can be attributed to excitations between higher-energy spin states. The transverse anisotropy field couples basis states of the local spin which opens for transitions between spin states that are otherwise forbidden by conservation of angular momentum. Finally, we explore the influences of temperature, which tend to enable in-gap transitions, and an external magnetic field, which enables deeper studies of the spin excitation spectrum. We especially notice the appearance of a low and high excitation peak on each side of the main coherence peak as an imprint of transitions between the Zeeman split ground states.

  8. 139La NMR investigation of the charge and spin order in a La1.885Sr0.115CuO4 single crystal

    Science.gov (United States)

    Arsenault, A.; Takahashi, S. K.; Imai, T.; He, W.; Lee, Y. S.; Fujita, M.

    2018-02-01

    139La NMR is suited for investigations into magnetic properties of La2CuO4 -based cuprates in the vicinity of their magnetic instabilities, owing to the modest hyperfine interactions between 139La nuclear spins and Cu electron spins. We report comprehensive 139La NMR measurements on a single-crystal sample of high-Tc superconductor La1.885Sr0.115CuO4 in a broad temperature range across the charge and spin order transitions (Tcharge≃80 K, Tspinneutron≃Tc=30 K). From the high-precision measurements of the linewidth for the nuclear spin Iz=+1 /2 to -1 /2 central transition, we show that paramagnetic line broadening sets in precisely at Tcharge due to enhanced spin correlations within the CuO2 planes. Additional paramagnetic line broadening ensues below ˜35 K, signaling that Cu spins in some segments of CuO2 planes are on the verge of three-dimensional magnetic order. A static hyperfine magnetic field arising from ordered Cu moments along the a b plane, however, begins to develop only below Tspinμ S R=15 -20 K, where earlier muon spin rotation measurements detected Larmor precession for a small volume fraction (˜20 % ) of the sample. Based on the measurement of 139La nuclear-spin-lattice relaxation rate 1 /T1 , we also show that charge order triggers enhancement of low-frequency Cu spin fluctuations inhomogeneously; a growing fraction of 139La sites is affected by enhanced low-frequency spin fluctuations toward the eventual magnetic order, whereas a diminishing fraction continues to exhibit a behavior analogous to the optimally superconducting phase even below Tcharge. These 139La NMR results corroborate our recent 63Cu NMR observation that a very broad, anomalous winglike signal gradually emerges below Tcharge, whereas the normally behaving, narrower main peak is gradually wiped out [T. Imai et al., Phys. Rev. B 96, 224508 (2017), 10.1103/PhysRevB.96.224508]. Furthermore, we show that the enhancement of low-energy spin excitations in the low-temperature regime

  9. Ground state properties of neutron-rich Mg isotopes the "island of inversion" studied with laser and $\\beta$-NMR spectroscopy

    CERN Document Server

    Kowalska, M

    2006-01-01

    Studies in regions of the nuclear chart in which the model predictions of properties of nuclei fail can bring a better understanding of the strong interaction in the nuclear medium. To such regions belongs the so called "island of inversion" centered around Ne, Na and Mg isotopes with 20 neutrons in which unexpected ground-state spins, large deformations and dense low-energy spectra appear. This is a strong argument that the magic N=20 is not a closed shell in this area. In this thesis investigations of isotope shifts of stable $^{24-26}$Mg, as well as spins and magnetic moments of short-lived $^{29,31}$Mg are presented. The successful studies were performed at the ISOLDE facility at CERN using collinear laser and $\\beta$-NMR spectroscopy techniques. The isotopes were investigated as single-charged ions in the 280 nm transition from the atomic ground state $^2\\!$S$_{1/2}$ to one of the two lowest excited states $^2\\!$P$_{1/2 ,\\,3/2}$ using continuous wave laser beams. The isotope-shift measurements with fluor...

  10. Double tuning a single input probe for heteronuclear NMR spectroscopy at low field

    Science.gov (United States)

    Tadanki, Sasidhar; Colon, Raul D.; Moore, Jay; Waddell, Kevin W.

    2012-10-01

    Applications of PASADENA in biomedicine are continuing to emerge due to recent demonstrations that hyperpolarized metabolic substrates and the corresponding reaction products persist sufficiently long to be detected in vivo. Biomedical applications of PASADENA typically differ from their basic science counterparts in that the polarization endowed by addition of parahydrogen is usually transferred from nascent protons to coupled storage nuclei for subsequent detection on a higher field imaging instrument. These pre-imaging preparations usually take place at low field, but commercial spectrometers capable of heteronuclear pulsed NMR at frequencies in the range of 100 kHz to 1 MHz are scarce though, in comparison to single channel consoles in that field regime. Reported here is a probe circuit that can be used in conjunction with a phase and amplitude modulation scheme we have developed called PANORAMIC (Precession And Nutation for Observing Rotations At Multiple Intervals about the Carrier), that expands a single channel console capability to double or generally multiple resonance with minimal hardware modifications. The demands of this application are geared towards uniform preparation, and since the hyperpolarized molecules are being detected externally at high field, detection sensitivity is secondary to applied field uniformity over a large reaction volume to accommodate heterogeneous chemistry of gas molecules at a liquid interface. The probe circuit was therefore configured with a large (40 mL) Helmholtz sample coil for uniformity, and double-tuned to the Larmor precession frequencies of 13C/1H (128/510 kHz) within a custom solenoidal electromagnet at a static field of 12 mT. Traditional (on-resonant) as well as PANORAMIC NMR signals with signal to noise ratios of approximately 75 have been routinely acquired with this probe and spectrometer setup from 1024 repetitions on the high frequency channel. The proton excitation pulse width was 240 μs at 6.31 W

  11. Proton Nuclear Magnetic Resonance (1H NMR) Spectroscopy-Based Analysis of Lipid Components in Serum/Plasma of Patients with Duchenne Muscular Dystrophy (DMD).

    Science.gov (United States)

    Srivastava, Niraj Kumar

    2018-01-01

    Proton nuclear magnetic resonance spectroscopy ( 1 H NMR) is a useful tool for the analysis of lipid components in biofluids such as serum/plasma. Such tool is applied for the analysis of lipid components in serum/plasma of patients with Duchenne muscular dystrophy (DMD). The practical approach of sampling, storage, lipid extraction procedure, sample preparation before performing the 1 H NMR spectroscopy experiments is presented. All the experimental parameters of NMR spectroscopy are also described. Details of the assignments of lipid components (qualitative analysis) and quantification of particular lipid components (quantitative analysis) are explained.

  12. Magic angle spinning NMR below 6 K with a computational fluid dynamics analysis of fluid flow and temperature gradients

    Science.gov (United States)

    Sesti, Erika L.; Alaniva, Nicholas; Rand, Peter W.; Choi, Eric J.; Albert, Brice J.; Saliba, Edward P.; Scott, Faith J.; Barnes, Alexander B.

    2018-01-01

    We report magic angle spinning (MAS) up to 8.5 kHz with a sample temperature below 6 K using liquid helium as a variable temperature fluid. Cross polarization 13C NMR spectra exhibit exquisite sensitivity with a single transient. Remarkably, 1H saturation recovery experiments show a 1H T1 of 21 s with MAS below 6 K in the presence of trityl radicals in a glassy matrix. Leveraging the thermal spin polarization available at 4.2 K versus 298 K should result in 71 times higher signal intensity. Taking the 1H longitudinal relaxation into account, signal averaging times are therefore predicted to be expedited by a factor of >500. Computer assisted design (CAD) and finite element analysis were employed in both the design and diagnostic stages of this cryogenic MAS technology development. Computational fluid dynamics (CFD) models describing temperature gradients and fluid flow are presented. The CFD models bearing and drive gas maintained at 100 K, while a colder helium variable temperature fluid stream cools the center of a zirconia rotor. Results from the CFD were used to optimize the helium exhaust path and determine the sample temperature. This novel cryogenic experimental platform will be integrated with pulsed dynamic nuclear polarization and electron decoupling to interrogate biomolecular structure within intact human cells.

  13. Structure Elucidation of Mixed-Linker Zeolitic Imidazolate Frameworks by Solid-State (1)H CRAMPS NMR Spectroscopy and Computational Modeling.

    Science.gov (United States)

    Jayachandrababu, Krishna C; Verploegh, Ross J; Leisen, Johannes; Nieuwendaal, Ryan C; Sholl, David S; Nair, Sankar

    2016-06-15

    Mixed-linker zeolitic imidazolate frameworks (ZIFs) are nanoporous materials that exhibit continuous and controllable tunability of properties like effective pore size, hydrophobicity, and organophilicity. The structure of mixed-linker ZIFs has been studied on macroscopic scales using gravimetric and spectroscopic techniques. However, it has so far not been possible to obtain information on unit-cell-level linker distribution, an understanding of which is key to predicting and controlling their adsorption and diffusion properties. We demonstrate the use of (1)H combined rotation and multiple pulse spectroscopy (CRAMPS) NMR spin exchange measurements in combination with computational modeling to elucidate potential structures of mixed-linker ZIFs, particularly the ZIF 8-90 series. All of the compositions studied have structures that have linkers mixed at a unit-cell-level as opposed to separated or highly clustered phases within the same crystal. Direct experimental observations of linker mixing were accomplished by measuring the proton spin exchange behavior between functional groups on the linkers. The data were then fitted to a kinetic spin exchange model using proton positions from candidate mixed-linker ZIF structures that were generated computationally using the short-range order (SRO) parameter as a measure of the ordering, clustering, or randomization of the linkers. The present method offers the advantages of sensitivity without requiring isotope enrichment, a straightforward NMR pulse sequence, and an analysis framework that allows one to relate spin diffusion behavior to proposed atomic positions. We find that structures close to equimolar composition of the two linkers show a greater tendency for linker clustering than what would be predicted based on random models. Using computational modeling we have also shown how the window-type distribution in experimentally synthesized mixed-linker ZIF-8-90 materials varies as a function of their composition. The

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

    Science.gov (United States)

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

    2015-06-10

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

  15. Selectively Labeling the Heterologous Protein in Escherichia coli for NMR Studies: A Strategy to Speed Up NMR Spectroscopy

    Science.gov (United States)

    Almeida, F. C. L.; Amorim, G. C.; Moreau, V. H.; Sousa, V. O.; Creazola, A. T.; Américo, T. A.; Pais, A. P. N.; Leite, A.; Netto, L. E. S.; Giordano, R. J.; Valente, A. P.

    2001-01-01

    Nuclear magnetic resonance is an important tool for high-resolution structural studies of proteins. It demands high protein concentration and high purity; however, the expression of proteins at high levels often leads to protein aggregation and the protein purification step can correspond to a high percentage of the overall time in the structural determination process. In the present article we show that the step of sample optimization can be simplified by selective labeling the heterologous protein expressed in Escherichia coli by the use of rifampicin. Yeast thioredoxin and a coix transcription factor Opaque 2 leucine zipper (LZ) were used to show the effectiveness of the protocol. The 1H/15N heteronuclear correlation two-dimensional NMR spectrum (HMQC) of the selective 15N-labeled thioredoxin without any purification is remarkably similar to the spectrum of the purified protein. The method has high yields and a good 1H/15N HMQC spectrum can be obtained with 50 ml of M9 growth medium. Opaque 2 LZ, a difficult protein due to the lower expression level and high hydrophobicity, was also probed. The 15N-edited spectrum of Opaque 2 LZ showed only the resonances of the protein of heterologous expression (Opaque 2 LZ) while the 1H spectrum shows several other resonances from other proteins of the cell lysate. The demand for a fast methodology for structural determination is increasing with the advent of genome/proteome projects. Selective labeling the heterologous protein can speed up NMR structural studies as well as NMR-based drug screening. This methodology is especially effective for difficult proteins such as hydrophobic transcription factors, membrane proteins, and others.

  16. Combining STMAS and CRAMPS NMR spectroscopy: High-resolution HETCOR NMR spectra of quadrupolar and 1H nuclei in solids

    Science.gov (United States)

    Siegel, Renée; Rocha, João; Mafra, Luís

    2009-03-01

    High-resolution two-dimensional (2D) heteronuclear correlation spectra between half-integer quadrupolar and 1H nuclei have been obtained combining Satellite Transition Magic-Angle Spinning (STMAS) and wPMLG3 CRAMPS methods. The experiments use split-t 1 versions of DQ/DQF-STMAS adapted to 3/2 and 5/2 spins to obtain a 23Na and 27Al isotropic dimension, respectively. Transfer of magnetization from quadrupolar nuclei to protons has been achieved by cross-polarization, and high-resolution 1H spectra have been recorded using the wPMLG3 decoupling during the t 2 evolution period. The performance of the pulse sequences have been tested on the templated microporous aluminophosphate IST-1 and trisodium citrate employing a B0 field of 9.4 T.

  17. Chemical behavior of methylpyranomalvidin-3-O-glucoside in aqueous solution studied by NMR and UV-visible spectroscopy.

    Science.gov (United States)

    Oliveira, Joana; Petrov, Vesselin; Parola, A Jorge; Pina, Fernando; Azevedo, Joana; Teixeira, Natércia; Brás, Natércia F; Fernandes, Pedro A; Mateus, Nuno; Ramos, Maria João; de Freitas, Victor

    2011-02-17

    In the present work, the proton-transfer reactions of the methylpyranomalvidin-3-O-glucoside pigment in water with different pH values was studied by NMR and UV-visible spectroscopies. The results showed four equilibrium forms: the methylpyranomalvidin-3-O-glucoside cation, the neutral quinoidal base, the respective anionic quinoidal base, and a dianionic base unprotonated at the methyl group. According to the NMR data, it seems that for methylpyranomalvidin-3-O-glucoside besides the acid-base equilibrium between the pyranoflavylium cation and the neutral quinoidal base, a new species is formed at pD 4.88-6.10. This is corroborated by the appearance of a new set of signals in the NMR spectrum that may be assigned to the formation of hemiketal/cis-chalcone species to a small extent. The two ionization constants (pK(a1) and pK(a2)) obtained by both methods (NMR and UV-visible) for methylpyranomalvidin-3-O-glucoside are in agreement (pK(a1) = 5.17 ± 0.03; pK(a2) = 8.85 ± 0.08; and pK(a1) = 4.57 ± 0.07; pK(a2) = 8.23 ± 0.04 obtained by NMR and UV-visible spectroscopies, respectively). Moreover, the fully dianionic unprotonated form (at the methyl group) of the methylpyranomalvidin-3-O-glucoside is converted slowly into a new structure that displays a yellow color at basic pH. On the basis of the results obtained through LC-MS and NMR, the proposed structure was found to correspond to the flavonol syringetin-3-glucoside.

  18. Coherent Two-Dimensional Terahertz Magnetic Resonance Spectroscopy of Collective Spin Waves.

    Science.gov (United States)

    Lu, Jian; Li, Xian; Hwang, Harold Y; Ofori-Okai, Benjamin K; Kurihara, Takayuki; Suemoto, Tohru; Nelson, Keith A

    2017-05-19

    We report a demonstration of two-dimensional (2D) terahertz (THz) magnetic resonance spectroscopy using the magnetic fields of two time-delayed THz pulses. We apply the methodology to directly reveal the nonlinear responses of collective spin waves (magnons) in a canted antiferromagnetic crystal. The 2D THz spectra show all of the third-order nonlinear magnon signals including magnon spin echoes, and 2-quantum signals that reveal pairwise correlations between magnons at the Brillouin zone center. We also observe second-order nonlinear magnon signals showing resonance-enhanced second-harmonic and difference-frequency generation. Numerical simulations of the spin dynamics reproduce all of the spectral features in excellent agreement with the experimental 2D THz spectra.

  19. Enhanced solid-state NMR correlation spectroscopy of quadrupolar nuclei using dynamic nuclear polarization.

    Science.gov (United States)

    Lee, Daniel; Takahashi, Hiroki; Thankamony, Aany S L; Dacquin, Jean-Philippe; Bardet, Michel; Lafon, Olivier; Paëpe, Gaël De

    2012-11-14

    By means of a true sensitivity enhancement for a solid-state NMR spectroscopy (SSNMR) experiment performed under dynamic nuclear polarization (DNP) conditions, corresponding to 4-5 orders of magnitude of time savings compared with a conventional SSNMR experiment, it is shown that it is possible to record interface-selective (27)Al-(27)Al two-dimensional dipolar correlation spectra on mesoporous alumina, an advanced material with potential industrial applications. The low efficiency of cross-polarization and dipolar recoupling for quadrupolar nuclei is completely negated using this technique. The important presence of pentacoordinated Al has not only been observed, but its role in bridging interfacial tetra- and hexacoordinated Al has been determined. Such structural information, collected at low temperature (∼103 K) and 9.4 T with the use of DNP, would have been impossible to obtain under standard conditions, even using a higher magnetic field. However, here it is demonstrated that this information can be obtained in only 4 h. This work clearly opens a new avenue for the application of SSNMR to quadrupolar nuclei and notably the atomic-scale structure determination of catalysis materials such as mesoporous alumina.

  20. Analysis of the hydrolysis of inulin using real time 1H NMR spectroscopy

    Science.gov (United States)

    Barclay, Thomas; Ginic-Markovic, Milena; Johnston, Martin R.; Cooper, Peter D.; Petrovsky, Nikolai

    2012-01-01

    The hydrolysis of various carbohydrates was investigated under acidic conditions in real time by 1H NMR spectroscopy, with a focus on the polysaccharide inulin. Sucrose was used as a model compound to illustrate the applicability of this technique. The hydrolysis of sucrose was shown to follow pseudo first order kinetics and have an activation energy of 107.0 kJ.mol−1 (s.d. 1.7 kJ.mol−1). Inulin, pullulan and glycogen also all followed pseudo first order kinetics, but had an initiation phase at least partially generated by the protonation of the glycosidic bonds. It was also demonstrated that polysaccharide chain length has an effect on the hydrolysis of inulin. For short chain inulin (DPn 18, s.d. 0.70) the activation energy calculated for the hydrolytic cleavage of glucose was similar to sucrose at 108.5 kJ.mol−1 (std. dev. 0.60). For long chain inulin (DPn 30, s.d. 1.3) the activation energy for the hydrolytic cleavage of glucose was reduced to 80.5 kJ.mol−1 (s.d. 2.3 kJ.mol−1). This anomaly has been attributed to varied conformations for the two different lengths of inulin chain in solution. PMID:22464225

  1. Utilizing NMR and EPR spectroscopy to probe the role of copper in prion diseases

    KAUST Repository

    Emwas, Abdul-Hamid M.

    2013-02-24

    Copper is an essential nutrient for the normal development of the brain and nervous system, although the hallmark of several neurological diseases is a change in copper concentrations in the brain and central nervous system. Prion protein (PrP) is a copper-binding, cell-surface glycoprotein that exists in two alternatively folded conformations: a normal isoform (PrPC) and a disease-associated isoform (PrPSc). Prion diseases are a group of lethal neurodegenerative disorders that develop as a result of conformational conversion of PrPC into PrPSc. The pathogenic mechanism that triggers this conformational transformation with the subsequent development of prion diseases remains unclear. It has, however, been shown repeatedly that copper plays a significant functional role in the conformational conversion of prion proteins. In this review, we focus on current research that seeks to clarify the conformational changes associated with prion diseases and the role of copper in this mechanism, with emphasis on the latest applications of NMR and EPR spectroscopy to probe the interactions of copper with prion proteins. Copyright © 2013 John Wiley & Sons, Ltd.

  2. Quantification of Water-Soluble Metabolites in Medicinal Mushrooms Using Proton NMR Spectroscopy.

    Science.gov (United States)

    Lo, Yu-Chang; Chien, Shih-Chang; Mishchuk, Darya O; Slupsky, Carolyn M; Mau, Jeng-Leun

    2016-01-01

    The water-soluble metabolites in 5 mushrooms were identified and quantified using proton nuclear magnetic resonance (NMR) spectroscopy and software for targeted metabolite detection and quantification. In total, 35 compounds were found in Agaricus brasiliensis, 25 in Taiwanofungus camphoratus, 23 in Ganoderma lucidum (Taiwan) and Lentinus edodes, and 16 in G. lucidum (China). Total amounts of all identified metabolites in A. brasiliensis, T. camphoratus, G. lucidum, G. lucidum (China), and L. edodes were 149,950.51, 12,834.18, 9,549.09, 2,788.41, and 111,726.51 mg/kg dry weight, respectively. These metabolites were categorized into 4 groups: free amino acids and derivatives, carbohydrates, carboxylic acids, and nucleosides. Carbohydrates were the most abundant metabolites among all 4 groups, with mannitol having the highest concentration among all analyzed metabolites (848-94,104 mg/kg dry weight). Principal components analysis (PCA) showed obvious distinction among the metabolites of the 5 different kinds of mushrooms analyzed in this study. Thus PCA could provide an optional analytical way of identifying and recognizing the compositions of flavor products. Furthermore, the results of this study demonstrate that NMRbased metabolomics is a powerful tool for differentiating between various medicinal mushrooms.

  3. 1H NMR Spectroscopy and MVA Analysis of Diplodus sargus Eating the Exotic Pest Caulerpa cylindracea.

    Science.gov (United States)

    De Pascali, Sandra A; Del Coco, Laura; Felline, Serena; Mollo, Ernesto; Terlizzi, Antonio; Fanizzi, Francesco P

    2015-06-05

    The green alga Caulerpa cylindracea is a non-autochthonous and invasive species that is severely affecting the native communities in the Mediterranean Sea. Recent researches show that the native edible fish Diplodus sargus actively feeds on this alga and cellular and physiological alterations have been related to the novel alimentary habits. The complex effects of such a trophic exposure to the invasive pest are still poorly understood. Here we report on the metabolic profiles of plasma from D. sargus individuals exposed to C. cylindracea along the southern Italian coast, using 1H NMR spectroscopy and multivariate analysis (Principal Component Analysis, PCA, Orthogonal Partial Least Square, PLS, and Orthogonal Partial Least Square Discriminant Analysis, OPLS-DA). Fish were sampled in two seasonal periods from three different locations, each characterized by a different degree of algal abundance. The levels of the algal bisindole alkaloid caulerpin, which is accumulated in the fish tissues, was used as an indicator of the trophic exposure to the seaweed and related to the plasma metabolic profiles. The profiles appeared clearly influenced by the sampling period beside the content of caulerpin, while the analyses also supported a moderate alteration of lipid and choline metabolism related to the Caulerpa-based diet.

  4. NMR spectroscopy reveals the presence and association of lipids and keratin in adhesive gecko setae

    Science.gov (United States)

    Jain, Dharamdeep; Stark, Alyssa Y.; Niewiarowski, Peter H.; Miyoshi, Toshikazu; Dhinojwala, Ali

    2015-01-01

    Lipid and protein aggregates are one of the fundamental materials of biological systems. Examples include cell membranes, insect cuticle, vertebrate epidermis, feathers, hair and adhesive structures known as ‘setae’ on gecko toes. Until recently gecko setae were assumed to be composed entirely of keratin, but analysis of footprints left behind by geckos walking on surfaces revealed that setae include various kinds of lipids. However, the arrangement and molecular-level behavior of lipids and keratin in the setae is still not known. In the present study we demonstrate, for the first time, the use of Nuclear Magnetic Resonance (NMR) spectroscopy techniques to confirm the presence of lipids and investigate their association with keratin in ‘pristine' sheds, or natural molts of the adhesive toe pad and non-adhesive regions of the skin. Analysis was also carried on the sheds after they were ‘delipidized’ to remove surface lipids. Our results show a distribution of similar lipids in both the skin and toe shed but with different dynamics at a molecular level. The present study can help us understand the gecko system both biologically and for design of synthetic adhesives, but the findings may be relevant to the characteristics of lipid-protein interactions in other biological systems. PMID:25902194

  5. Thermal heterogeneity within aqueous materials quantified by 1H NMR spectroscopy: Multiparametric validation in silico and in vitro

    Science.gov (United States)

    Lutz, Norbert W.; Bernard, Monique

    2018-02-01

    We recently suggested a new paradigm for statistical analysis of thermal heterogeneity in (semi-)aqueous materials by 1H NMR spectroscopy, using water as a temperature probe. Here, we present a comprehensive in silico and in vitro validation that demonstrates the ability of this new technique to provide accurate quantitative parameters characterizing the statistical distribution of temperature values in a volume of (semi-)aqueous matter. First, line shape parameters of numerically simulated water 1H NMR spectra are systematically varied to study a range of mathematically well-defined temperature distributions. Then, corresponding models based on measured 1H NMR spectra of agarose gel are analyzed. In addition, dedicated samples based on hydrogels or biological tissue are designed to produce temperature gradients changing over time, and dynamic NMR spectroscopy is employed to analyze the resulting temperature profiles at sub-second temporal resolution. Accuracy and consistency of the previously introduced statistical descriptors of temperature heterogeneity are determined: weighted median and mean temperature, standard deviation, temperature range, temperature mode(s), kurtosis, skewness, entropy, and relative areas under temperature curves. Potential and limitations of this method for quantitative analysis of thermal heterogeneity in (semi-)aqueous materials are discussed in view of prospective applications in materials science as well as biology and medicine.

  6. Metabolic profiling for studying chemotype variations in Withania somnifera (L.) Dunal fruits using GC-MS and NMR spectroscopy.

    Science.gov (United States)

    Bhatia, Anil; Bharti, Santosh K; Tewari, Shri K; Sidhu, Om P; Roy, Raja

    2013-09-01

    Withania somnifera (L.) Dunal (Solanaceae), commonly known as Ashwagandha, is one of the most valued Indian medicinal plant with several pharmaceutical and nutraceutical applications. Metabolic profiling was performed by GC-MS and NMR spectroscopy on the fruits obtained from four chemotypes of W. somnifera. A combination of (1)H NMR spectroscopy and GC-MS identified 82 chemically diverse metabolites consisting of organic acids, fatty acids, aliphatic and aromatic amino acids, polyols, sugars, sterols, tocopherols, phenolic acids and withanamides in the fruits of W. somnifera. The range of metabolites identified by GC-MS and NMR of W. somnifera fruits showed various known and unknown metabolites. The primary and secondary metabolites observed in this study represent MVA, DOXP, shikimic acid and phenylpropanoid biosynthetic metabolic pathways. Squalene and tocopherol have been rated as the most potent naturally occurring compounds with antioxidant properties. These compounds have been identified by us for the first time in the fruits of W. somnifera. Multivariate principal component analysis (PCA) on GC-MS and NMR data revealed clear distinctions in the primary and secondary metabolites among the chemotypes. The variation in the metabolite concentration among different chemotypes of the fruits of W. somnifera suggest that specific chemovars can be used to obtain substantial amounts of bioactive ingredients for use as potential pharmacological and nutraceuticals agents. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Determination and Quantification of the Local Environments in Stoichiometric and Defect Jarosite by Solid-State 2H NMR Spectroscopy

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Grey, Clare P.; Majzlan, Juraj

    2008-01-01

    illustrate that 2H MAS NMR spectroscopy is an excellent probe of the local environments and defects, on the atomic/molecular level, providing information that is complementary to diffraction techniques and that will help to rationalize the magnetic properties of these materials.......The nature and concentrations of the local environments in a series of deuterated jarosite (nominally AFe3(SO4)2(OD)6 with A = K, Na, and D3O) samples with different levels of iron and cation vacancies have been determined by 2H MAS NMR spectroscopy at ambient temperatures. Three different local...... deuteron environments, Fe2OD, FeOD2, and D2O/D3O+, can be separated based on their very different Fermi contact shifts of delta approximate to 237, 70, and 0 ppm, respectively. The FeOD2 group arises from the charge, compensation of the Fe3+ vacancies, allowing the concentrations of the vacancies...

  8. Protein residue linking in a single spectrum for magic-angle spinning NMR assignment

    Energy Technology Data Exchange (ETDEWEB)

    Andreas, Loren B.; Stanek, Jan; Marchand, Tanguy Le; Bertarello, Andrea; Paepe, Diane Cala-De; Lalli, Daniela; Krejčíková, Magdaléna; Doyen, Camille; Öster, Carl [Université de Lyon, Centre de RMN à Très Hauts Champs, Institut des Sciences Analytiques (CNRS, ENS Lyon, UCB Lyon 1) (France); Knott, Benno; Wegner, Sebastian; Engelke, Frank [Bruker Biospin (Germany); Felli, Isabella C.; Pierattelli, Roberta [University of Florence, Department of Chemistry “Ugo Schiff“and Magnetic Resonance Center (CERM) (Italy); Dixon, Nicholas E. [University of Wollongong, School of Chemistry (Australia); Emsley, Lyndon; Herrmann, Torsten; Pintacuda, Guido, E-mail: guido.pintacuda@ens-lyon.fr [Université de Lyon, Centre de RMN à Très Hauts Champs, Institut des Sciences Analytiques (CNRS, ENS Lyon, UCB Lyon 1) (France)

    2015-07-15

    Here we introduce a new pulse sequence for resonance assignment that halves the number of data sets required for sequential linking by directly correlating sequential amide resonances in a single diagonal-free spectrum. The method is demonstrated with both microcrystalline and sedimented deuterated proteins spinning at 60 and 111 kHz, and a fully protonated microcrystalline protein spinning at 111 kHz, with as little as 0.5 mg protein sample. We find that amide signals have a low chance of ambiguous linkage, which is further improved by linking in both forward and backward directions. The spectra obtained are amenable to automated resonance assignment using general-purpose software such as UNIO-MATCH.

  9. Numerical calculation of spin echo amplitude in pulsed NMR: effects of quadrupole interaction

    International Nuclear Information System (INIS)

    Sobral, R.R.

    1986-01-01

    The spin echo obtained by nuclear magnetic resonance, in systems which atomic nuclei interact with magnetic fields and electric field gradients, present oscillations in function of the time interval between two excitations pulses. Using the density matrix formalism, the amplitudes of these echo is calculated, analytically. In this work, echo amplitudes obtained under different excitation conditions for nuclei of different nuclear spin values are calculated. The numerical results are compared with disposable analytical solutions. Applications of this method to the case of electric field gradient without axial symmetry were studied. Within the used approximation limits, an expression for attnuation of oscillatory behaviour of echo amplitude in function of the time interval between experimentally observed pulses was obtained. (M.C.K.) [pt

  10. 1H HR-MAS NMR and S180 cells: metabolite assignment and evaluation of pulse sequence

    International Nuclear Information System (INIS)

    Oliveira, Aline L. de; Martinelli, Bruno César B.; Lião, Luciano M.; Pereira, Flávia C.; Silveira-Lacerda, Elisangela P.; Alcantara, Glaucia B.

    2014-01-01

    High resolution magic angle spinning 1 H nuclear magnetic resonance spectroscopy (HR-MAS NMR) is a useful technique for evaluation of intact cells and tissues. However, optimal NMR parameters are crucial in obtaining reliable results. To identify the key steps for the optimization of HR-MAS NMR parameters, we assessed different pulse sequences and NMR parameters using sarcoma 180 (S180) cells. A complete assignment of the metabolites of S180 is given to assist future studies. (author)

  11. {sup 1}H HR-MAS NMR and S180 cells: metabolite assignment and evaluation of pulse sequence

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Aline L. de; Martinelli, Bruno César B.; Lião, Luciano M. [Universidade Federal de Goiás (UFG), Goiânia, GO (Brazil). Instituto de Química. Lab. de RMN; Pereira, Flávia C.; Silveira-Lacerda, Elisangela P. [Universidade Federal de Goiás (UFG), Goiânia, GO (Brazil). Instituto de Ciências Biológicas. Laboratório Genética Molecular e Citogenética; Alcantara, Glaucia B., E-mail: glaucia.alcantara@ufms.br [Universidade Federal de Mato Grosso do Sul (UFMS), Campo Grande, MS (Brazil). Inst. de Química

    2014-07-01

    High resolution magic angle spinning {sup 1}H nuclear magnetic resonance spectroscopy (HR-MAS NMR) is a useful technique for evaluation of intact cells and tissues. However, optimal NMR parameters are crucial in obtaining reliable results. To identify the key steps for the optimization of HR-MAS NMR parameters, we assessed different pulse sequences and NMR parameters using sarcoma 180 (S180) cells. A complete assignment of the metabolites of S180 is given to assist future studies. (author)

  12. Fragment-Linking Approach Using (19)F NMR Spectroscopy To Obtain Highly Potent and Selective Inhibitors of β-Secretase.

    Science.gov (United States)

    Jordan, John B; Whittington, Douglas A; Bartberger, Michael D; Sickmier, E Allen; Chen, Kui; Cheng, Yuan; Judd, Ted

    2016-04-28

    Fragment-based drug discovery (FBDD) has become a widely used tool in small-molecule drug discovery efforts. One of the most commonly used biophysical methods in detecting weak binding of fragments is nuclear magnetic resonance (NMR) spectroscopy. In particular, FBDD performed with (19)F NMR-based methods has been shown to provide several advantages over (1)H NMR using traditional magnetization-transfer and/or two-dimensional methods. Here, we demonstrate the utility and power of (19)F-based fragment screening by detailing the identification of a second-site fragment through (19)F NMR screening that binds to a specific pocket of the aspartic acid protease, β-secretase (BACE-1). The identification of this second-site fragment allowed the undertaking of a fragment-linking approach, which ultimately yielded a molecule exhibiting a more than 360-fold increase in potency while maintaining reasonable ligand efficiency and gaining much improved selectivity over cathepsin-D (CatD). X-ray crystallographic studies of the molecules demonstrated that the linked fragments exhibited binding modes consistent with those predicted from the targeted screening approach, through-space NMR data, and molecular modeling.

  13. Spin Dynamics and Quantum Tunneling in Fe8 Nanomagnet and in AFM Rings by NMR

    Energy Technology Data Exchange (ETDEWEB)

    Ho-Baek, Seung [Iowa State Univ., Ames, IA (United States)

    2004-01-01

    In this thesis, our main interest has been to investigate the spin dynamics and quantum tunneling in single molecule magnets (SMMs), For this we have selected two different classes of SMMs: a ferrimagnetic total high spin S = 10 cluster Fe8 and antiferromagnetic (AFM) ring-type clusters. For Fe8, our efforts have been devoted to the investigation of the quantum tunneling of magnetization in the very low temperature region. The most remarkable experimental finding in Fe8 is that the nuclear spin-lattice relaxation rate (1/T{sub l}) at low temperatures takes place via strong collision mechanism, and thus it allows to measure directly the tunneling rate vs T and H for the first time. For AFM rings, we have shown that 1/T{sub l} probes the thermal fluctuations of the magnetization in the intermediate temperature range. We find that the fluctuations are dominated by a single characteristic frequency which has a power law T-dependence indicative of fluctuations due to electron-acoustic phonon interactions.

  14. Spin Dynamics and Quantum Tunneling in Fe8 Nanomagnet and in AFM Rings by NMR

    International Nuclear Information System (INIS)

    Seung-Ho-Baek

    2004-01-01

    In this thesis, our main interest has been to investigate the spin dynamics and quantum tunneling in single molecule magnets (SMMs), For this we have selected two different classes of SMMs: a ferrimagnetic total high spin S = 10 cluster Fe8 and antiferromagnetic (AFM) ring-type clusters. For Fe8, our efforts have been devoted to the investigation of the quantum tunneling of magnetization in the very low temperature region. The most remarkable experimental finding in Fe8 is that the nuclear spin-lattice relaxation rate (1/T l ) at low temperatures takes place via strong collision mechanism, and thus it allows to measure directly the tunneling rate vs T and H for the first time. For AFM rings, we have shown that 1/T l probes the thermal fluctuations of the magnetization in the intermediate temperature range. We find that the fluctuations are dominated by a single characteristic frequency which has a power law T-dependence indicative of fluctuations due to electron-acoustic phonon interactions

  15. Spin dynamics and quantum tunneling in Fe8 nanomagnet and in AFM rings by NMR

    Science.gov (United States)

    Baek, Seung-Ho

    In this thesis, our main interest has been to investigate the spin dynamics and quantum tunneling in single molecule magnets (SMMs). For this we have selected two different classes of SMMs: a ferromagnetic total high spin S = 10 cluster Fe8 and antiferromagnetic (AFM) ring-type clusters. For Fe8, our efforts have been devoted to the investigation of the quantum tunneling of magnetization in the very low temperature region. The most remarkable experimental finding in Fe8 is that the nuclear spin-lattice relaxation rate (1/T1) at low temperatures takes place via strong collision mechanism, and thus it allows to measure directly the tunneling rate vs. T and H for the first time. For AFM rings, we have shown that 1/T1 probes the thermal fluctuations of the magnetization in the intermediate temperature range. We find that the fluctuations are dominated by a single characteristic frequency which has a power-law T-dependence indicative of fluctuations due to electron-acoustic phonon interactions.

  16. Solid-state C-13 and Co-59 NMR spectroscopy of C-13-methylcobalt(III) complexes with amine ligands

    DEFF Research Database (Denmark)

    Ooms, Kristopher J.; Bernard, Guy M.; Kadziola, Anders

    2009-01-01

    Five octahedral Co(III) cations, [trans-Co(en)(2)(X)((CH)-C-13)(3)](n+) where en = ethylenediamine, X = CN-, N-3(-), NH3, NO2- or H2O and n = 1 or 2, well as [Co(NH3)(5)(CH3)-C-13](2+), have been investigated by solid-state C-13 Co-59 NMR spectroscopy. We show that the determination of the Co-59 ...

  17. Human in vivo cardiac phosphorus NMR spectroscopy at 3.0 Tesla

    Science.gov (United States)

    Bruner, Angela Properzio

    One of the newest methods with great potential for use in clinical diagnosis of heart disease is human, cardiac, phosphorus NMR spectroscopy (cardiac p 31 MRS). Cardiac p31 MRS is able to provide quantitative, non-invasive, functional information about the myocardial energy metabolites such as pH, phosphocreatine (PCr), and adenosinetriphosphate (ATP). In addition to the use of cardiac p3l MRS for other types of cardiac problems, studies have shown that the ratio of PCr/ATP and pH are sensitive and specific markers of ischemia at the myocardial level. In human studies, typically performed at 1.5 Tesla, PCr/ATP has been relatively easy to measure but often requires long scan times to provide adequate signal-to-noise (SNR). In addition, pH which relies on identification of inorganic phosphate (Pi), has rarely been obtained. Significant improvement in the quality of cardiac p31 MRS was achieved through the use of the General Electric SIGNATM 3.0 Tesla whole body magnet, improved coil designs and optimized pulse sequences. Phantom and human studies performed on many types of imaging and spectroscopy sequences, identified breathhold gradient-echo imaging and oblique DRESS p31 spectroscopy as the best compromises between SNR, flexibility and quality localization. Both single-turn and quadrature 10-cm diameter, p31 radiofrequency coils, were tested with the quadrature coil providing greater SNR, but at a greater depth to avoid skeletal muscle contamination. Cardiac p31 MRS obtained in just 6 to 8 minutes, gated, showed both improved SNR and discernment of Pi allowing for pH measurement. A handgrip, in-magnet exerciser was designed, created and tested at 1.5 and 3.0 Tesla on volunteers and patients. In ischemic patients, this exercise was adequate to cause a repeated drop in PCr/ATP and pH with approximately eight minutes of isometric exercise at 30% maximum effort. As expected from literature, this exercise did not cause a drop in PCr/ATP for reference volunteers.

  18. 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.

  19. Active site dynamics in NADH oxidase from Thermus thermophilus studied by NMR spin relaxation

    International Nuclear Information System (INIS)

    Miletti, Teresa; Farber, Patrick J.; Mittermaier, Anthony

    2011-01-01

    We have characterized the backbone dynamics of NADH oxidase from Thermus thermophilus (NOX) using a recently-developed suite of NMR experiments designed to isolate exchange broadening, together with 15 N R 1 , R 1ρ , and { 1 H}- 15 N steady-state NOE relaxation measurements performed at 11.7 and 18.8 T. NOX is a 54 kDa homodimeric enzyme that belongs to a family of structurally homologous flavin reductases and nitroreductases with many potential biotechnology applications. Prior studies have suggested that flexibility is involved in the catalytic mechanism of the enzyme. The active site residue W47 was previously identified as being particularly important, as its level of solvent exposure correlates with enzyme activity, and it was observed to undergo “gating” motions in computer simulations. The NMR data are consistent with these findings. Signals from W47 are dynamically broadened beyond detection and several other residues in the active site have significant R ex contributions to transverse relaxation rates. In addition, the backbone of S193, whose side chain hydroxyl proton hydrogen bonds directly with the FMN cofactor, exhibits extensive mobility on the ns–ps timescale. We hypothesize that these motions may facilitate structural rearrangements of the active site that allow NOX to accept both FMN and FAD as cofactors.

  20. THz Dynamic Nuclear Polarization NMR.

    Science.gov (United States)

    Nanni, Emilio A; Barnes, Alexander B; Griffin, Robert G; Temkin, Richard J

    2011-08-29

    Dynamic nuclear polarization (DNP) increases the sensitivity of nuclear magnetic resonance (NMR) spectroscopy by using high frequency microwaves to transfer the polarization of the electrons to the nuclear spins. The enhancement in NMR sensitivity can amount to a factor of well above 100, enabling faster data acquisition and greatly improved NMR measurements. With the increasing magnetic fields (up to 23 T) used in NMR research, the required frequency for DNP falls into the THz band (140-600 GHz). Gyrotrons have been developed to meet the demanding specifications for DNP NMR, including power levels of tens of watts; frequency stability of a few megahertz; and power stability of 1% over runs that last for several days to weeks. Continuous gyrotron frequency tuning of over 1 GHz has also been demonstrated. The complete DNP NMR system must include a low loss transmission line; an optimized antenna; and a holder for efficient coupling of the THz radiation to the sample. This paper describes the DNP NMR process and illustrates the THz systems needed for this demanding spectroscopic application. THz DNP NMR is a rapidly developing, exciting area of THz science and technology.

  1. Experimental Determination of pK[subscript a] Values and Metal Binding for Biomolecular Compounds Using [superscript 31]P NMR Spectroscopy

    Science.gov (United States)

    Swartz, Mason A.; Tubergen, Philip J.; Tatko, Chad D.; Baker, Rachael A.

    2018-01-01

    This lab experiment uses [superscript 31]P NMR spectroscopy of biomolecules to determine pK[subscript a] values and the binding energies of metal/biomolecule complexes. Solutions of adenosine nucleotides are prepared, and a series of [superscript 31]P NMR spectra are collected as a function of pH and in the absence and presence of magnesium or…

  2. High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

    International Nuclear Information System (INIS)

    Wang, Xin

    1996-12-01

    X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). The spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of Kα and Kβ emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS

  3. High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xin [Univ. of California, Davis, CA (United States). Dept. of Applied Science

    1996-12-01

    X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). The spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.

  4. COVALENT BINDING OF REDUCED METABOLITES OF [15N3] TNT TO SOIL ORGANIC MATTER DURING A BIOREMEDIATION PROCESS ANALYZED BY 15N NMR SPECTROSCOPY. (R826646)

    Science.gov (United States)

    Evidence is presented for the covalent binding ofbiologically reduced metabolites of 2,4,6-15N3-trinitrotoluene(TNT) to different soil fractions (humic acids, fulvicacids, and humin) using liquid 15N NMR spectroscopy. Asilylation p...

  5. ^51V NMR Study of the Magnetic Structure of the Frustrated Zig-Zag Spin-1 Chain Compound CaV2O4

    Science.gov (United States)

    Zong, X.; Suh, B. J.; Niazi, A.; Johnston, D. C.

    2007-03-01

    ^51V NMR measurements have been performed on a single crystal of orthorhombic (at room temperature) CaV2O4 in zero applied magnetic field and with a small perturbing field up to H = 2 T, at temperatures well below the N'eel temperature TN= 78 K@. The c-axis is parallel to the chains. At H = 0, a broad ^51V NMR spectrum with a peak at 237 MHz was observed. The effective local hyperfine field Heff = 21.2 T corresponding to the peak frequency 237 MHz is in good agreement with expectation for the V^3+ S = 1 spin state. In Hc, the spectrum splits into two parts that are equally separated from the peak position at zero field. The separation of the parts depends strongly both on the magnitude and direction of H with respect to the crystal axes. Our NMR results are consistent with a collinear antiferromagnetic spin structure with the spin direction along the b-axis, which together with the magnetization data suggest that the antiferromagnetic long-range order arises from an order-from-disorder mechanism. We also present the temperature and orientation dependence of the spin-lattice relaxation rate 1/T1.

  6. 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...

  7. An automated framework for NMR resonance assignment through simultaneous slice picking and spin system forming

    KAUST Repository

    Abbas, Ahmed

    2014-04-19

    Despite significant advances in automated nuclear magnetic resonance-based protein structure determination, the high numbers of false positives and false negatives among the peaks selected by fully automated methods remain a problem. These false positives and negatives impair the performance of resonance assignment methods. One of the main reasons for this problem is that the computational research community often considers peak picking and resonance assignment to be two separate problems, whereas spectroscopists use expert knowledge to pick peaks and assign their resonances at the same time. We propose a novel framework that simultaneously conducts slice picking and spin system forming, an essential step in resonance assignment. Our framework then employs a genetic algorithm, directed by both connectivity information and amino acid typing information from the spin systems, to assign the spin systems to residues. The inputs to our framework can be as few as two commonly used spectra, i.e., CBCA(CO)NH and HNCACB. Different from the existing peak picking and resonance assignment methods that treat peaks as the units, our method is based on \\'slices\\', which are one-dimensional vectors in three-dimensional spectra that correspond to certain (N, H) values. Experimental results on both benchmark simulated data sets and four real protein data sets demonstrate that our method significantly outperforms the state-of-the-art methods while using a less number of spectra than those methods. Our method is freely available at http://sfb.kaust.edu.sa/Pages/Software.aspx. © 2014 Springer Science+Business Media.

  8. Synthesis, spectroscopy, and hydrogen/deuterium exchange in high-spin iron(II) hydride complexes.

    Science.gov (United States)

    Dugan, Thomas R; Bill, Eckhard; MacLeod, K Cory; Brennessel, William W; Holland, Patrick L

    2014-03-03

    Very few hydride complexes are known in which the metals have a high-spin electronic configuration. We describe the characterization of several high-spin iron(II) hydride/deuteride isotopologues and their exchange reactions with one another and with H2/D2. Though the hydride/deuteride signal is not observable in NMR spectra, the choice of isotope has an influence on the chemical shifts of distant protons in the dimers through the paramagnetic isotope effect on chemical shift. This provides the first way to monitor the exchange of H and D in the bridging positions of these hydride complexes. The rate of exchange depends on the size of the supporting ligand, and this is consistent with the idea that H2/D2 exchange into the hydrides occurs through the dimeric complexes rather than through a transient monomer. The understanding of H/D exchange mechanisms in these high-spin iron hydride complexes may be relevant to postulated nitrogenase mechanisms.

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

    International Nuclear Information System (INIS)

    Zamar, R.C.; Gonzalez, C.E.; Mensio, O.

    1998-01-01

    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 1D ), in addition to the conventional Zeeman relaxation time (T 1Z ) in a frequency range of several decades. When applying this technique to nematic thermotropic liquid crystals, T 1D showed to depend almost exclusively on the order fluctuation of the director mechanism in the whole frequency range. This unique characteristic of T 1D makes dipolar order relaxation experiments specially useful for studying the frequency and temperature dependence of the spectral properties of the collective motions. (author)

  10. Magic-Angle-Spinning NMR Magnet Development: Field Analysis and Prototypes

    Science.gov (United States)

    Voccio, John; Hahn, Seungyong; Park, Dong Keun; Ling, Jiayin; Kim, Youngjae; Bascuñán, Juan; Iwasa, Yukikazu

    2013-01-01

    We are currently working on a program to complete a 1.5 T/75 mm RT bore magic-angle-spinning nuclear magnetic resonance magnet. The magic-angle-spinning magnet comprises a z-axis 0.866-T solenoid and an x-axis 1.225-T dipole, each to be wound with NbTi wire and operated at 4.2 K in persistent mode. A combination of the fields creates a 1.5-T field pointed at 54.74 degrees (magic angle) from the rotation (z) axis. In the first year of this 3-year program, we have completed magnetic analysis and design of both coils. Also, using a winding machine of our own design and fabrication, we have wound several prototype dipole coils with NbTi wire. As part of this development, we have repeatedly made successful persistent NbTi-NbTi joints with this multifilamentary NbTi wire. PMID:24058275

  11. Impact of Adenovirus infection in host cell metabolism evaluated by (1)H-NMR spectroscopy.

    Science.gov (United States)

    Silva, Ana Carina; P Teixeira, Ana; M Alves, Paula

    2016-08-10

    Adenovirus-based vectors are powerful vehicles for gene transfer applications in vaccination and gene therapy. Although highly exploited in the clinical setting, key aspects of the adenovirus biology are still not well understood, in particular the subversion of host cell metabolism during viral infection and replication. The aim of this work was to gain insights on the metabolism of two human cell lines (HEK293 and an amniocyte-derived cell line, 1G3) after infection with an adenovirus serotype 5 vector (AdV5). In order to profile metabolic alterations, we used (1)H-NMR spectroscopy, which allowed the quantification of 35 metabolites in cell culture supernatants with low sample preparation and in a relatively short time. Significant differences between both cell lines in non-infected cultures were identified, namely in glutamine and acetate metabolism, as well as by-product secretion. The main response to AdV5 infection was an increase in glucose consumption and lactate production rates. Moreover, cultures performed with or without glutamine supplementation confirmed the exhaustion of this amino acid as one of the main causes of lower AdV5 production at high cell densities (10- and 1.5-fold less specific yields in HEK293 and 1G3 cells, respectively), and highlighted different degrees of glutamine dependency of adenovirus replication in each cell line. The observed metabolic alterations associated with AdV5 infection and specificity of the host cell line can be useful for targeted bioprocess optimization. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. NMR spectroscopy of cultured astrocytes: effects of glutamine and the gliotoxin fluorocitrate.

    Science.gov (United States)

    Hassel, B; Sonnewald, U; Unsgård, G; Fonnum, F

    1994-06-01

    Glial synthesis of glutamine, citrate, and other carbon skeletons, as well as metabolic effects of the gliotoxin fluorocitrate, were studied in cultured astrocytes with 13C and 31P NMR spectroscopy. [2-13C]Acetate and [1-13C]glucose were used as labeled precursors. In some experiments glutamine (2.5 mM) was added to the culture medium. Fluorocitrate (20 microM) inhibited the tricarboxylic acid (TCA) cycle without affecting the level of ATP. The net export of glutamine was reduced significantly, and that of citrate increased similarly, consistent with an inhibition of aconitase. Fluorocitrate (100 microM) inhibited TCA cycle activity even more and (without addition of glutamine) caused a 40% reduction in the level of ATP. In the presence of 2.5 mM glutamine, 100 microM fluorocitrate did not affect ATP levels, although glutamine synthesis was nearly fully blocked. The consumption of the added glutamine increased with increasing concentrations of fluorocitrate, whereas the consumption of glucose decreased. This shows that glutamine fed into the TCA cycle, substituting for glucose as an energy substrate. These findings may explain how fluorocitrate selectively lowers the level of glutamine and inhibits glutamine formation in the brain in vivo, viz., not by depleting glial cells of ATP, but by causing a rerouting of 2-oxoglutarate from glutamine synthesis into the TCA cycle during inhibition of aconitase. Analysis of the 13C labeling of the C-2 versus the C-4 positions in glutamine obtained with [2-13C]acetate revealed that 57% of the TCA cycle intermediates were lost per turn of the cycle.(ABSTRACT TRUNCATED AT 250 WORDS)

  13. Chemical profile of beans cultivars (Phaseolus vulgaris) by 1H NMR - high resolution magic angle spinning (HR-MAS);Perfil quimico de cultivares de feijao (Phaseolus vulgaris) pela tecnica de high resolution magic angle spinning (HR-MAS)

    Energy Technology Data Exchange (ETDEWEB)

    Liao, Luciano Morais; Choze, Rafael; Cavalcante, Pedro Paulo Araujo; Santos, Suzana da Costa; Ferri, Pedro Henrique, E-mail: luciano@quimica.ufg.b [Universidade Federal de Goias (UFG), Goiania, GO (Brazil). Inst. de Quimica; Ferreira, Antonio Gilberto [Universidade Federal de Sao Carlos (UFScar), SP (Brazil). Dept. de Quimica

    2010-07-01

    The application of one-dimensional proton high-resolution magic angle spinning ({sup 1}H HR-MAS) NMR combined with a typical advantages of solid and liquid-state NMR techniques was used as input variables for the multivariate statistical analysis. In this paper, different cultivars of beans (Phaseolus vulgaris) developed and in development by EMBRAPA - Arroz e Feijao were analyzed by {sup 1}H HR-MAS, which have been demonstrated to be a valuable tool in its differentiation according chemical composition and avoid the manipulation of the samples as used in other techniques. (author)

  14. Correlating the P-31 NMR Chemical Shielding Tensor and the (2)J(P,C) Spin-Spin Coupling Constants with Torsion Angles zeta and alpha in the Backbone of Nucleic Acids

    Czech Academy of Sciences Publication Activity Database

    Benda, Ladislav; Sochorová Vokáčová, Zuzana; Straka, Michal; Sychrovský, Vladimír

    2012-01-01

    Roč. 116, č. 12 (2012), s. 3823-3833 ISSN 1520-6106 R&D Projects: GA ČR GAP205/10/0228; GA ČR GPP208/10/P398; GA ČR GA203/09/2037 Institutional research plan: CEZ:AV0Z40550506 Keywords : nucleic acids * phosphorus NMR * NMR calculations * cross-correlated relaxation * spin–spin coupling constants Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.607, year: 2012

  15. 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…

  16. beta-Ureidopropionase deficiency: a novel inborn error of metabolism discovered using NMR spectroscopy on urine

    NARCIS (Netherlands)

    Moolenaar, S. H.; Göhlich-Ratmann, G.; Engelke, U. F.; Spraul, M.; Humpfer, E.; Dvortsak, P.; Voit, T.; Hoffmann, G. F.; Bräutigam, C.; van Kuilenburg, A. B.; van Gennip, A.; Vreken, P.; Wevers, R. A.

    2001-01-01

    In this work, NMR investigations that led to the discovery of a new inborn error of metabolism, beta-ureidopropionase (UP) deficiency, are reported. 1D (1)H-NMR experiments were performed using a patient's urine. 3-Ureidopropionic acid was observed in elevated concentrations in the urine spectrum. A

  17. Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations.

    Science.gov (United States)

    Wang, Tuo; Yang, Hui; Kubicki, James D; Hong, Mei

    2016-06-13

    The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iβ, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D (13)C-(13)C correlation spectra of uniformly (13)C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose (13)C chemical shifts differ significantly from the (13)C chemical shifts of the Iα and Iβ allomorphs, indicating that plant primary-wall cellulose has different conformations, packing, and hydrogen bonding from celluloses of other organisms. 2D (13)C-(13)C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Celluloses f and g are well mixed chains on the microfibril surface, celluloses a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of

  18. NMR study of spin fluctuations and superconductivity in LaFeAsO1-xHx

    Science.gov (United States)

    Fujiwara, Naoki; Sakurai, Ryosuke; Iimura, Soushi; Matsuishi, Satoru; Hosono, Hideo; Yamakawa, Yoichi; Kontani, Hiroshi

    2013-03-01

    We have performed NMR measurements in LaFeAsO1-xHx, an isomorphic compound of LaFeAsO1-xFx. LaFeAsO1-xHx is most recently known for having double superconducting (SC) domes on H doping. LaFeAsO1-xHx is an electron- doped system, and protons act as H-1 as well as F-1. The first SC dome is very similar between F and H doping, suggesting that H doping supplies the same amount of electrons as F doping. Interestingly, an excess amount of H up to x=0.5 can be replaced with O2-. In the H-overdoped regime (x > 0 . 2), LaFeAsO1-xHx undergoes the second superconducting state. We measured the relaxation rate of LaFeAsO1-xHx for x=0.2 and 0.4, and fond an anomalous electronic state; spin fluctuations measured from 1 /T1 T is enhanced with increasing the doping level from x = 0 . 2 to 0.4. The enhancement of spin fluctuations with increasing carrier doping is a new phenomenon that has not observed in LaFeAsO1-xFx in which the upper limit of the doping level is at most x = 0 . 2 . We will discuss the phenomenon in relation to superconductivity. Grant (KAKENHI 23340101) from the Ministry of Education, Sports and Science, Japan

  19. Pneumatic switched angle spinning NMR probe with capacitively coupled double saddle coil.

    Science.gov (United States)

    Litvak, Ilya M; Espinosa, Catalina A; Shapiro, Rebecca A; Oldham, Andrew N; Duong, Vincent V; Martin, Rachel W

    2010-10-01

    Switched angle spinning (SAS) experiments can be used for generating isotropic-anisotropic correlations in oriented samples in a single experiment. In order for these methods to become widespread, specialized hardware is required. Here we describe the electronic and mechanical design and performance of a double-resonance SAS probe. Unlike many previous SAS probe implementations, the focus here is on systems where the dipolar couplings are partially averaged by molecular motion. This probe has a moving double saddle coil capacitively coupled to the stationary circuit. Angle switching is accomplished by a steam engine-type pneumatic mechanism. The speed and stability of the switching hardware for SAS experiments are demonstrated using spectra of model compounds. Copyright © 2010 Elsevier Inc. All rights reserved.

  20. Microwave field distribution in a magic angle spinning dynamic nuclear polarization NMR probe.

    Science.gov (United States)

    Nanni, Emilio A; Barnes, Alexander B; Matsuki, Yoh; Woskov, Paul P; Corzilius, Björn; Griffin, Robert G; Temkin, Richard J

    2011-05-01

    We present a calculation of the microwave field distribution in a magic angle spinning (MAS) probe utilized in dynamic nuclear polarization (DNP) experiments. The microwave magnetic field (B(1S)) profile was obtained from simulations performed with the High Frequency Structure Simulator (HFSS) software suite, using a model that includes the launching antenna, the outer Kel-F stator housing coated with Ag, the RF coil, and the 4mm diameter sapphire rotor containing the sample. The predicted average B(1S) field is 13μT/W(1/2), where S denotes the electron spin. For a routinely achievable input power of 5W the corresponding value is γ(S)B(1S)=0.84MHz. The calculations provide insights into the coupling of the microwave power to the sample, including reflections from the RF coil and diffraction of the power transmitted through the coil. The variation of enhancement with rotor wall thickness was also successfully simulated. A second, simplified calculation was performed using a single pass model based on Gaussian beam propagation and Fresnel diffraction. This model provided additional physical insight and was in good agreement with the full HFSS simulation. These calculations indicate approaches to increasing the coupling of the microwave power to the sample, including the use of a converging lens and fine adjustment of the spacing of the windings of the RF coil. The present results should prove useful in optimizing the coupling of microwave power to the sample in future DNP experiments. Finally, the results of the simulation were used to predict the cross effect DNP enhancement (ϵ) vs. ω(1S)/(2π) for a sample of (13)C-urea dissolved in a 60:40 glycerol/water mixture containing the polarizing agent TOTAPOL; very good agreement was obtained between theory and experiment. Copyright © 2011 Elsevier Inc. All rights reserved.

  1. 1H-detected 1H- 1H correlation spectroscopy of a stereo-array isotope labeled amino acid under fast magic-angle spinning

    Science.gov (United States)

    Takahashi, Hiroki; Kainosho, Masatsune; Akutsu, Hideo; Fujiwara, Toshimichi

    2010-04-01

    The combined use of selective deuteration, stereo-array isotope labeling (SAIL), and fast magic-angle spinning effectively suppresses the 1H-1H dipolar couplings in organic solids. This method provided the high-field 1H NMR linewidths comparable to those achieved by combined rotation and multiple-pulse spectroscopy. This technique was applied to two-dimensional 1H-detected 1H-1H polarization transfer CHH experiments of valine. The signal sensitivity for the 1H-detected CHH experiments was greater than that for the 13C-detected 1H-1H polarization transfer experiments by a factor of 2-4. We obtained the 1H-1H distances in SAIL valine by CHH experiments with an accuracy of about 0.2 Å by using a theory developed for 1H-1H polarization transfer in 13C-labeled organic compounds.

  2. The structure of phosphate and borosilicate glasses and their structural evolution at high temperatures as studied with solid state NMR spectroscopy: Phase separation, crystallisation and dynamic species exchange

    International Nuclear Information System (INIS)

    Wegner, S.; Van Wullen, L.; Tricot, G.; Tricot, G.

    2010-01-01

    In this contribution we present an in-depth study of the network structure of different phosphate based and borosilicate glasses and its evolution at high temperatures. Employing a range of advanced solid state NMR methodologies, complemented by the results of XPS, the structural motifs on short and intermediate length scales are identified. For the phosphate based glasses, at temperatures above the glass transition temperature Tg, structural relaxation processes and the devitrification of the glasses were monitored in situ employing MAS NMR spectroscopy and X-ray diffraction. Dynamic species exchange involving rapid P-O-P and P-O-Al bond breaking and reforming was observed employing in situ 27 Al and 31 P MAS NMR spectroscopy and could be linked to viscous flow. For the borosilicate glasses, an atomic scale investigation of the phase separation processes was possible in a combined effort of ex situ NMR studies on glass samples with different thermal histories and in situ NMR studies using high temperature MAS NMR spectroscopy including 11 B MAS, 29 Si MAS and in situ 29 Si{ 11 B} REAPDOR NMR spectroscopy. (authors)

  3. A new carbamidemethyl-linked lanthanoid chelating tag for PCS NMR spectroscopy of proteins in living HeLa cells

    Energy Technology Data Exchange (ETDEWEB)

    Hikone, Yuya [Tokyo Metropolitan University, Department of Chemistry, Graduate School of Science and Engineering (Japan); Hirai, Go [RIKEN, Synthetic Organic Chemistry Laboratory (Japan); Mishima, Masaki [Tokyo Metropolitan University, Department of Chemistry, Graduate School of Science and Engineering (Japan); Inomata, Kohsuke [RIKEN, Quantitative Biology Center (Japan); Ikeya, Teppei; Arai, Souichiro [Tokyo Metropolitan University, Department of Chemistry, Graduate School of Science and Engineering (Japan); Shirakawa, Masahiro [Japan Agency for Medical Research and Development, AMED-CREST (Japan); Sodeoka, Mikiko [RIKEN, Synthetic Organic Chemistry Laboratory (Japan); Ito, Yutaka, E-mail: ito-yutaka@tmu.ac.jp [Tokyo Metropolitan University, Department of Chemistry, Graduate School of Science and Engineering (Japan)

    2016-10-15

    Structural analyses of proteins under macromolecular crowding inside human cultured cells by in-cell NMR spectroscopy are crucial not only for explicit understanding of their cellular functions but also for applications in medical and pharmaceutical sciences. In-cell NMR experiments using human cultured cells however suffer from low sensitivity, thus pseudocontact shifts from protein-tagged paramagnetic lanthanoid ions, analysed using sensitive heteronuclear two-dimensional correlation NMR spectra, offer huge potential advantage in obtaining structural information over conventional NOE-based approaches. We synthesised a new lanthanoid-chelating tag (M8-CAM-I), in which the eight-fold, stereospecifically methylated DOTA (M8) scaffold was retained, while a stable carbamidemethyl (CAM) group was introduced as the functional group connecting to proteins. M8-CAM-I successfully fulfilled the requirements for in-cell NMR: high-affinity to lanthanoid, low cytotoxicity and the stability under reducing condition inside cells. Large PCSs for backbone N–H resonances observed for M8-CAM-tagged human ubiquitin mutant proteins, which were introduced into HeLa cells by electroporation, demonstrated that this approach readily provides the useful information enabling the determination of protein structures, relative orientations of domains and protein complexes within human cultured cells.

  4. A new carbamidemethyl-linked lanthanoid chelating tag for PCS NMR spectroscopy of proteins in living HeLa cells

    International Nuclear Information System (INIS)

    Hikone, Yuya; Hirai, Go; Mishima, Masaki; Inomata, Kohsuke; Ikeya, Teppei; Arai, Souichiro; Shirakawa, Masahiro; Sodeoka, Mikiko; Ito, Yutaka

    2016-01-01

    Structural analyses of proteins under macromolecular crowding inside human cultured cells by in-cell NMR spectroscopy are crucial not only for explicit understanding of their cellular functions but also for applications in medical and pharmaceutical sciences. In-cell NMR experiments using human cultured cells however suffer from low sensitivity, thus pseudocontact shifts from protein-tagged paramagnetic lanthanoid ions, analysed using sensitive heteronuclear two-dimensional correlation NMR spectra, offer huge potential advantage in obtaining structural information over conventional NOE-based approaches. We synthesised a new lanthanoid-chelating tag (M8-CAM-I), in which the eight-fold, stereospecifically methylated DOTA (M8) scaffold was retained, while a stable carbamidemethyl (CAM) group was introduced as the functional group connecting to proteins. M8-CAM-I successfully fulfilled the requirements for in-cell NMR: high-affinity to lanthanoid, low cytotoxicity and the stability under reducing condition inside cells. Large PCSs for backbone N–H resonances observed for M8-CAM-tagged human ubiquitin mutant proteins, which were introduced into HeLa cells by electroporation, demonstrated that this approach readily provides the useful information enabling the determination of protein structures, relative orientations of domains and protein complexes within human cultured cells.

  5. Spin polarized auger electron spectroscopy (SPAES): An element specific local magnetization probe of magnetic materials

    Science.gov (United States)

    Anilturk, Onder S.

    Spin Polarized Auger Electron Spectroscopy (SPAES) is found to have application for investigating fundamental properties as well as element specific local magnetization information on magnetic materials. By using the uniqueness of the UTA-SEMPA tool, one can obtain the surface magnetic domain microstructure and also perform SPAES studies by probing a single domain at the surface. In the current study, knowing the probed domain, spin polarization of electrons from super Coster-Kronig MVV Auger emissions on 3%Si-Fe sheets have been investigated. It is observed that on both sides of 180° domains, separated by a domain wall with an out-of-plane component of magnetization, the spin polarized Auger spectra exhibit similar distributions with high polarization structures, which are consistent with the published data. The element specificity of the system is applied to Gd-Co composite system. Details of 4d core hole initiated Auger transitions showed that the 5d states have enhanced spin polarization, confirming the coupling of moments in the composite system via 5d states of Gd. It is also unambiguously observed that Co magnetic moments are indeed aligned antiparallel to the Gd ones via 4f-5d positive exchange and 3d-5d hybridization.

  6. Highly efficient F-19 heteronuclear decoupling in solid-state NMR spectroscopy using supercycled refocused-CW irradiation

    DEFF Research Database (Denmark)

    Equbal, Asif; Basse, Kristoffer; Nielsen, Niels Christian

    2016-01-01

    We present heteronuclear F-19 refocused CW (rCW) decoupling pulse sequences for solid-state magic-angle- spinning NMR applications. The decoupling sequences have been designed specifically to ensure suppression of the pertinent C-13-F-19 dipolar coupling interactions while simultaneously suppress......We present heteronuclear F-19 refocused CW (rCW) decoupling pulse sequences for solid-state magic-angle- spinning NMR applications. The decoupling sequences have been designed specifically to ensure suppression of the pertinent C-13-F-19 dipolar coupling interactions while simultaneously...... suppressing strong anisotropic chemical shift as well as homonuclear F-19-F-19 dipolar coupling effects as typically present in perfluorated compounds. In an extensive numerical and experimental analysis using a rigid, organic solid as a model compound, it becomes evident that the supercycled rCW schemes...... of which clearly render the new rCW schemes the methods of choice for 19F decoupling in rigid, fluorinated compounds - which is further supported by a Floquet-based theoretical analysis....

  7. Non-polymeric asymmetric binary glass-formers. I. Main relaxations studied by dielectric, 2H NMR, and 31P NMR spectroscopy

    Science.gov (United States)

    Pötzschner, B.; Mohamed, F.; Bächer, C.; Wagner, E.; Lichtinger, A.; Minikejew, R.; Kreger, K.; Schmidt, H.-W.; Rössler, E. A.

    2017-04-01

    In Paper I of this series of two papers we study the main relaxations of a binary glass former made of the low-Tg component tripropyl phosphate (TPP, Tg = 134 K) and of a specially synthesized (deuterated) spirobichroman derivative (SBC, Tg = 356 K) as the non-polymeric high-Tg component for the full concentration range. A large Tg contrast of the neat components is put into effect. Dielectric spectroscopy and different techniques of 2H nuclear magnetic resonance (NMR) as well as of 31P NMR spectroscopy allow to selectively probe the dynamics of the components. For all concentrations, two well separated liquid-like processes are identified. The faster α2-process associated with the low-Tg component TPP shows pronounced dynamic heterogeneities reflected by quasi-logarithmic correlation functions at low TPP concentrations. The slower α1-process involves the reorientation of the high-Tg component SBC. Its correlation function is Kohlrausch-like as in neat glass formers. The corresponding time constants and consequently their glass transition temperatures Tg1 and Tg2 differ more the lower the TPP concentration is. Plasticizer and anti-plasticizer effect, respectively, is observed. At low temperatures a situation arises that the TPP molecules isotropically reorient in an arrested SBC matrix (Tg2 TPP gets arrested too. We find indications that a fraction of the TPP molecule takes part in the slower α1-process of the high-Tg component. All the features known from polymer-plasticizer systems are rediscovered in this non-polymeric highly asymmetric binary mixture. In Paper II [B. Pötzschner et al., J. Chem. Phys. 146, 164504 (2017)] we study the secondary (β-) relaxations of the mixtures.

  8. HIV-1 Capsid Function is Regulated by Dynamics: Quantitative Atomic-Resolution Insights by Integrating Magic-Angle-Spinning NMR, QM/MM, and MD.

    Science.gov (United States)

    Zhang, Huilan; Hou, Guangjin; Lu, Manman; Ahn, Jinwoo; Byeon, In-Ja L; Langmead, Christopher J; Perilla, Juan R; Hung, Ivan; Gor'kov, Peter L; Gan, Zhehong; Brey, William W; Case, David A; Schulten, Klaus; Gronenborn, Angela M; Polenova, Tatyana

    2016-10-05

    HIV-1 CA capsid protein possesses intrinsic conformational flexibility, which is essential for its assembly into conical capsids and interactions with host factors. CA is dynamic in the assembled capsid, and residues in functionally important regions of the protein undergo motions spanning many decades of timescales. Chemical shift anisotropy (CSA) tensors, recorded in magic-angle-spinning NMR experiments, provide direct residue-specific probes of motions on nano- to microsecond timescales. We combined NMR, MD, and Density-Functional-Theory calculations, to gain quantitative understanding of internal backbone dynamics in CA assemblies, and found that the dynamically averaged 15 N CSA tensors calculated by this joined protocol are in remarkable agreement with experiment. Thus, quantitative atomic-level understanding of the relationships between CSA tensors, local backbone structure and motions in CA assemblies is achieved, demonstrating the power of integrating NMR experimental data and theory for characterizing atomic-resolution dynamics in biological systems.

  9. Solid-state NMR basic principles and practice

    CERN Document Server

    Apperley, David C; Hodgkinson, Paul

    2014-01-01

    Nuclear Magnetic Resonance (NMR) has proved to be a uniquely powerful and versatile tool for analyzing and characterizing chemicals and materials of all kinds. This book focuses on the latest developments and applications for "solid-state" NMR, which has found new uses from archaeology to crystallography to biomaterials and pharmaceutical science research. The book will provide materials engineers, analytical chemists, and physicists, in and out of lab, a survey of the techniques and the essential tools of solid-state NMR, together with a practical guide on applications. In this concise introduction to the growing field of solid-state nuclear magnetic resonance spectroscopy The reader will find: * Basic NMR concepts for solids, including guidance on the spin-1/2 nuclei concept * Coverage of the quantum mechanics aspects of solid state NMR and an introduction to the concept of quadrupolar nuclei * An understanding relaxation, exchange and quantitation in NMR * An analysis and interpretation of NMR data, with e...

  10. Direct detection of the mercury-nitrogen bond in the thymine-Hg-II-thymine base-pair with Hg-199 NMR spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Dairaku, T.; Furuita, K.; Sato, H.; Šebera, Jakub; Yamanaka, D.; Otaki, H.; Kikkawa, S.; Kondo, Y.; Katahira, R.; Bickelhaupt, F. M.; Guerra, C. F.; Ono, A.; Sychrovský, Vladimír; Kojima, C.; Tanaka, Y.

    2015-01-01

    Roč. 51, č. 40 (2015), s. 8488-8491 ISSN 1359-7345 R&D Projects: GA ČR GAP205/10/0228 Institutional support: RVO:61388963 Keywords : T-Hg-T * NMR * spin-spin coupling * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.567, year: 2015 http://pubs.rsc.org/en/content/articlepdf/2015/cc/c5cc02423d

  11. Use of resonance ionization spectroscopy to detect DNA bands on ultrathin spin-coated gels.

    Science.gov (United States)

    Doktycz, M J; Gibson, W A; Arlinghaus, H F; Allen, R C; Jacobson, K B

    1993-01-01

    Development of alternative electrophoresis procedures are necessary for large volume sequencing and mapping studies. The use of stable isotopes as DNA labels and ultrathin gels promises to greatly increase the rate of sequencing. Spin coating is presented as an alternative method for producing ultrathin polyacrylamide gels. The technique has the potential of producing gels of micron to submicron thicknesses by varying the viscosity of the acrylamide solution and the spinning speed. Thirty micron thick 6% (weight %) gels were produced in this manner. Tin-labeled DNA oligomers were electrophoresed and detected using sputter-initiated resonance ionization spectroscopy (SIRIS). The usefulness of SIRIS and laser atomization RIS (LARIS) to sample the surface and deeper layers of 240 microns thick gels was investigated. With LARIS, whole cross-sections of the gel can be atomized, possibly allowing complete sampling of labels.

  12. Study of spin-temperature effects using energy-ordered continuum gamma-ray spectroscopy technique

    Energy Technology Data Exchange (ETDEWEB)

    Baktash, C.; Halbert, M.L.; Hensley, D.C.; Johnson, N.R.; Lee, I.Y.; McConnell, J.W.; McGowan, F.K.

    1990-01-01

    We have investigated a new continuum {gamma}-ray spectroscopy technique which is based on the detection of all emitted {gamma} rays in a 4{pi} detector system, and ordering them according to their energies on an event-by-event basis. The technique allows determination of gamma strength functions, and rotational damping width as a function of spin and temperature. Thus, it opens up the possibility of studying the onset of motional narrowing, order-to-chaos transition, and the mapping of the evolution of nuclear collectivity with a spin and temperature. Application of the technique for preferential entry-state population, exit-channel selection, and feeding of the discrete states via selective pathways will be discussed. 20 refs., 4 figs.

  13. Application of spatially resolved NMR spectroscopy for high resolution of heterogeneous samples

    International Nuclear Information System (INIS)

    Kozminski, W.

    2000-01-01

    An improved method for acquisition of high resolution NMR spectra, exclusively in an arbitrarily chosen volume element of the sample, is presented. The proposed pulse sequence utilizes the Double Pulsed Field Gradient Selective Echo (DPFGSE) element, that offers a high selectivity and superior phase and baseline properties of the resulted spectra. The discussed experiment is applicable in all NMR spectrometers, equipped with at least a single-axis PFG accessory. The effectiveness of the proposed technique is demonstrated by acquisition of 1 H NMR spectra from different volume elements of a heterogeneous CDCl 3 /D 2 O sample. (author)

  14. Investigation of structural transition of regenerated silk fibroin aqueous solution by Rheo-NMR spectroscopy.

    Science.gov (United States)

    Ohgo, Kosuke; Bagusat, Frank; Asakura, Tetsuo; Scheler, Ulrich

    2008-03-26

    In this study we applied Rheo-NMR to investigate the structural change of Bombyx mori silk fibroin in aqueous solution under shear. Monitoring the time dependence of 1H solution NMR spectra of silk fibroin subjected to constant shear strain, signal intensities of random coil decreased suddenly during shear while peaks from beta-sheet structure did not arise in the solution spectra. After these experiments, an aggregate of silk was found in the Couette flow cell and its secondary structure was determined as beta-sheet by 13C solid-state NMR. In conclusion the moderate shear applied here triggered the change in the secondary structure.

  15. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shasha [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhu, Yuanrong, E-mail: zhuyuanrong07@mails.ucas.ac.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Meng, Wei, E-mail: mengwei@craes.org.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Zhongqi [USDA-ARS Southern Regional Research Center, 1100 Robert E Lee Blvd, New Orleans, LA 70124 (United States); Feng, Weiying [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhang, Chen [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Giesy, John P. [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Biomedical and Veterinary Biosciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)

    2016-02-01

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O–C–O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH{sub 3} and COO/N–C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH{sub 3} and COO/N–C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. - Highlights: • WEOM derived from aquatic macrophytes was characterized. • C and P in WEOM were characterized by solid {sup 13}C NMR and solution {sup 31}P NMR. • Degradation and transformation of macrophyte-derived C and P were investigated. • Macrophyte-derived WEOM are important source for bioavailable nutrients in lakes.

  16. Novel nuclear laser spectroscopy method using superfluid helium for measurement of spins and moments of exotic nuclei

    International Nuclear Information System (INIS)

    Furukawa, Takeshi; Wakui, Takashi; Yang, Xiaofei; Fujita, Tomomi; Imamura, Kei; Yamaguchi, Yasuhiro; Tetsuka, Hiroki; Tsutsui, Yoshiki; Mitsuya, Yosuke; Ichikawa, Yuichi; Ishibashi, Yoko; Yoshida, Naoki; Shirai, Hazuki; Ebara, Yuta; Hayasaka, Miki; Arai, Shino; Muramoto, Sosuke

    2013-01-01

    Highlights: • Development of a novel nuclear laser spectroscopy method using superfluid helium. • Observation of the Zeeman resonance with the 85 Rb beam introduced into helium. • Demonstration of deducing the nuclear spins from the observed resonance spectrum. -- Abstract: We have been developing a novel nuclear laser spectroscopy method “OROCHI” for determining spins and moments of exotic radioisotopes. In this method, we use superfluid helium as a stopping material of energetic radioisotope beams and then stopped radioisotope atoms are subjected to in situ laser spectroscopy in superfluid helium. To confirm the feasibility of this method for rare radioisotopes, we carried out a test experiment using a 85 Rb beam. In this experiment, we have successfully measured the Zeeman resonance signals from the 85 Rb atoms stopped in superfluid helium by laser-RF double resonance spectroscopy. This method is efficient for the measurement of spins and moments of more exotic nuclei

  17. Novel nuclear laser spectroscopy method using superfluid helium for measurement of spins and moments of exotic nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Furukawa, Takeshi, E-mail: takeshi@tmu.ac.jp [Department of Physics, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397 (Japan); RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Wakui, Takashi [Cyclotron and Radioisotope Center, Tohoku University, 6-3 Aoba, Aramaki, Aoba, Sendai, Miyagi 980-8578 (Japan); Yang, Xiaofei [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); School of Physics, Peking University, Chengfu Road, Haidian District, Beijing 100871 (China); Fujita, Tomomi [Department of Physics, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043 (Japan); Imamura, Kei; Yamaguchi, Yasuhiro [Department of Physics, Meiji University, 1-1-1 Higashi-Mita, Tama, Kawasaki, Kanagawa 214-8571 (Japan); Tetsuka, Hiroki; Tsutsui, Yoshiki [Department of Physics, Tokyo Gakugei University, 4-1-1 Nukuikitamachi, Koganei, Tokyo 184-8501,Japan (Japan); Mitsuya, Yosuke [Department of Physics, Meiji University, 1-1-1 Higashi-Mita, Tama, Kawasaki, Kanagawa 214-8571 (Japan); Ichikawa, Yuichi [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Department of Physics, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo 152-8551 (Japan); Ishibashi, Yoko [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Department of Physics, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Yoshida, Naoki; Shirai, Hazuki [RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Department of Physics, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo 152-8551 (Japan); Ebara, Yuta; Hayasaka, Miki [Department of Physics, Tokyo Gakugei University, 4-1-1 Nukuikitamachi, Koganei, Tokyo 184-8501,Japan (Japan); Arai, Shino; Muramoto, Sosuke [Department of Physics, Meiji University, 1-1-1 Higashi-Mita, Tama, Kawasaki, Kanagawa 214-8571 (Japan); and others

    2013-12-15

    Highlights: • Development of a novel nuclear laser spectroscopy method using superfluid helium. • Observation of the Zeeman resonance with the {sup 85}Rb beam introduced into helium. • Demonstration of deducing the nuclear spins from the observed resonance spectrum. -- Abstract: We have been developing a novel nuclear laser spectroscopy method “OROCHI” for determining spins and moments of exotic radioisotopes. In this method, we use superfluid helium as a stopping material of energetic radioisotope beams and then stopped radioisotope atoms are subjected to in situ laser spectroscopy in superfluid helium. To confirm the feasibility of this method for rare radioisotopes, we carried out a test experiment using a {sup 85}Rb beam. In this experiment, we have successfully measured the Zeeman resonance signals from the {sup 85}Rb atoms stopped in superfluid helium by laser-RF double resonance spectroscopy. This method is efficient for the measurement of spins and moments of more exotic nuclei.

  18. 18O isotope shift in 15N NMR spectroscopy. 2. Synthesis of 15N, 18O-labeled hydroxylamine hydrochloride

    International Nuclear Information System (INIS)

    Rajendran, G.; Van Etten, R.L.

    1986-01-01

    Since hydroxylamine can serve as a key intermediate in the synthesis of a variety of compounds, the synthesis of [ 15 N, 18 O]-labelled hydroxylamine hydrochloride was undertaken. Published procedures for the synthesis of hydroxylamine resulted in poor yields in some cases and in lower percentage of 18 O in the product than expected in other cases. The compound was synthesized in dry tetrahydrofuran (THF) by treating NaNO 2 with borane-methyl sulfide. The course of the reaction was examined using 11 B NMR spectroscopy, and the product yield was 74%. The 18 O enrichment was demonstrated by both mass spectrometry and 15 N NMR of the isolated acetoxime. 23 references, 1 figure

  19. Structure and function of the Juxta membrane domain of the human epidermal growth factor receptor by NMR spectroscopy

    International Nuclear Information System (INIS)

    Choowongkomon, Kiattawee; Carlin, Cathleen; Sonnichsen, Frank D.

    2005-10-01

    The epidermal growth factor receptor (EGFR) is a member of the receptor tyrosine kinase family involved in the regulation of cellular proliferation and differentiation. Its juxta membrane domain (JX), the region located between the transmembrane and kinase domains, plays important roles in receptor trafficking since both basolateral sorting in polarized epithelial cells and lysosomal sorting signals are identified in this region. In order to understand the regulation of these signals, we characterized the structural properties of recombinant JX domain in dodecyl phosphocholine detergent (DPC) by nuclear magnetic resonance (NMR) spectroscopy. In DPC micelles, structures derived from NMR data showed three amphipathic, helical segments. Two equivalent average structural models on the surface of micelles were obtained that differ only in the relative orientation between the first and second helices. Our data suggests that the activity of sorting signals may be regulated by their membrane association and restricted accessibility in the intact receptor

  20. 5-Chlorouracil and 5-bromouracil acid-base equilibrium study in water and DMSO by NMR spectroscopy

    Science.gov (United States)

    Abdrakhimova, G. S.; Ovchinnikov, M. Yu; Lobov, A. N.; Spirikhin, L. V.; Khursan, S. L.; Ivanov, S. P.

    2018-04-01

    Mechanism of 5-chloro- and 5-bromouracil deprotonation in water and dimethyl sulfoxide (DMSO) has been studied by the 13C and 1H NMR spectroscopy. NMR spectra were interpreted using DFT quantum chemical calculations at the CSGT-PCM-TPSSTPSS/6-311+G(d, p) level of theory. It was found that 5-chloro- (5ClU) and 5-bromouracil (5BrU) are present as a mixture of two anionic forms where the deprotonation is realized at the first (N1) and the third (N3) positions of the pyrimidine ring. N1 form is major for water-alkaline [xAN1/xAN3 (5ClU) = 0.65/0.35 and xAN1/xAN3 (5BrU) = 0.72/0.28, x - molar fraction] and the only one for DMSO solution.

  1. Zero-field NMR study on a spin glass: iron-doped 2H-niobium diselenide

    International Nuclear Information System (INIS)

    Chen, M.C.

    1982-01-01

    Spin echoes are used to study the 93 Nb NQR in 2H-NbSe 2 Fe/sub x/. Measured are (intensity) x (temperature), and T/sub 1P/ (spin-lattice relaxation parameter) and T 2 (spin-spin relaxation time) as a function of temperature. Data reveal dramatic differences between non-spin glass samples (x = 0, 0.25%, 1% and 5%) and spin glass samples (x = 8%, 10% and 12%). All of the NQR results and the model calculation of the correlation times of Fe spins are best described by the phase transition picture of spin glasses

  2. Application of high resolution NMR, ESR, and gamma-ray scintillation spectroscopy to the study of ligand binding in proteins

    International Nuclear Information System (INIS)

    Lancione, G.V.

    1982-01-01

    Electron spin resonance spectroscopy has been employed to study the nature of the ligand binding site of alpha-1-antitrypsin. Spectra of spin-labeled alpha-1-antitrypsin were recorded at pH's ranging from 2.4 to 12.5. This data demonstrates the tight binding of the spin-label to the protease, and the sensitivity of the bound spin-label to informational changes in the protease inhibitor. A molecular dipstick approach has also been applied to this system and has yielded information on the geometry of the cleft accommodating the spin-label. 160 Terbium(III) exchange experiments have been performed on the acetylcholine receptor protein isolated from Torpedo californica, employing a specially designed flow dialysis apparatus constructed in the laboratory. The apparatus is designed to allow continuous monitoring of 160 Tb(III) gamma-ray emission from the protein compartment of the flow dialysis cell. Nicotinic ligand-induced displacement of 160 Tb(III) from the nicotinic binding site of the receptor was monitored as a funtion of (1) the concentration of nicotinic ligand in the washout buffer, and (2) the nature of the nicotinic ligand in the buffer. Measured 160 Tb(III) exchange half-lives indicate (1) a direct relationship between 160 Tb(III) displacement and nicotinic ligand concentration in the wash-out buffer, and (2) an enhanced 160 Tb(III) displacement for nicotinic agents possessing quaternary ammonium functions

  3. Estimating side-chain order in methyl-protonated, perdeuterated proteins via multiple-quantum relaxation violated coherence transfer NMR spectroscopy

    International Nuclear Information System (INIS)

    Sun Hechao; Godoy-Ruiz, Raquel; Tugarinov, Vitali

    2012-01-01

    Relaxation violated coherence transfer NMR spectroscopy (Tugarinov et al. in J Am Chem Soc 129:1743–1750, 2007) is an established experimental tool for quantitative estimation of the amplitudes of side-chain motions in methyl-protonated, highly deuterated proteins. Relaxation violated coherence transfer experiments monitor the build-up of methyl proton multiple-quantum coherences that can be created in magnetically equivalent spin-systems as long as their transverse magnetization components relax with substantially different rates. The rate of this build-up is a reporter of the methyl-bearing side-chain mobility. Although the build-up of multiple-quantum 1 H coherences is monitored in these experiments, the decay of the methyl signal during relaxation delays occurs when methyl proton magnetization is in a single-quantum state. We describe a relaxation violated coherence transfer approach where the relaxation of multiple-quantum 1 H– 13 C methyl coherences during the relaxation delay period is quantified. The NMR experiment and the associated fitting procedure that models the time-dependence of the signal build-up, are applicable to the characterization of side-chain order in [ 13 CH 3 ]-methyl-labeled, highly deuterated protein systems up to ∼100 kDa in molecular weight. The feasibility of extracting reliable measures of side-chain order is experimentally verified on methyl-protonated, perdeuterated samples of an 8.5-kDa ubiquitin at 10°C and an 82-kDa Malate Synthase G at 37°C.

  4. Practical aspects of Lee Goldburg based CRAMPS techniques for high-resolution 1H NMR spectroscopy in solids: Implementation and applications

    Science.gov (United States)

    Coelho, Cristina; Rocha, João; Madhu, P. K.; Mafra, Luís

    2008-10-01

    Elucidating the local environment of the hydrogen atoms is an important problem in materials science. Because 1H spectra in solid-state nuclear magnetic resonance (NMR) suffer from low resolution due to homogeneous broadening, even under magic-angle spinning (MAS), information of chemical interest may only be obtained using certain high-resolution 1H MAS techniques. 1H Lee-Goldburg (LG) CRAMPS (Combined Rotation And Multiple-Pulse Spectroscopy) methods are particularly well suited for studying inorganic-organic hybrid materials, rich in 1H nuclei. However, setting up CRAMPS experiments is time-consuming and not entirely trivial, facts that have discouraged their widespread use by materials scientists. To change this status quo, here we describe and discuss some important aspects of the experimental implementation of CRAMPS techniques based on LG decoupling schemes, such as FSLG (Frequency Switched), and windowed and windowless PMLG (Phase Modulated). In particular, we discuss the influence on the quality of the 1H NMR spectra of the different parameters at play, for example LG (Lee-Goldburg) pulses, radio-frequency ( rf) phase, frequency switching, and pulse imperfections, using glycine and adamantane as model compounds. The efficiency and robustness of the different LG-decoupling schemes is then illustrated on the following materials: organo-phosphorus ligand, N-(phosphonomethyl)iminodiacetic acid [H 4pmida] [I], and inorganic-organic hybrid materials (C 4H 12N 2)[Ge 2(pmida) 2OH 2]·4H 2O [II] and (C 2H 5NH 3)[Ti(H 1.5PO 4)(PO 4)] 2·H 2O [III].

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

    Science.gov (United States)

    Waller, Francis J.; And Others

    1977-01-01

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

  6. Acetone-induced Polymerization of 3-Aminopropyltrimethoxysilane (APTMS) as Revealed by NMR Spectroscopy - Revisited.

    Czech Academy of Sciences Publication Activity Database

    Schraml, Jan; Korec, S.; Krump, M.; Čermák, Jan

    2015-01-01

    Roč. 53, č. 2 (2015), s. 154-159 ISSN 0749-1581 Institutional support: RVO:67985858 Keywords : NMR * polymerization * 3-aminopropyltrimethoxysilane Subject RIV: CC - Organic Chemistry Impact factor: 1.226, year: 2015

  7. Antenna design for propagating spin wave spectroscopy in ferromagnetic thin films

    Science.gov (United States)

    Zhang, Yan; Yu, Ting; Chen, Ji-lei; Zhang, You-guang; Feng, Jian; Tu, Sa; Yu, Haiming

    2018-03-01

    In this paper, we investigate the characteristics of antenna for propagating-spin-wave-spectroscopy (PSWS) experiment in ferromagnetic thin films. Firstly, we simulate the amplitude and phase distribution of the high-frequency magnetic field around antenna by high frequency structure simulator (HFSS). And then k distribution of the antenna is obtained by fast Fourier transformation (FFT). Furthermore, three kinds of antenna designs, i.e. micro-strip line, coplanar waveguide (CPW), loop, are studied and compared. How the dimension parameter of antenna influence the corresponding high-frequency magnetic field amplitude and k distribution are investigated in details.

  8. Metabolic profiling of human lung cancer blood plasma using 1H NMR spectroscopy

    Science.gov (United States)

    Kokova, Daria; Dementeva, Natalia; Kotelnikov, Oleg; Ponomaryova, Anastasia; Cherdyntseva, Nadezhda; Kzhyshkowska, Juliya

    2017-11-01

    Lung cancer (both small cell and non-small cell) is the second most common cancer in both men and women. The article represents results of evaluating of the plasma metabolic profiles of 100 lung cancer patients and 100 controls to investigate significant metabolites using 400 MHz 1H NMR spectrometer. The results of multivariate statistical analysis show that a medium-field NMR spectrometer can obtain the data which are already sufficient for clinical metabolomics.

  9. 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.

  10. Characterization of nonderivatized plant cell walls using high-resolution solution-state NMR spectroscopy

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2008-01-01

    A recently described plant cell wall dissolution system has been modified to use perdeuterated solvents to allow direct in-NMR-tube dissolution and high-resolution solution-state NMR of the whole cell wall without derivatization. Finely ground cell wall material dissolves in a solvent system containing dimethylsulfoxide-d6 and 1-methylimidazole-d6 in a ratio of 4:1 (v/...

  11. In-cell NMR spectroscopy of proteins inside Xenopus laevis oocytes

    International Nuclear Information System (INIS)

    Sakai, Tomomi; Tochio, Hidehito; Tenno, Takeshi; Ito, Yutaka; Kokubo, Tetsuro; Hiroaki, Hidekazu; Shirakawa, Masahiro

    2006-01-01

    In-cell NMR is an application of solution NMR that enables the investigation of protein conformations inside living cells. We have measured in-cell NMR spectra in oocytes from the African clawed frog Xenopus laevis. 15 N-labeled ubiquitin, its derivatives and calmodulin were injected into Xenopus oocytes and two-dimensional 1 H- 15 N correlation spectra of the proteins were obtained. While the spectrum of wild-type ubiquitin in oocytes had rather fewer cross-peaks compared to its in vitro spectrum, ubiquitin derivatives that are presumably unable to bind to ubiquitin-interacting proteins gave a markedly larger number of cross-peaks. This observation suggests that protein-protein interactions between ubiquitin and ubiquitin-interacting proteins may cause NMR signal broadening, and hence spoil the quality of the in-cell HSQC spectra. In addition, we observed the maturation of ubiquitin precursor derivative in living oocytes using the in-cell NMR technique. This process was partly inhibited by pre-addition of ubiquitin aldehyde, a specific inhibitor for ubiquitin C-terminal hydrolase (UCH). Our work demonstrates the potential usefulness of in-cell NMR with Xenopus oocytes for the investigation of protein conformations and functions under intracellular environmental conditions

  12. Parallel β-Sheet Structure of Alanine Tetrapeptide in the Solid State As Studied by Solid-State NMR Spectroscopy.

    Science.gov (United States)

    Asakura, Tetsuo; Horiguchi, Kumiko; Aoki, Akihiro; Tasei, Yugo; Naito, Akira

    2016-09-01

    The structural analysis of alanine oligopeptides is important for understanding the crystalline region in silks from spiders and wild silkworms and also the mechanism of cellular toxicity of human diseases arising from expansion in polyalanine sequences. The atomic-level structures of alanine tripeptide and tetrapeptide with antiparallel β-sheet structures (AP-Ala3 and AP-Ala4, respectively) together with alanine tripeptide with parallel β-sheet structures (P-Ala3) have been determined, but alanine tetrapeptide with a parallel β-sheet structure (P-Ala4) has not been reported yet. In this article, first, we established the preparation protocol of P-Ala4 from more stable AP-Ala4. Second, complete assignments of the (13)C, (15)N, and (1)H solid-state NMR spectra were performed with (13)C- and (15)N-labeled Ala4 samples using several solid-state NMR techniques. Then, the structural constraints were obtained, for example, the amide proton peaks of P-Ala4 in the (1)H double-quantum magic-angle spinning NMR spectrum were heavily overlapped and observed at about 7.4 ppm, which was a much higher field than that of 8.7-9.1 ppm observed for AP-Ala4, indicating that the intermolecular hydrogen-bond lengths across strands (N-H···O═C) were considerably longer for P-Ala4, that is, 2.21-2.34 Å, than those reported for AP-Ala4, that is, 1.8-1.9 Å. The structural model was proposed for P-Ala4 by NMR results and MD calculations.

  13. Three-dimensional solution structure of Cucurbita maxima trypsin inhibitor-V determined by NMR spectroscopy.

    Science.gov (United States)

    Cai, M; Gong, Y; Kao, J L; Krishnamoorthi, R

    1995-04-18

    The solution structure of Cucurbita maxima trypsin inhibitor-V (CMTI-V), which is also a specific inhibitor of the blood coagulation protein, factor XIIa, was determined by 1H NMR spectroscopy in combination with a distance-geometry and simulated annealing algorithm. Sequence-specific resonance assignments were made for all the main-chain and most of the side-chain hydrogens. Stereospecific assignments were also made for some of the beta-, gamma-, delta-, and epsilon-hydrogens and valine methyl hydrogens. The ring conformations of all six prolines in the inhibitor were determined on the basis of 1H-1H vicinal coupling constant patterns; most of the proline ring hydrogens were stereospecifically assigned on the basis of vicinal coupling constant and intraresidue nuclear Overhauser effect (NOE) patterns. Distance constraints were determined on the basis of NOEs between pairs of hydrogens. Dihedral angle constraints were determined from estimates of scalar coupling constants and intraresidue NOEs. On the basis of 727 interproton distance and 111 torsion angle constraints, which included backbone phi angles and side-chain chi 1, chi 2, chi 3, and chi 4 angles, 22 structures were calculated by a distance geometry algorithm and refined by energy minimization and simulated annealing methods. Both main-chain and side-chain atoms are well-defined, except for a loop region, two terminal residues, and some side-chain atoms located on the molecular surface. The average root mean squared deviation in the position for equivalent atoms between the 22 individual structures and the mean structure obtained by averaging their coordinates is 0.58 +/- 0.06 A for the main-chain atoms and 1.01 +/- 0.07 A for all the non-hydrogen atoms of residues 3-40 and 49-67. These structures were compared to the X-ray crystallographic structure of another protein of the same inhibitor family-chymotrypsin inhibitor-2 from barley seeds [CI-2; McPhalen, C. A., & James, M. N. G. (1987) Biochemistry 26

  14. Mapping protein–protein interactions by double-REDOR-filtered magic angle spinning NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Changmiao; Hou, Guangjin, E-mail: hou@udel.edu; Lu, Xingyu; Polenova, Tatyana, E-mail: tpolenov@udel.edu [University of Delaware, Department of Chemistry and Biochemistry (United States)

    2017-02-15

    REDOR-based experiments with simultaneous {sup 1}H–{sup 13}C and {sup 1}H−{sup 15}N dipolar dephasing are explored for investigating intermolecular protein–protein interfaces in complexes formed by a U–{sup 13}C,{sup 15}N-labeled protein and its natural abundance binding partner. The application of a double-REDOR filter (dREDOR) results in a complete dephasing of proton magnetization in the U–{sup 13}C,{sup 15}N-enriched molecule while the proton magnetization of the unlabeled binding partner is not dephased. This retained proton magnetization is then transferred across the intermolecular interface by {sup 1}H–{sup 13}C or {sup 1}H–{sup 15}N cross polarization, permitting to establish the residues of the U–{sup 13}C,{sup 15}N-labeled protein, which constitute the binding interface. To assign the interface residues, this dREDOR-CPMAS element is incorporated as a building block into {sup 13}C–{sup 13}C correlation experiments. We established the validity of this approach on U–{sup 13}C,{sup 15}N-histidine and on a structurally characterized complex of dynactin’s U–{sup 13}C,{sup 15}N-CAP-Gly domain with end-binding protein 1 (EB1). The approach introduced here is broadly applicable to the analysis of intermolecular interfaces when one of the binding partners in a complex cannot be isotopically labeled.

  15. Implementation of picoSpin Benchtop NMR Instruments into Organic Chemistry Teaching Laboratories through Spectral Analysis of Fischer Esterification Products

    Science.gov (United States)

    Yearty, Kasey L.; Sharp, Joseph T.; Meehan, Emma K.; Wallace, Doyle R.; Jackson, Douglas M.; Morrison, Richard W.

    2017-01-01

    [Superscript 1]H NMR analysis is an important analytical technique presented in introductory organic chemistry courses. NMR instrument access is limited for undergraduate organic chemistry students due to the size of the instrument, price of NMR solvents, and the maintenance level required for instrument upkeep. The University of Georgia Chemistry…

  16. The stoichiometry of synthetic alunite as a function of hydrothermal ageing investigated by solid-state NMR spectroscopy, powder X-ray diffraction, and infrared spectroscopy

    DEFF Research Database (Denmark)

    Grube, Elisabeth; Nielsen, U. G.

    2014-01-01

    The stoichiometry of a series of synthetic alunite (nominally KAl3(SO4)2(OH)6) samples prepared by hydrothermal methods as a function of reaction time (1 – 31 days) has been investigated by powder X-ray diffraction, Fourier transform infrared spectroscopy as well as solid-state 1H and 27Al magic...... of potassium defects present, from 17.261(1) to 17.324(5) Å. Solid-state 27Al MAS NMR revealed a decrease in the defect concentration as a function of time and showed the presence of 7-10 % impurities in the samples....

  17. LOCUS MR: Localization of unaffected spins in MR tomography and MR spectroscopy

    International Nuclear Information System (INIS)

    Matthael, D.; Haase, A.

    1986-01-01

    Different pulse sequences have been proposed for localized in vivo MR spectroscopy. For localized MR tomography and MR spectroscopy, a method is proposed, dubbed LOCUS (LOCalization of Unaffected Spins) MR. The method uses the initial saturation of regions surrounding the region of interest (ROI) in the presence of gradients. This is followed by a conventional MR study of the unaffected ROI. In animals, human extremities, and phantoms, proton MR studies demonstrated that the method provides an optimal signal-to-noise ratio, an easily variable ROI, and ROI shim. The method can be combined with two- and three-dimensional imaging, and it allows localized measurement of MR parameters. The multinuclear capability is discussed

  18. In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO42 during Heating by High Temperature Raman and 27Al NMR Spectroscopies

    Directory of Open Access Journals (Sweden)

    Min Wang

    2017-03-01

    Full Text Available Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family MIMIII(MVIO42 (MI = alkali metal, MIII = Al, In, Sc, Fe, Bi, lanthanide; MVI = Mo, W. The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO42 have been investigated by in-situ high temperature Raman scattering and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO6] octahedra in both KAl(MoO42 glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K+, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.

  19. Ligand-receptor binding affinities from saturation transfer difference (STD) NMR spectroscopy: the binding isotherm of STD initial growth rates.

    Science.gov (United States)

    Angulo, Jesús; Enríquez-Navas, Pedro M; Nieto, Pedro M

    2010-07-12

    The direct evaluation of dissociation constants (K(D)) from the variation of saturation transfer difference (STD) NMR spectroscopy values with the receptor-ligand ratio is not feasible due to the complex dependence of STD intensities on the spectral properties of the observed signals. Indirect evaluation, by competition experiments, allows the determination of K(D), as long as a ligand of known affinity is available for the protein under study. Herein, we present a novel protocol based on STD NMR spectroscopy for the direct measurements of receptor-ligand dissociation constants (K(D)) from single-ligand titration experiments. The influence of several experimental factors on STD values has been studied in detail, confirming the marked impact on standard determinations of protein-ligand affinities by STD NMR spectroscopy. These factors, namely, STD saturation time, ligand residence time in the complex, and the intensity of the signal, affect the accumulation of saturation in the free ligand by processes closely related to fast protein-ligand rebinding and longitudinal relaxation of the ligand signals. The proposed method avoids the dependence of the magnitudes of ligand STD signals at a given saturation time on spurious factors by constructing the binding isotherms using the initial growth rates of the STD amplification factors, in a similar way to the use of NOE growing rates to estimate cross relaxation rates for distance evaluations. Herein, it is demonstrated that the effects of these factors are cancelled out by analyzing the protein-ligand association curve using STD values at the limit of zero saturation time, when virtually no ligand rebinding or relaxation takes place. The approach is validated for two well-studied protein-ligand systems: the binding of the saccharides GlcNAc and GlcNAcbeta1,4GlcNAc (chitobiose) to the wheat germ agglutinin (WGA) lectin, and the interaction of the amino acid L-tryptophan to bovine serum albumin (BSA). In all cases, the

  20. Identification and quantitative determination of carbohydrates in ethanolic extracts of two conifers using 13C NMR spectroscopy.

    Science.gov (United States)

    Duquesnoy, Emilie; Castola, Vincent; Casanova, Joseph

    2008-04-07

    We developed a method for the direct identification and quantification of carbohydrates in raw vegetable extracts using (13)C NMR spectroscopy without any preliminary step of precipitation or reduction of the components. This method has been validated (accuracy, precision and response linearity) using pure compounds and artificial mixtures before being applied to authentic ethanolic extracts of pine needles, pine wood and pine cones and fir twigs. We determined that carbohydrates represented from 15% to 35% of the crude extracts in which pinitol was the principal constituent accompanied by arabinitol, mannitol, glucose and fructose.