Science.gov

Sample records for oxygen-17 nmr studies

  1. An oxygen-17 dynamic NMR study of the Pr-DOTA complex.

    PubMed

    Fusaro, Luca; Luhmer, Michel

    2014-01-21

    The complex between (17)O-enriched DOTA (tetraazacyclododecanetetraacetic acid) and praseodymium(III) (Pr(3+)) was studied in aqueous solution by variable-temperature (17)O NMR at 14.1 T. pH effects as well as the influence of metal ions free in solution were investigated. At low temperature, the so-called TSAP and SAP conformations give rise to distinct signals for the oxygen atoms coordinated to the metal ion (O2); coalescence occurs between 20 and 30 °C. In contrast, a single signal was detected for the noncoordinated oxygen atoms (O1) in the entire investigated temperature range, i.e. between -3 and 135 °C. At high temperature, the spectra exhibit signal broadening that reveals the interchange of the O1 and O2 oxygen atoms of the carboxylate groups. The linewidths measured for O1 were deconvolved into contributions from quadrupole relaxation and chemical exchange, allowing the corresponding activation barriers to be determined. The present (17)O dynamic NMR study provides the first quantitative experimental data characterizing the interchange of the oxygen atoms in a DOTA chelate of a lanthanide metal ion. The activation entropy of this process is negligible and the activation enthalpy is found to range between 66 and 77 kJ mol(-1), depending on the pH and the presence of free Pr(3+) ions in solution. These data support the results of a previous computational study according to which the exchange mechanism involves the internal rotation of the carboxylate groups.

  2. An oxygen-17 dynamic NMR study of the Pr-DOTA complex.

    PubMed

    Fusaro, Luca; Luhmer, Michel

    2014-01-21

    The complex between (17)O-enriched DOTA (tetraazacyclododecanetetraacetic acid) and praseodymium(III) (Pr(3+)) was studied in aqueous solution by variable-temperature (17)O NMR at 14.1 T. pH effects as well as the influence of metal ions free in solution were investigated. At low temperature, the so-called TSAP and SAP conformations give rise to distinct signals for the oxygen atoms coordinated to the metal ion (O2); coalescence occurs between 20 and 30 °C. In contrast, a single signal was detected for the noncoordinated oxygen atoms (O1) in the entire investigated temperature range, i.e. between -3 and 135 °C. At high temperature, the spectra exhibit signal broadening that reveals the interchange of the O1 and O2 oxygen atoms of the carboxylate groups. The linewidths measured for O1 were deconvolved into contributions from quadrupole relaxation and chemical exchange, allowing the corresponding activation barriers to be determined. The present (17)O dynamic NMR study provides the first quantitative experimental data characterizing the interchange of the oxygen atoms in a DOTA chelate of a lanthanide metal ion. The activation entropy of this process is negligible and the activation enthalpy is found to range between 66 and 77 kJ mol(-1), depending on the pH and the presence of free Pr(3+) ions in solution. These data support the results of a previous computational study according to which the exchange mechanism involves the internal rotation of the carboxylate groups. PMID:24158053

  3. Investigations of Transport in Non-Stoichiometric Oxides Using High-Temperature OXYGEN-17 NMR.

    NASA Astrophysics Data System (ADS)

    Adler, Stuart Blake

    Non-stoichiometric oxides show promise in a variety of chemical processing applications, including fuel cell technology, electrocatalysis, and air separation. Our current understanding of non-stoichiometric oxides is limited, however, and further progress toward improved materials and effective process development requires expanded fundamental research. This work discusses the use of high-temperature oxygen-17 NMR for studying the microscopic origins of transport in these materials. We report on theoretical results that lend insight into the interpretation of NMR measurements and how these measurements relate to microscopic dynamics and macroscopic transport. We then discuss experimental approaches for probing microscopic dynamics with NMR, and apply them to understanding order-disorder phenomena in an oxide-ion conductor of known structure. The techniques and concepts learned from these studies are then applied to the understanding of oxygen transport in more complex materials of current industrial interest: the defective perovskites. Finally, we also analyze information that NMR provides us regarding electronic structure and electron transport in defective perovskites. We find that perovskite oxides with cubic crystal structures possess layered structures locally, and this profoundly influences their ionic and electronic transport properties.

  4. Solution oxygen-17 NMR application for observing a peroxidized cysteine residue in oxidized human SOD1

    NASA Astrophysics Data System (ADS)

    Fujiwara, Noriko; Yoshihara, Daisaku; Sakiyama, Haruhiko; Eguchi, Hironobu; Suzuki, Keiichiro

    2016-12-01

    NMR active nuclei, 1H, 13C and 15N, are usually used for determination of protein structure. However, solution 17O-NMR application to proteins is extremely limited although oxygen is an essential element in biomolecules. Proteins are oxidized through cysteine residues by two types of oxidation. One is reversible oxidation such as disulphide bonding (Cys-S-S-Cys) and the other is irreversible oxidation to cysteine sulfinic acid (Cys-SO 2H) and cysteine sulfonic acid (Cys-SO 3H). Copper,Zinc-superoxide dismutase (SOD1) is a key enzyme in the protection of cells from the superoxide anion radical. The SH group at Cys 111 residue in human SOD1 is selectively oxidized to -SO 2H and -SO 3H with atmospheric oxygen, and this oxidized human SOD1 is also suggested to play an important role in the pathophysiology of various neurodegenerative diseases, probably mainly via protein aggregation. Therefore, information on the structural and the dynamics of the oxidized cysteine residue would be crucial for the understanding of protein aggregation mechanism. Although the -SO 3H group on proteins cannot be directly detected by conventional NMR techniques, we successfully performed the site-specific 17O-labeling of Cys 111 in SOD1 using ^{17}it {O}2 gas and the 17O-NMR analysis for the first time. We observed clear 17O signal derived from a protein molecule and show that 17O-NMR is a sensitive probe for studying the structure and dynamics of the 17O-labeled protein molecule. This novel and unique strategy can have great impact on many research fields in biology and chemistry.

  5. Oxygen-17 NMR Shifts Caused by Cr{Sup ++} in Aqueous Solutions

    DOE R&D Accomplishments Database

    Jackson, J. A.; Lemons, J. F.; Taube, H.

    1962-01-01

    Cr{sup ++} in solution produces a paramagnetic shift in the NMR absorption of O{sup 17} in ClO{sub 4}{sup -}, as well as the expected paramagnetic shift for O{sup 17} in H{sub 2}O. As the concentration of ClO{sub 4}{sup -} increases, the shift in the H{sub 2}O{sup 17} absorption is diminished, and eventually changes sign. The effects are ascribed to preferential replacement by ClO{sub 4}{sup -} of water molecules from the axial positions in the first coordination sphere about Cr{sup ++}.

  6. Water dynamics on ice and hydrate lattices studied by second-order central-line stimulated-echo oxygen-17 nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Adjei-Acheamfour, Mischa; Tilly, Julius F.; Beerwerth, Joachim; Böhmer, Roland

    2015-12-01

    Oxygen-17 stimulated-echo spectroscopy is a novel nuclear magnetic resonance (NMR) technique that allows one to investigate the time scale and geometry of ultraslow molecular motions in materials containing oxygen. The method is based on detecting orientationally encoded frequency changes within oxygen's central-transition NMR line that are caused by second-order quadrupolar interactions. In addition to the latter, the present theoretical analysis of various two-pulse echo and stimulated-echo pulse sequences takes also heteronuclear dipolar interactions into account. As an experimental example, the ultraslow water motion in polycrystals of tetrahydrofuran clathrate hydrate is studied via two-time oxygen-17 stimulated-echo correlation functions. The resulting correlation times and those of hexagonal ice are similar to those from previous deuteron NMR measurements. Calculations of the echo functions' final-state correlations for various motional models are compared with the experimental data of the clathrate hydrate. It is found that a six-site model including the oxygen-proton dipolar interaction describes the present results.

  7. Water dynamics on ice and hydrate lattices studied by second-order central-line stimulated-echo oxygen-17 nuclear magnetic resonance

    SciTech Connect

    Adjei-Acheamfour, Mischa; Tilly, Julius F.; Beerwerth, Joachim; Böhmer, Roland

    2015-12-07

    Oxygen-17 stimulated-echo spectroscopy is a novel nuclear magnetic resonance (NMR) technique that allows one to investigate the time scale and geometry of ultraslow molecular motions in materials containing oxygen. The method is based on detecting orientationally encoded frequency changes within oxygen’s central-transition NMR line that are caused by second-order quadrupolar interactions. In addition to the latter, the present theoretical analysis of various two-pulse echo and stimulated-echo pulse sequences takes also heteronuclear dipolar interactions into account. As an experimental example, the ultraslow water motion in polycrystals of tetrahydrofuran clathrate hydrate is studied via two-time oxygen-17 stimulated-echo correlation functions. The resulting correlation times and those of hexagonal ice are similar to those from previous deuteron NMR measurements. Calculations of the echo functions’ final-state correlations for various motional models are compared with the experimental data of the clathrate hydrate. It is found that a six-site model including the oxygen-proton dipolar interaction describes the present results.

  8. Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy

    SciTech Connect

    Horner, D.A.

    1984-08-01

    The nuclear magnetic relaxation times of oxygen-17 have been measured in aqueous sodium bisulfite solutions in the pH range from 2.5 to 5 as a function of temperature, pH, and S(IV) concentration, at an ionic strength of 1.0 m. The rate law for oxygen exchange between bisulfite ion and water was obtained from an analysis of the data, and is consistent with oxygen exchange occurring via the reaction SO/sub 2/ + H/sub 2/O right reversible H/sup +/ + SHO/sub 3//sup -/. The value of k/sub -1/ is in agreement with relaxation measurements. Direct spectroscopic evidence was found for the existence of two isomers of bisulfite ion: one with the proton bonded to the sulfur (HSO/sub 3//sup -/) and the other with the proton bonded to an oxygen (SO/sub 3/H/sup -/). (The symbol SHO/sub 3//sup -/ in the above chemical equation refers to both isomeric forms of bisulfite ion.) The relative amounts of the two isomers were determined as a function of temperature, and the rate and mechanism of oxygen exchange between the two was investigated. One of the two isomers, presumably SO/sub 3/H/sup -/, exchanges oxygens with water much more rapidly than does the other. A two-pulse sequence was developed which greatly diminished the solvent peak in the NMR spectrum.

  9. High-resolution solid-state oxygen-17 NMR of actinide-bearing compounds: an insight into the 5f chemistry.

    PubMed

    Martel, Laura; Magnani, Nicola; Vigier, Jean-Francois; Boshoven, Jacobus; Selfslag, Chris; Farnan, Ian; Griveau, Jean-Christophe; Somers, Joseph; Fanghänel, Thomas

    2014-07-01

    A massive interest has been generated lately by the improvement of solid-state magic-angle spinning (MAS) NMR methods for the study of a broad range of paramagnetic organic and inorganic materials. The open-shell cations at the origin of this paramagnetism can be metals, transition metals, or rare-earth elements. Actinide-bearing compounds and their 5f unpaired electrons remain elusive in this intensive research area due to their well-known high radiotoxicity. A dedicated effort enabling the handling of these highly radioactive materials now allows their analysis using high-resolution MAS NMR (>55 kHz). Here, the study of the local structure of a series of actinide dioxides, namely, ThO2, UO2, NpO2, PuO2, and AmO2, using solid-state (17)O MAS NMR is reported. An important increase of the spectral resolution is found due to the removal of the dipolar broadening proving the efficiency of this technique for structural analysis. The NMR parameters in these systems with numerous and unpaired 5f electrons were interpreted using an empirical approach. Single-ion model calculations were performed for the first time to determine the z component of electron spin on each of the actinide atoms, which is proportional to the shifts. A similar variation thereof was observed only for the heavier actinides of this study.

  10. NMR studies of metalloproteins.

    PubMed

    Li, Hongyan; Sun, Hongzhe

    2012-01-01

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

  11. NMR Studies of Peroxidases.

    NASA Astrophysics Data System (ADS)

    Veitch, Nigel Charles

    Available from UMI in association with The British Library. Requires signed TDF. Peroxidases are a haem-containing group of enzymes with a wide diversity of function within biological systems. While a common characteristic is the ability to catalyse the conversion of hydrogen peroxide to water, it is the accompanying processes of hormone synthesis and degradation which have generated such a high level of interest. However, information at the molecular level is limited to a single well-resolved crystal structure, that of yeast cytochrome c peroxidase. This thesis presents a strategy for the investigation of peroxidase structure and function based on proton nuclear magnetic resonance spectroscopy, a technique which has the ability to address aspects of both protein structure and protein dynamics in solution. The application of one- and two-dimensional NMR techniques has been developed in the context of plant peroxidases, notably the isoenzyme HRP-C derived from the horseradish root. Characterisation of the proton NMR spectra of HRP -C in resting and ligated states provided new information enabling the structure of the binding site for aromatic donor molecules, such as indole-3-propionic, ferulic and benzhydroxamic acids, to be resolved. In order to overcome difficulties encountered with a protein of the complexity of peroxidase, additional information was obtained from chemical shift parameters and the use of peroxidase variants produced by site-directed mutagenesis. A comparative study using NMR spectroscopy was undertaken for wild-type recombinant HRP-C expressed in Escherichia coli, and two protein variants with substitutions made to residues located on the distal side of the haem pocket, Phe41 to Val and Arg38 to Lys. NMR analyses of a plant peroxidase from barley grains and the fungal peroxidase from Coprinus cinereus were also successful using methods conceived with HRP-C. Examination of three specifically constructed recombinant protein variants of C. cinereus

  12. NMR studies of oriented molecules

    SciTech Connect

    Sinton, S.W.

    1981-11-01

    Deuterium and proton magnetic resonance are used in experiments on a number of compounds which either form liquid crystal mesophases themselves or are dissolved in a liquid crystal solvent. Proton multiple quantum NMR is used to simplify complicated spectra. The theory of nonselective multiple quantum NMR is briefly reviewed. Benzene dissolved in a liquid crystal are used to demonstrate several outcomes of the theory. Experimental studies include proton and deuterium single quantum (..delta..M = +-1) and proton multiple quantum spectra of several molecules which contain the biphenyl moiety. 4-Cyano-4'-n-pentyl-d/sub 11/-biphenyl (5CB-d/sub 11/) is studied as a pure compound in the nematic phase. The obtained chain order parameters and dipolar couplings agree closely with previous results. Models for the effective symmetry of the biphenyl group in 5CB-d/sub 11/ are tested against the experimental spectra. The dihedral angle, defined by the planes containing the rings of the biphenyl group, is found to be 30 +- 2/sup 0/ for 5DB-d/sub 11/. Experiments are also described for 4,4'-d/sub 2/-biphenyl, 4,4' - dibromo-biphenyl, and unsubstituted biphenyl.

  13. Structural Role of Alkali Cations in Calcium Aluminosilicate Glasses as Examined Using Oxygen-17 Solid-State Nuclear Magnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sukenaga, Sohei; Kanehashi, Koji; Shibata, Hiroyuki; Saito, Noritaka; Nakashima, Kunihiko

    2016-08-01

    The structural roles of alkali and calcium cations are important for understanding the physical and chemical properties of aluminosilicate melts and glasses. Recently, oxygen-17 nuclear magnetic resonance (17O NMR) studies of calcium-sodium aluminosilicate glasses showed that these structural roles are not randomly given, but rather each cation has its own preferential role. However, the relationship between cation type and role preference in calcium aluminosilicate glass is not completely understood. In the present study, the structural roles of lithium, sodium, and potassium cations in selected calcium aluminosilicate glasses are investigated using 17O solid-state NMR experiments. Data from these experiments clearly show that potassium cations have a notably stronger tendency to act as charge compensators within the network structure, compared to sodium and lithium cations. The result of 17O NMR experiment also showed that sodium and lithium cations in part act as network modifier alongside with calcium cations.

  14. NMR studies of isotopically labeled RNA

    SciTech Connect

    Pardi, A.

    1994-12-01

    In summary, the ability to generate NMR quantities of {sup 15}N and {sup 13}C-labeled RNAs has led to the development of heteronuclear multi-dimensional NMR techniques for simplifying the resonance assignment and structure determination of RNAs. These methods for synthesizing isotopically labeled RNAs are only several years old, and thus there are still relatively few applications of heteronuclear multi-dimensional NMR techniques to RNA. However, given the critical role that RNAs play in cellular function, one can expect to see an increasing number of NMR structural studies of biologically active RNAs.

  15. NMR studies of borates and borides

    NASA Astrophysics Data System (ADS)

    Bray, P. J.

    1986-04-01

    Nuclear magnetic resonance (NMR) has been employed for some 25 years to study the structure of boron-containing compounds.1-3 The earliest works employed the 11B nuclear isotope in a study of glasses containing boron oxide. Many additional NMR studies3-10 of boron-containing glasses have utilized both the 11B and 10B isotopes. Crystalline materials were also studied2,3 at an early date, with particular attention given to borides and boron carbide. After a discussion of the features of NMR spectroscopy particularly pertinent for the study of boron-containing compounds, highlights of the early work and more recent studies will be summarized to indicate the usefulness of 10B and 11B NMR for structural studies.

  16. NMR studies of cation transport across membranes

    SciTech Connect

    Shochet, N.R.

    1985-01-01

    /sup 23/Na NMR Studies of cation transport across membranes were conducted both on model and biological membranes. Two ionophores, the carrier monensin and the channel-former gramicidin, were chosen to induce cation transport in large unilamellar phosphatidylcholine vesicles. The distinction between the NMR signals arising from the two sides of the membrane was achieved by the addition of an anionic paramagnetic shift reagent to the outer solution. The kinetics of the cation transport across the membrane was observed simultaneously monitoring the changes in the /sup 23/Na NMR signals of both compartments. Two mathematical models were developed for the estimation of the transport parameters of the monensin- and gramicidin-induced cation transport. The models were able to fit the experimental data very well. A new method for the estimation of the volume trapped inside the vesicles was developed. The method uses the relative areas of the intra- and extravesicular NMR signals arising from a suspension of vesicles bathed in the same medium they contain, as a measure for the relative volumes of these compartments. Sodium transport across biological membranes was studied by /sup 23/ NMR, using suspensions of cultured nerve cells. The sodium influx through voltage-gated channels was studied using the channel modifier batrachotoxin in combination with scorpion toxin.

  17. Structural Studies of Biological Solids Using NMR

    NASA Astrophysics Data System (ADS)

    Ramamoorthy, Ayyalusamy

    2011-03-01

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

  18. An NMR Study of Microvoids in Polymers

    NASA Technical Reports Server (NTRS)

    Toy, James; Mattrix, Larry

    1996-01-01

    An understanding of polymer defect structures, like microvoids in polymeric matrices, is most crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally not be found naturally in polymer or in NMR probe materials. There are two NMR active Xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb and Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe-129-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts in Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of Xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A series of spectra were obtained interspersed with applications of vacuum and heating to drive out the adsorbed Xe and determine the role of Xe-Xe interactions in the observed chemical shift.

  19. Solid-state NMR studies of supercapacitors.

    PubMed

    Griffin, John M; Forse, Alexander C; Grey, Clare P

    2016-01-01

    Electrochemical double-layer capacitors, or 'supercapacitors' are attracting increasing attention as high-power energy storage devices for a wide range of technological applications. These devices store charge through electrostatic interactions between liquid electrolyte ions and the surfaces of porous carbon electrodes. However, many aspects of the fundamental mechanism of supercapacitance are still not well understood, and there is a lack of experimental techniques which are capable of studying working devices. Recently, solid-state NMR has emerged as a powerful tool for studying the local environments and behaviour of electrolyte ions in supercapacitor electrodes. In this Trends article, we review these recent developments and applications. We first discuss the basic principles underlying the mechanism of supercapacitance, as well as the key NMR observables that are relevant to the study of supercapacitor electrodes. We then review some practical aspects of the study of working devices using ex situ and in situ methodologies and explain the key advances that these techniques have allowed on the study of supercapacitor charging mechanisms. NMR experiments have revealed that the pores of the carbon electrodes contain a significant number of electrolyte ions in the absence of any charging potential. This has important implications for the molecular mechanisms of supercapacitance, as charge can be stored by different ion adsorption/desorption processes. Crucially, we show how in situ NMR experiments can be used to quantitatively study and characterise the charging mechanism, with the experiments providing the most detailed picture of charge storage to date, offering the opportunity to design enhanced devices. Finally, an outlook for future directions for solid-state NMR in supercapacitor research is offered. PMID:26974032

  20. Solid-state NMR studies of supercapacitors.

    PubMed

    Griffin, John M; Forse, Alexander C; Grey, Clare P

    2016-01-01

    Electrochemical double-layer capacitors, or 'supercapacitors' are attracting increasing attention as high-power energy storage devices for a wide range of technological applications. These devices store charge through electrostatic interactions between liquid electrolyte ions and the surfaces of porous carbon electrodes. However, many aspects of the fundamental mechanism of supercapacitance are still not well understood, and there is a lack of experimental techniques which are capable of studying working devices. Recently, solid-state NMR has emerged as a powerful tool for studying the local environments and behaviour of electrolyte ions in supercapacitor electrodes. In this Trends article, we review these recent developments and applications. We first discuss the basic principles underlying the mechanism of supercapacitance, as well as the key NMR observables that are relevant to the study of supercapacitor electrodes. We then review some practical aspects of the study of working devices using ex situ and in situ methodologies and explain the key advances that these techniques have allowed on the study of supercapacitor charging mechanisms. NMR experiments have revealed that the pores of the carbon electrodes contain a significant number of electrolyte ions in the absence of any charging potential. This has important implications for the molecular mechanisms of supercapacitance, as charge can be stored by different ion adsorption/desorption processes. Crucially, we show how in situ NMR experiments can be used to quantitatively study and characterise the charging mechanism, with the experiments providing the most detailed picture of charge storage to date, offering the opportunity to design enhanced devices. Finally, an outlook for future directions for solid-state NMR in supercapacitor research is offered.

  1. NMR techniques in the study of cardiovascular structure and functions

    SciTech Connect

    Osbakken, M.; Haselgrove, J.

    1987-01-01

    The chapter titles of this book are: Introduction to NMR Techniques;Theory of NMR Probe Design;Overview of Magnetic Resonance Imaging to Study the Cardiovascular System;Vascular Anatomy and Physiology Studied with NMR Techniques;Assessment of Myocardial Ischemia and Infarction by Nuclear Magnetic Resonance Imaging;The Use of MRI in Congenital Heart Disease;Cardiomyopathies and Myocarditis Studied with NMR Techniques;Determination of Myocardial Mechanical Function with Magnetic Resonance Imaging Techniques;Determination of Flow Using NMR Techniques;The Use of Contrast Agents in Cardiac MRI;Can Cardiovascular Disease Be Effectively Evaluated with NMR Spectroscopy. NMR Studies of ATP Synthesis Reactions in the Isolated Heart;Studies of Intermediary Metabolism in the Heart by 13C NMR Spectroscopy;23Na and 39K NMR Spectroscopic Studies of the Intact Beating Heart;and Evaluation of Skeletal Muscle Metabolism in Patients with Congestive Heart Failure Using Phosphorus Nuclear Magnetic Resonance.

  2. An NMR study of microvoids in polymers

    NASA Technical Reports Server (NTRS)

    Toy, James; Mattix, Larry

    1995-01-01

    An understanding of polymer defect structures, like microvoids in polymeric matrices, is crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally be found naturally in polymer or in NMR probe materials. There are two NMR active xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb the Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe(129)-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts line Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A single Xe-129 line at 83.003498 Mhz (with protons at 300 Mhz) was observed for the gas. With the xenon charged PMR-15 samples, a second broader line is observed 190 ppm downfield from the gas line (also observed). The width of the NMR line from the Xe-129 absorbed in the polymer is at least partially due to the distribution of microvoid sizes. From the chemical shift (relative to the gas line) and the line width, we estimate the average void sizes to be 2.74 +/- 0.20 angstroms. Since Xe-129 has such a large chemical shift range (approximately 5000 ppm), we expect the chemical shift anisotropy to contribute to the

  3. Multinuclear NMR studies of relaxor ferroelectrics

    NASA Astrophysics Data System (ADS)

    Zhou, Donghua

    Multinuclear NMR of 93Nb, 45Sc, and 207Pb has been carried out to study the structure, disorder, and dynamics of a series of important solid solutions: perovskite relaxor ferroelectric materials (1-x) Pb(Mg1/3Nb 2/3)O3-x Pb(Sc1/2Nb1/2)O 3 (PMN-PSN). 93Nb NMR investigations of the local structure and cation order/disorder are presented as a function of PSN concentration, x. The superb fidelity and accuracy of 3QMAS allows us to make clear and consistent assignments of spectral intensities to the 28 possible nearest B-site neighbor (nBn) configurations, (NMg, NSc, NNb), where each number ranges from 0 to 6 and their sum is 6. For most of the 28 possible nBn configurations, isotropic chemical shifts and quadrupole product constants have been extracted from the data. The seven configurations with only larger cations, Mg 2+ and Sc3+ (and no Nb5+) are assigned to the seven observed narrow peaks, whose deconvoluted intensities facilitate quantitative evaluation of, and differentiation between, different models of B-site (chemical) disorder. The "completely random" model is ruled out and the "random site" model is shown to be in qualitative agreement with the NMR experiments. To obtain quantitative agreement with observed NMR intensities, the random site model is slightly modified by including unlike-pair interaction energies. To date, 45Sc studies have not been as fruitful as 93Nb NMR because the resolution is lower in the 45Sc spectra. The lower resolution of 45Sc spectra is due to a smaller span of isotropic chemical shift (40 ppm for 45Sc vs. 82 ppm for 93Nb) and to the lack of a fortuitous mechanism that simplifies the 93Nb spectra; for 93Nb the overlap of the isotropic chemical shifts of 6-Sc and 6-Nb configurations results in the alignment of all the 28 configurations along only seven quadrupole distribution axes. Finally we present variable temperature 207Pb static, MAS, and 2D-PASS NMR studies. Strong linear correlations between isotropic and anisotropic chemical

  4. NMR Studies of Cartilage Dynamics, Diffusion, Degradation

    NASA Astrophysics Data System (ADS)

    Huster, Daniel; Schiller, Jurgen; Naji, Lama; Kaufmann Jorn; Arnold, Klaus

    An increasing number of people is suffering from rheumatic diseases, and, therefore, methods of early diagnosis of joint degeneration are urgently required. For their establishment, however, an improved knowledge about the molecular organisation of cartilage would be helpful. Cartilage consists of three main components: Water, collagen and chondroitin sulfate (CS) that is (together with further polysaccharides and proteins) a major constituent of the proteoglycans of cartilage. 1H and 13C MAS (magic-angle spinning) NMR (nuclear magnetic resonance) opened new perspectives for the study of the macromolecular components in cartilage. We have primarily studied the mobilities of CS and collagen in bovine nasal and pig articular cartilage (that differ significantly in their collagen/polysaccharide content) by measuring 13C NMR relaxation times as well as the corresponding 13C CP (cross polarisation) MAS NMR spectra. These data clearly indicate that the mobility of cartilage macromolecules is broadly distributed from almost completely rigid (collagen) to highly mobile (polysaccharides), which lends cartilage its mechanical strength and shock-absorbing properties.

  5. Using NMR to study full intact wine bottles

    NASA Astrophysics Data System (ADS)

    Weekley, A. J.; Bruins, P.; Sisto, M.; Augustine, M. P.

    2003-03-01

    A nuclear magnetic resonance (NMR) probe and spectrometer capable of investigating full intact wine bottles is described and used to study a series of Cabernet Sauvignons with high resolution 1H NMR spectroscopy. Selected examples of full bottle 13C NMR spectra are also provided. The application of this full bottle NMR method to the measurement of acetic acid content, the detection of complex sugars, phenols, and trace elements in wine is discussed.

  6. NMR study of magnetism and superparamagnetism

    NASA Astrophysics Data System (ADS)

    Yuan, Shaojie

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

  7. Solid state NMR study of bone mineral

    SciTech Connect

    Wu, Y.

    1992-01-01

    In high field (9.4 T) CP MASS (cross polarization magic angle sample spinning) studies, in contrast to the scheme in the literature that infers the presence of minor constituents in spectra, we developed a new scheme to suppress the main part of the spectra to show the minor constituents. In order to perform in vivo solid state NMR studies, a double tuned two port surface coil probe was constructed. This probe is a modified version of the traditional Cross probe, which utilizes two 1/4 wave length 50 ohm transmission line, one with open ended and the other with shorted end, to isolate the high and low frequency circuits. The two resonance frequencies in Cross probe were proton and carbon. Our probe is designed to resonate at the proton and phosphorus frequencies, which are much closer to each other and hence more difficult to be tuned and matched simultaneously. Our approach to solve this problem is that instead of using standard 50 ohm transmission lines, we constructed a low capacity open end coaxial transmission line and low inductance shorted end coaxial transmission line. The Q of the phosphorus channel is high. We developed a short contact time cross polarization technique for non-MASS spectroscopy which reduces the signal of the major component of bone mineral to emphasize the minor component. By applying this technique on intact pork bone samples with our home made surface coil, we observed the wide line component, acid phosphate, for the first time. Hydroxyapatite, brushite and octacalcium are considered in the literature to be the model compounds for bone mineral. Cross polarization dynamics has been studied on hydroxyapatite and brushite, which yielded an NMR value for the distance between proton and phosphorus. One and two dimensional CP MASS spectroscopy of octacalcium phosphate were also studied, which revealed the different cross polarization rates and anisotropic channel shifts of acid phosphate and phosphate ions in octacalcium phosphate.

  8. Isotope labeling for NMR studies of macromolecular structure and interactions

    SciTech Connect

    Wright, P.E.

    1994-12-01

    Implementation of biosynthetic methods for uniform or specific isotope labeling of proteins, coupled with the recent development of powerful heteronuclear multidimensional NMR methods, has led to a dramatic increase in the size and complexity of macromolecular systems that are now amenable to NMR structural analysis. In recent years, a new technology has emerged that combines uniform {sup 13}C, {sup 15}N labeling with heteronuclear multidimensional NMR methods to allow NMR structural studies of systems approaching 25 to 30 kDa in molecular weight. In addition, with the introduction of specific {sup 13}C and {sup 15}N labels into ligands, meaningful NMR studies of complexes of even higher molecular weight have become feasible. These advances usher in a new era in which the earlier, rather stringent molecular weight limitations have been greatly surpassed and NMR can begin to address many central biological problems that involve macromolecular structure, dynamics, and interactions.

  9. NMR-Metabolic Methodology in the Study of GM Foods

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The 1H NMR methodology used in the study of genetically modified (GM) foodstuff is discussed. The study of transgenic lettuce (Lactuca sativa cv "Luxor") over-expressing the KNAT1 gene from Arabidopsis is presented as a novel study-case. The 1H NMR metabolic profiling was carried out. Twenty-two wat...

  10. {sup 13}C and {sup 17}O NMR binding constant studies of uranyl carbonate complexes in near-neutral aqueous solution. Yucca Mountain Project Milestone Report 3351

    SciTech Connect

    Clark, D.L.; Newton, T.W.; Palmer, P.D.; Zwick, B.D.

    1995-01-01

    Valuable structural information, much of it unavailable by other methods, can be obtained about complexes in solution through NMR spectroscopy. From chemical shift and intensity measurements of complexed species, NMR can serve as a species-specific structural probe for molecules in solution and can be used to validate thermodynamic constants used in geochemical modeling. Fourier-transform nuclear magnetic resonance (FT-NMR) spectroscopy has been employed to study the speciation of uranium(VI) ions in aqueous carbonate solutions as a function of pH, ionic strength, carbonate concentration, uranium concentration, and temperature. Carbon-13 and oxygen-17 NMR spectroscopy were used to monitor the fractions, and hence thermodynamic binding constants of two different uranyl species U0{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} and (UO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} in aqueous solution. Synthetic buffer solutions were prepared under the ionic strength conditions used in the NMR studies in order to obtain an accurate measure of the hydrogen ion concentration, and a discussion of pH = {minus}log(a{sub H}{sup +}) versus p[H] = {minus}log[H+] is provided. It is shown that for quantitative studies, the quantity p[H] needs to be used. Fourteen uranium(VI) binding constants recommended by the OECD NEA literature review were corrected to the ionic strengths employed in the NMR study using specific ion interaction theory (SIT), and the predicted species distributions were compared with the actual species observed by multinuclear NMR. Agreement between observed and predicted stability fields is excellent. This establishes the utility of multinuclear NMR as a species-specific tool for the study of the actinide carbonate complexation constants, and serves as a means for validating the recommendations provided by the OECD NEA.

  11. NMR studies of multiphase flows II

    SciTech Connect

    Altobelli, S.A.; Caprihan, A.; Fukushima, E.

    1995-12-31

    NMR techniques for measurements of spatial distribution of material phase, velocity and velocity fluctuation are being developed and refined. Versions of these techniques which provide time average liquid fraction and fluid phase velocity have been applied to several concentrated suspension systems which will not be discussed extensively here. Technical developments required to further extend the use of NMR to the multi-phase flow arena and to provide measurements of previously unobtainable parameters are the focus of this report.

  12. Chemical Equilibrium in Supramolecular Systems as Studied by NMR Spectrometry

    ERIC Educational Resources Information Center

    Gonzalez-Gaitano, Gustavo; Tardajos, Gloria

    2004-01-01

    Undergraduate students are required to study the chemical balance in supramolecular assemblies constituting two or more interacting species, by using proton NMR spectrometry. A good knowledge of physical chemistry, fundamentals of chemical balance, and NMR are pre-requisites for conducting this study.

  13. A multinuclear static NMR study of geopolymerisation

    SciTech Connect

    Favier, Aurélie; Habert, Guillaume; Roussel, Nicolas; D'Espinose de Lacaillerie, Jean-Baptiste

    2015-09-15

    Geopolymers are inorganic binders obtained by alkali activation of aluminosilicates. While the structure of geopolymers is now well understood, the details of the geopolymerisation reaction and their impact on the rheology of the paste remain uncertain. In this work, we follow the elastic properties of a paste made with metakaolin and sodium silicate solution. After the first sharp increase of elastic modulus occurring a few hundred of seconds after mixing and related to the heterogeneous formation of an alumina–silicate gel with a molar ratio Si/Al < 4 located at the grains boundaries, we focus on the progressive increase in elastic modulus on a period of few hours during the setting of the geopolymer. In this study, we combine the study of rheological properties of the paste with {sup 23}Na, {sup 27}Al and {sup 29}Si static NMR measurement in order to better understand the origin of this second increase in elastic modulus. Our results show that, after a few hours, Al and Na evolution in the liquid phase are concomitant. This suggests the precipitation of an aluminosilicate phase where Al is in tetrahedral position and Na compensates the charge. Furthermore, Si speciation confirms this result and allows us to identify the precipitation of a product, which has a chemical composition close to the final composition of geopolymer. This study provides strong evidence for a heterogeneous formation of an aluminosilicate glass directly from the first gel and the silicate solution without the need for a reorganisation of Gel 1 into Gel 2.

  14. NMR Studies of Protein Structure and Dynamics

    NASA Astrophysics Data System (ADS)

    Li, Xiang

    Available from UMI in association with The British Library. Requires signed TDF. This thesis describes applications of 2D homonuclear NMR techniques to the study of protein structure and dynamics in solution. The sequential assignments for the 3G-residue bovine Pancreatic Polypeptide (bPP) are reported. The secondary and tertiary structure of bPP in solution has been determined from experimental NMR data. bPP has a well defined C-terminal alpha-helix and a rather ordered conformation in the N-terminal region. The two segments are joined by a turn which is poorly defined. Both the N- and the C-terminus are highly disordered. The mean solution structure of bPP is remarkably similar to the crystal structure of avian Pancreatic Polypeptide (aPP). The average conformations of most side-chains from the alpha-helix of bPP in solution are closely similar to those of aPP in the crystalline state. A large number of side-chains of bPP, however, show significant conformational averaging in solution. The 89-residue kringle domain of urokinase from both human and recombinant sources has been investigated. Sequential assignments based primarily on the recombinant sample and the determination of secondary structure are presented. Two helices have been identified; one of these corresponds to that reported for t-PA kringle 2, but does not exist in other kringles with known structures. The second helix is thus far unique to the urokinase kringle. Three antiparallel beta-sheets and three tight turns have also been identified. The tertiary fold of the molecule conforms broadly to that found for other kringles. Three regions in the urokinase kringle exhibit high local mobility; one of these, the Pro56-Pro62 segment, forms part of the proposed binding site. The other two mobile regions are the N- and C-termini which are likely to form the interfaces between the kringle and the other two domains (EGF and protease) in urokinase. The differential dynamic behaviours of the kringle and

  15. Dynamic NMR study of trans-cyclodecene

    SciTech Connect

    Pawar, D.M.; Noe, E.A.

    1996-12-18

    The slow-exchange {sup 13}C spectrum of trans-cyclodecene at -154.9{degree}C shows eight peaks of the olefinic carbons, and these are interpreted in terms of five conformations. Three of the conformations are of C{sub 1} symmetry, and two are of C{sub 2} symmetry. Further evidence for the number of conformations and their symmetries came from a proton NMR spectrum of the olefinic hydrogens taken at -154.9{degree}C with decoupling the allylic hydrogens. Populations ranged from 3.0% to 37.6% with the least-populated conformation having a free energy of 0.59 kcal/mol, relative to the most stable conformer. The conformations studied by Saunders and Jimenez-Vazquez using Allinger`s MM3 force field are described, and the calculated strain energies and populations are discussed. Energies for six conformations were also obtained from ab initio calculations at the HF/6-311G{sup *} level. 22 refs., 4 figs., 3 tabs.

  16. Studies on metabolic regulation using NMR spectroscopy.

    PubMed

    Bachelard, H; Badar-Goffer, R; Ben-Yoseph, O; Morris, P; Thatcher, N

    1993-01-01

    The effects of hypoxia and hypoglycaemia on cerebral metabolism and calcium have been studied using multinuclear magnetic resonance spectroscopy. 13C MRS showed that severe hypoxia did not cause any further increase in metabolic flux into lactate seen in mild hypoxia, but there was a further increase in 13C labelling of alanine and glycerol 3-phosphate. These results are discussed in terms of the ability of lactate dehydrogenase to maintain normal levels of NADH in mild hypoxia, but not in severe hypoxia. We conclude that glycerol 3-phosphate and alanine may provide novel means of monitoring severe hypoxia whereas lactate is a reliable indicator only of mild hypoxia. 19F- and 31P NMR spectroscopy showed that neither hypoxia nor hypoglycaemia alone caused any significant change in [Ca2+]i. Combined sequential insults (hypoxia, followed by hypoxia plus hypoglycaemia), or vice versa, produced a 100% increase in [Ca2+]i, whereas immediate exposure to the combined insult (hypoxia plus hypoglycaemia) resulted in a large 5-fold increase in [Ca2+]i, with severe irreversible effects on the energy state. These results are discussed in terms of metabolic adaptation to the single type of insult, which renders the tissue less vulnerable to the combined insult. The effects of this combined insult are far more severe than those caused by glutamate or NMDA, which throws doubt on the current excitoxic hypothesis of cell damage.

  17. Conformational NMR Study of Bistriazolyl Anion Receptors.

    PubMed

    Makuc, Damjan; Merckx, Tamara; Dehaen, Wim; Plavec, Janez

    2016-01-01

    Conformational features of pyridine- and pyrimidine-based bistriazolyl anion receptors dissolved in acetonitrile-d3 were assessed by multidimensional, heteronuclear NMR spectroscopy. NOESY correlation signals suggested preorganization of both host molecules in solution in the absence of anions. In addition, only a single set of signals was observed in the 1H NMR spectra, which suggested a symmetrical conformation of anion receptors or their conformational exchange that is fast on the NMR time-scale. Furthermore, the predominant conformations of the pyridine- and pyrimidine-based anion receptors are preserved upon addition of chloride, bromide, and acetate anions. Chemical shift changes observed upon addition of anions showed that the NH (thio)urea and triazole protons are involved in anion-receptor interactions through hydrogen bonding. PMID:27640375

  18. NMR studies of metallic tin confined within porous matrices

    SciTech Connect

    Charnaya, E. V.; Tien, Cheng; Lee, M. K.; Kumzerov, Yu. A.

    2007-04-01

    {sup 119}Sn NMR studies were carried out for metallic tin confined within synthetic opal and porous glass. Tin was embedded into nanoporous matrices in the melted state under pressure. The Knight shift for liquid confined tin was found to decrease with decreasing pore size. Correlations between NMR line shapes, Knight shift, and pore filling were observed. The melting and freezing phase transitions of tin under confinement were studied through temperature dependences of NMR signals upon warming and cooling. Melting of tin within the opal matrix agreed well with the liquid skin model suggested for small isolated particles. The influence of the pore filling on the melting process was shown.

  19. NMR contributions to structural dynamics studies of intrinsically disordered proteins☆

    PubMed Central

    Konrat, Robert

    2014-01-01

    Intrinsically disordered proteins (IDPs) are characterized by substantial conformational plasticity. Given their inherent structural flexibility X-ray crystallography is not applicable to study these proteins. In contrast, NMR spectroscopy offers unique opportunities for structural and dynamic studies of IDPs. The past two decades have witnessed significant development of NMR spectroscopy that couples advances in spin physics and chemistry with a broad range of applications. This article will summarize key advances in basic physical-chemistry and NMR methodology, outline their limitations and envision future R&D directions. PMID:24656082

  20. NMR studies of nucleic acid dynamics

    PubMed Central

    Al-Hashimi, Hashim M.

    2014-01-01

    Nucleic acid structures have to satisfy two diametrically opposite requirements; on one hand they have to adopt well-defined 3D structures that can be specifically recognized by proteins; on the other hand, their structures must be sufficiently flexible to undergo very large conformational changes that are required during key biochemical processes, including replication, transcription, and translation. How do nucleic acids introduce flexibility into their 3D structure without losing biological specificity? Here, I describe the development and application of NMR spectroscopic techniques in my laboratory for characterizing the dynamic properties of nucleic acids that tightly integrate a broad set of NMR measurements, including residual dipolar couplings, spin relaxation, and relaxation dispersion with sample engineering and computational approaches. This approach allowed us to obtain fundamental new insights into directional flexibility in nucleic acids that enable their structures to change in a very specific functional manner. PMID:24149218

  1. Some nitrogen-14 NMR studies in solids

    SciTech Connect

    Pratum, T.K.

    1983-11-01

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

  2. NMR Studies of Dynamic Biomolecular Conformational Ensembles

    PubMed Central

    Torchia, Dennis A.

    2015-01-01

    Multidimensional heteronuclear NMR approaches can provide nearly complete sequential signal assignments of isotopically enriched biomolecules. The availability of assignments together with measurements of spin relaxation rates, residual spin interactions, J-couplings and chemical shifts provides information at atomic resolution about internal dynamics on timescales ranging from ps to ms, both in solution and in the solid state. However, due to the complexity of biomolecules, it is not possible to extract a unique atomic-resolution description of biomolecular motions even from extensive NMR data when many conformations are sampled on multiple timescales. For this reason, powerful computational approaches are increasingly applied to large NMR data sets to elucidate conformational ensembles sampled by biomolecules. In the past decade, considerable attention has been directed at an important class of biomolecules that function by binding to a wide variety of target molecules. Questions of current interest are: “Does the free biomolecule sample a conformational ensemble that encompasses the conformations found when it binds to various targets; and if so, on what time scale is the ensemble sampled?” This article reviews recent efforts to answer these questions, with a focus on comparing ensembles obtained for the same biomolecules by different investigators. A detailed comparison of results obtained is provided for three biomolecules: ubiquitin, calmodulin and the HIV-1 trans-activation response RNA. PMID:25669739

  3. Dihydroflavanonols from Cedrus deodara, A (13)C NMR study.

    PubMed

    Agrawal, P K; Agarwal, S K; Rastogi, R P; Osterdahal, B G

    1981-09-01

    High resolution (13)C NMR study of taxifolin, cedeodarin, cedrin and their methyl ethers allowed unambiguous placement of the Me in 5,7-dihydroxyflavanonol nucleus, besides providing other valuable information on the substitution pattern in the molecule.

  4. NMR studies on polyphosphide Ce6Ni6P17

    NASA Astrophysics Data System (ADS)

    Koyama, T.; Yamada, H.; Ueda, K.; Mito, T.; Aoyama, Y.; Nakano, T.; Takeda, N.

    2016-02-01

    We report the result of 31P nuclear magnetic resonance (NMR) studies on Ce6Ni6P17. The observed NMR spectra show a Lorentzian-type and an asymmetric shapes, reflecting the local symmetry around each P site in the cubic unit cell. We have identified the observed NMR lines corresponding to three inequivalent P sites and deduced the temperature dependence of the Knight shift for each site. The Knight shifts increase with decreasing temperature down to 1.5 K, indicating a localized spin system of Ce6Ni6P17. Antiferromagnetic correlation between 4f spins is suggested from the negative sign of the Weiss-temperature.

  5. Protein folding on the ribosome studied using NMR spectroscopy

    PubMed Central

    Waudby, Christopher A.; Launay, Hélène; Cabrita, Lisa D.; Christodoulou, John

    2013-01-01

    NMR spectroscopy is a powerful tool for the investigation of protein folding and misfolding, providing a characterization of molecular structure, dynamics and exchange processes, across a very wide range of timescales and with near atomic resolution. In recent years NMR methods have also been developed to study protein folding as it might occur within the cell, in a de novo manner, by observing the folding of nascent polypeptides in the process of emerging from the ribosome during synthesis. Despite the 2.3 MDa molecular weight of the bacterial 70S ribosome, many nascent polypeptides, and some ribosomal proteins, have sufficient local flexibility that sharp resonances may be observed in solution-state NMR spectra. In providing information on dynamic regions of the structure, NMR spectroscopy is therefore highly complementary to alternative methods such as X-ray crystallography and cryo-electron microscopy, which have successfully characterized the rigid core of the ribosome particle. However, the low working concentrations and limited sample stability associated with ribosome–nascent chain complexes means that such studies still present significant technical challenges to the NMR spectroscopist. This review will discuss the progress that has been made in this area, surveying all NMR studies that have been published to date, and with a particular focus on strategies for improving experimental sensitivity. PMID:24083462

  6. Protein folding on the ribosome studied using NMR spectroscopy.

    PubMed

    Waudby, Christopher A; Launay, Hélène; Cabrita, Lisa D; Christodoulou, John

    2013-10-01

    NMR spectroscopy is a powerful tool for the investigation of protein folding and misfolding, providing a characterization of molecular structure, dynamics and exchange processes, across a very wide range of timescales and with near atomic resolution. In recent years NMR methods have also been developed to study protein folding as it might occur within the cell, in a de novo manner, by observing the folding of nascent polypeptides in the process of emerging from the ribosome during synthesis. Despite the 2.3 MDa molecular weight of the bacterial 70S ribosome, many nascent polypeptides, and some ribosomal proteins, have sufficient local flexibility that sharp resonances may be observed in solution-state NMR spectra. In providing information on dynamic regions of the structure, NMR spectroscopy is therefore highly complementary to alternative methods such as X-ray crystallography and cryo-electron microscopy, which have successfully characterized the rigid core of the ribosome particle. However, the low working concentrations and limited sample stability associated with ribosome-nascent chain complexes means that such studies still present significant technical challenges to the NMR spectroscopist. This review will discuss the progress that has been made in this area, surveying all NMR studies that have been published to date, and with a particular focus on strategies for improving experimental sensitivity.

  7. NMR studies of protein-ligand interactions.

    PubMed

    Maurer, Till

    2005-01-01

    Interaction between biological macromolecules or of macromolecules with low-molecular-weight ligands is a central paradigm in the understanding of function in biological systems. It is also the major goal in pharmaceutical research to find and optimize ligands that modulate the function of biological macromolecules. Both technological advances and new methods in the field of nuclear magnetic resonance (NMR) have led to the development of several tools by which the interaction of proteins or DNA and low molecular weight-ligands can be characterized at an atomic level. Information can be gained quickly and easily with ligand-based techniques. These need only small amounts of nonisotope labeled, and thus readily available target macromolecules. As the focus is on the signals stemming only from the ligand, no further NMR information regarding the target is needed. Techniques based on the observation of isotopically labeled biological macromolecules open the possibility to observe interactions of proteins with low-molecular-weight ligands, DNA or other proteins. With these techniques, the structure of high-molecular-weight complexes can be determined. Here, the resonance signals of the macromolecule must be identified beforehand, which can be time consuming but with the benefit of obtaining more information with respect to the target ligand complex.

  8. High-Resolution NMR Studies of Human Tissue Factor

    PubMed Central

    Nuzzio, Kristin M.; Watt, Eric D.; Boettcher, John M.; Gajsiewicz, Joshua M.; Morrissey, James H.; Rienstra, Chad M.

    2016-01-01

    In normal hemostasis, the blood clotting cascade is initiated when factor VIIa (fVIIa, other clotting factors are named similarly) binds to the integral membrane protein, human tissue factor (TF). The TF/fVIIa complex in turn activates fX and fIX, eventually concluding with clot formation. Several X-ray crystal structures of the soluble extracellular domain of TF (sTF) exist; however, these structures are missing electron density in functionally relevant regions of the protein. In this context, NMR can provide complementary structural information as well as dynamic insights into enzyme activity. The resolution and sensitivity for NMR studies are greatly enhanced by the ability to prepare multiple milligrams of protein with various isotopic labeling patterns. Here, we demonstrate high-yield production of several isotopically labeled forms of recombinant sTF, allowing for high-resolution NMR studies both in the solid and solution state. We also report solution NMR spectra at sub-mM concentrations of sTF, ensuring the presence of dispersed monomer, as well as the first solid-state NMR spectra of sTF. Our improved sample preparation and precipitation conditions have enabled the acquisition of multidimensional NMR data sets for TF chemical shift assignment and provide a benchmark for TF structure elucidation. PMID:27657719

  9. Some specific features of the NMR study of fluid flows

    NASA Astrophysics Data System (ADS)

    Davydov, V. V.

    2016-07-01

    Some specific features of studying fluid flows with a NMR spectrometer are considered. The consideration of these features in the NMR spectrometer design makes it possible to determine the relative concentrations of paramagnetic ions and measure the longitudinal and transverse relaxation times ( T 1 and T 2, respectively) in fluid flows with an error no larger than 0.5%. This approach allows one to completely avoid errors in determining the state of a fluid from measured relaxation constants T 1 and T 2, which is especially urgent when working with medical suspensions and biological solutions. The results of an experimental study of fluid flows are presented.

  10. An NMR Protonation Study of Metal Diethylenetriaminepentaacetic Acid Complexes.

    ERIC Educational Resources Information Center

    Letkeman, Peter

    1979-01-01

    This experiment is suitable for an integrated laboratory course for senior chemistry majors. It introduces the student to a study of the relative basicity of different proton accepting sites. It serves as an opportunity to learn about nmr techniques and could extend to infrared, as well. (BB)

  11. The PAW/GIPAW approach for computing NMR parameters: a new dimension added to NMR study of solids.

    PubMed

    Charpentier, Thibault

    2011-07-01

    In 2001, Mauri and Pickard introduced the gauge including projected augmented wave (GIPAW) method that enabled for the first time the calculation of all-electron NMR parameters in solids, i.e. accounting for periodic boundary conditions. The GIPAW method roots in the plane wave pseudopotential formalism of the density functional theory (DFT), and avoids the use of the cluster approximation. This method has undoubtedly revitalized the interest in quantum chemical calculations in the solid-state NMR community. It has quickly evolved and improved so that the calculation of the key components of NMR interactions, namely the shielding and electric field gradient tensors, has now become a routine for most of the common nuclei studied in NMR. Availability of reliable implementations in several software packages (CASTEP, Quantum Espresso, PARATEC) make its usage more and more increasingly popular, maybe indispensable in near future for all material NMR studies. The majority of nuclei of the periodic table have already been investigated by GIPAW, and because of its high accuracy it is quickly becoming an essential tool for interpreting and understanding experimental NMR spectra, providing reliable assignments of the observed resonances to crystallographic sites or enabling a priori prediction of NMR data. The continuous increase of computing power makes ever larger (and thus more realistic) systems amenable to first-principles analysis. In the near future perspectives, as the incorporation of dynamical effects and/or disorder are still at their early developments, these areas will certainly be the prime target.

  12. Nitrogen-15 NMR studies of solid dipeptides

    SciTech Connect

    Hartzell, C.J.

    1987-01-01

    The first part of this study deals with the systematic determination of the /sup 15/N chemical shift tensor for the series of dipeptides N-acetyl(1-/sup 13/C)-glycyl-(/sup 15/N)-X-amide (GlyX: X = alanine, glycine, tyrosine), (1-/sup 13/C)-glycyl(/sup 15/N)-glycine/center dot/HCL and (1-/sup 13/C)-ananyl-(/sup 15/N)-alanine (AlaAla). The principal values and polar angles relating the chemical shift tensor to the peptide C-N bond are given for all dipeptides studied. The isotropic values for /sup 15/N varied from 105 ppm up to 119.7ppm for all the dipeptides studied and the angle ..beta../sub CN/ relating sigma/sub 33/to the C-N bond varied from 98/degree/ to 106/degree/. GlyAla and AlaAla showed striking differences in asymmetry parameter, .37 vs. .13, and anisotropy, 165 vs. 144, yet the isotropic values for these two are identical. The /sup 13/C chemical shift principal values and polar angles are determined for AlaAla. The second part of the study deals with an experiment to determine unambiguously the orientation of the chemical shift tensor in the molecular frame.

  13. An NMR Study of Enzyme Activity.

    ERIC Educational Resources Information Center

    Peterman, Keith E.; And Others

    1989-01-01

    A laboratory experiment designed as a model for studying enzyme activity with a basic spectrometer is presented. Included are background information, experimental procedures, and a discussion of probable results. Stressed is the value of the use of Nuclear Magnetic Resonance in biochemistry. (CW)

  14. NMR studies and applications of perfluorocarbon gases

    NASA Astrophysics Data System (ADS)

    Chang, Yulin

    Hyperpolarized 3He has been very successful in magnetic resonance imaging (MRI) of the lungs. It provides ways to study the physiological properties of the lungs and lung function. However, the high costs of the polarizing apparatus and the complicated polarizing procedure are preventing this technique from being clinically used routinely. Recent developments have shown that several fluorinated gases have the potential to replace 3He in some of its applications. This thesis presents some preliminary results of human excised lung imaging using C2F6 and C3F8. These two fluorinated gases were able to yield images with good signal-to-noise ratio and reasonable resolutions in a 1.5 T magnet. Using diffusion MRI of these two gases can distinguish emphysematous lungs from healthy ones. An important application of these gases would be to determine local lung surface-to-volume (S/V) ratio in vivo, which requires the unrestricted (free) diffusivity in each pixel to be known. We present data in this thesis which allow free diffusivities to be calculated from the relaxation time T1. Samples of pure C 2F6 and C3F8 at different pressures and in mixtures with oxygen at different concentrations were made. Measurements were done at two different magnetic fields and temperature was regulated to study the temperature dependence over a small range. These two gases were also used in studies of carbon-block filters, where the strong adsorption of the gases to the high surface-area carbon is beneficial. A brief review of our work on mouse lung imaging using hyperpolarized 3He is presented in Appendix A; Appendix B is a study of the longitudinal spin magnetization in the presence of a strong magnetic field gradient; the construction of the pulsed field gradient waveform measurement coils and some experimental results using these coils are contained in Appendix C.

  15. Proton NMR studies of functionalized nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Tataurova, Yulia Nikolaevna

    Nanoscience is an emerging field that can provide potential routes towards addressing critical issues such as clean and sustainable energy, environmental remediation and human health. Specifically, porous nanomaterials, such as zeolites and mesoporous silica, are found in a wide range of applications including catalysis, drug delivery, imaging, environmental protection, and sensing. The characterization of the physical and chemical properties of nanocrystalline materials is essential to the realization of these innovative applications. The great advantage of porous nanocrystals is their increased external surface area that can control their biological, chemical and catalytic activities. Specific functional groups synthesized on the surface of nanoparticles are able to absorb heavy metals from the solution or target disease cells, such as cancer cells. In these studies, three main issues related to functionalized nanomaterials will be addressed through the application of nuclear magnetic resonance (NMR) techniques including: 1) surface composition and structure of functionalized nanocrystalline particles; 2) chemical properties of the guest molecules on the surface of nanomaterials, and 3) adsorption and reactivity of surface bound functional groups. Nuclear magnetic resonance (NMR) is one of the major spectroscopic techniques available for the characterization of molecular structure and conformational dynamics with atomic level detail. This thesis deals with the application of 1H solution state NMR to porous nanomaterial in an aqueous environment. Understanding the aqueous phase behavior of functionalized nanomaterials is a key factor in the design and development of safe nanomaterials because their interactions with living systems are always mediated through the aqueous phase. This is often due to a lack of fundamental knowledge in interfacial chemical and physical phenomena that occur on the surface of nanoparticles. The use of solution NMR spectroscopy results

  16. Multinuclear NMR studies of water in solutions of simple carbohydrates.

    NASA Astrophysics Data System (ADS)

    Belton, P. S.; Ring, S. G.; Botham, R. L.; Hills, B. P.

    Oxygen-17 water relaxation is reported for the series of α(1 → 4) linked glucans, glucose to maltoheptaose over a wide range of sugar concentrations. The results can be interpreted quantitatively using a two-site exchange model where the 'bound' water reorients anisotropically. The effect of carbohydrate chain length on the fast and slow correlation times characterizing the bound water reorientation is discussed. Comparison is also made with the correlation times derived using deuterium relaxation.

  17. Double rotation NMR studies of zeolites and aluminophosphate molecular sieves

    SciTech Connect

    Jelinek, R. |

    1993-07-01

    Goal is to study the organization and structures of guest atoms and molecules and their reactions on internal surfaces within pores of zeolites and aluminophosphate molecular sieves. {sup 27}Al and {sup 23}Na double rotation NMR (DOR) is used since it removes the anisotropic broadening in NMR spectra of quadrupolar nuclei, thus increasing resolution. This work concentrates on probing aluminum framework atoms in aluminophosphate molecular sieves and sodium extra framework cations in porous aluminosilicates. In aluminophosphates, ordering and electronic environments of the framework {sup 27}Al nuclei are modified upon adsorption of water molecules within the channels; a relation is sought between the sieve channel topology and the organization of adsorbed water, as well as the interaction between the Al nuclei and the water molecules. Extra framework Na{sup +} cations are directly involved in adsorption processes and reactions in zeolite cavities.

  18. 2H NMR studies of supercooled and glassy aspirin

    NASA Astrophysics Data System (ADS)

    Nath, R.; Nowaczyk, A.; Geil, B.; Bohmer, R.

    2007-11-01

    Acetyl salicylic acid, deuterated at the methyl group, was investigated using 2H-NMR in its supercooled and glassy states. Just above the glass transition temperature the molecular reorientations were studied using stimulated-echo spectroscopy and demonstrated a large degree of similarity with other glass formers. Deep in the glassy phase the NMR spectra look similar to those reported for the crystal [A. Detken, P. Focke, H. Zimmermann, U. Haeberlen, Z. Olejniczak, Z. T. Lalowicz, Z. Naturforsch. A 50 (1995) 95] and below 20 K they are indicative for rotational tunneling with a relatively large tunneling frequency. Measurements of the spin-lattice relaxation times for temperatures below 150 K reveal a broad distribution of correlation times in the glass. The dominant energy barrier characterizing the slow-down of the methyl group is significantly smaller than the well defined barrier in the crystal.

  19. NMR study of stable radicals in the gas phase

    NASA Astrophysics Data System (ADS)

    Obynochny, A. A.; Maryasov, A. G.; Shakirov, M. M.; Grigoriev, I. A.

    1993-05-01

    The temperature dependence of the NMR spectrum of methyl-substituted nitroxyl radical of the imidazoline series has been studied. The NMR signal induced by radicals in the gas phase has been observed. A shift of the lines of the NMR spectrum in the gas phase according to the Curie law is observed which allows one to determine the value of the hfi constant of the protons of different racial groups. The hfi constant for methyl-substituted radical within experimental accuracy coincides with those measured by other methods in the liquid phase. In the absorbed phase of the samples under study, a substantial contribution is made by the volumetric susceptibility of the liquid film. The diamagnetic contribution to the magnetic susceptibility of the radical in the liquid state has been measured (in the film of 2 × 10 -6). When the thickness of the adsorbed film is small, the molecular exchange between the liquid and gas phases becomes noticeable, causing a corresponding additional shift of the lines. The gas-kinetic cross section for the radical (120 Å 2) has been estimated from the temperature dependence of the line width in the gas phase.

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

    PubMed

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

    2007-06-01

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

  1. A 13C-NMR study of azacryptand complexes.

    PubMed

    Wild, Aljoscha A C; Fennell, Kevin; Morgan, Grace G; Hewage, Chandralal M; Malthouse, J Paul G

    2014-09-28

    An azacryptand has been solubilised in aqueous media containing 50% (v/v) dimethyl sulphoxide. (13)C-NMR has been used to determine how the azacryptand is affected by zinc binding at pH 10. Using (13)C-NMR and (13)C-enriched bicarbonate we have been able to observe the formation of 4 different carbamate derivatives of the azacryptand at pH 10. The azacryptand was shown to solubilise zinc or cadmium at alkaline pHs. Two moles of zinc are bound per mole of azacryptand and this complex binds 1 mole of carbonate. By replacing the zinc with cadmium-113 we have shown that the (13)C-NMR signal of the (13)C-enriched carbon of the bound carbonate is split into two triplets at 2.2 °C. This shows that two cadmium complexes are formed and in each of these complexes the carbonate group is bound by two magnetically equivalent metal ions. It also demonstrates that these cadmium complexes are not in fast exchange. From temperature studies we show that in the zinc complexes both complexes are in fast exchange with each other but are in slow exchange with free bicarbonate. HOESY is used to determine the position of the carbonate carbon in the complex. The solution and crystal structures of the zinc-carbonate-azacryptand complexes are compared. PMID:25091182

  2. 7Li NMR study of normal human erythrocytes

    NASA Astrophysics Data System (ADS)

    Pettegrew, J. W.; Post, J. F. M.; Panchalingam, K.; Withers, G.; Woessner, D. E.

    The biological action of lithium is of great interest because of the therapeutic efficacy of the cation in manic-depressive illness. To investigate possible molecular interactions of lithium, 7Li NMR studies were conducted on normal human erythrocytes which had been incubated with lithium chloride. The uptake of lithium ions was followed by 7Li NMR, using a dysprosium, tripolyphosphate shift reagent. Lithium uptake followed single-exponential kinetics with a time constant of 14.7 h. The intracellular lithium relaxation times were T 1 ⋍ 5 s and T 2 ⋍ 0.15 s, which implies a lengthening of the lithium correlation time. It was found that lithium does not interact significantly with hemoglobin, the erythrocyte membrane, or artificial phospholipid membranes. Based on measurements of lithium T1 and T2 in concentrated agar gels, the large difference between T1 and T2 for intracellular lithium ions may be due to diffusion of the hydrated lithium ion through heterogeneous electrostatic field gradients created by the erythrocyte membrane-associated cytoskeletal network. Lithium binding to the membrane-associated cytoskeleton, however, cannot be ruled out. Because of the large differences between T1 and T2 of intracellular lithium ions, 1Li NMR may be a sensitive and promising noninvasive method to probe the intracellular environment.

  3. NMR Studies of Molecular Orientation and Dynamics in Spider silk

    NASA Astrophysics Data System (ADS)

    Michal, Carl; Eles, Philip

    2004-05-01

    Spider dragline silk has a unique combination of strength and extensibility that has been difficult to achieve in synthetic polymer fibres and has inspired industrial efforts to produce genetically engineered analogues. In light of these efforts elsewhere, we describe solid-state NMR experiments that elucidate the molecular structure and dynamics of this remarkable material. These experiments include the use of a 2-D exchange NMR experiment known as DECODER in which the sample is reoriented through a discrete angle during the mixing time. This experiment allows a reconstruction of the orientation distribution of the protein backbone. Our data is well described by a two-component distribution where the protein backbones of both components are preferentially aligned along the silk fibre. This experiment is also sensitive to molecular motion on a wide range of time-scales, and is employed to study changes in the silk as a function of fibre extension and hydration. Hydrated silk undergoes a remarkable phenomena known as supercontraction where fibres shrink by up to 50% in length while swelling in diameter. DECODER NMR of fully and partially supercontracted silk reveals that supercontraction occurs through a process of local phase transitions where water disrupts inter- and intra-chain hydrogen bonds.

  4. Lipid-ethanol interaction studied by NMR on bicelles.

    PubMed

    Koenig, Bernd W; Gawrisch, Klaus

    2005-04-21

    The interaction of ethanol with phospholipids was studied in bicelles at a physiologically relevant ethanol concentration of 20 mM and a lipid content of 14 wt % by high-resolution NMR. Transient association of ethanol with magnetically aligned bicelles imparts a small degree of anisotropy to the solute. This anisotropy allows detection of residual (1)H-(1)H and (1)H-(13)C dipolar couplings, which are superimposed on scalar couplings. Residual (2)H NMR quadrupole splittings of isotope-labeled ethanol were measured as well. The analysis of residual tensorial interactions yielded information on the orientation and motions of ethanol in the membrane-bound state. The fraction of phosphatidylcholine-bound ethanol was determined independently by gas chromatography and NMR. About 4% of ethanol is bound to phosphatidylcholine at a bicelle concentration of 14 wt % at 40 degrees C. Free and bound ethanol are in rapid exchange. The lifetime of ethanol association with phosphatidylcholine membranes is of the order of a few nanoseconds.

  5. MRI and unilateral NMR study of reindeer skin tanning processes.

    PubMed

    Zhu, Lizheng; Del Federico, Eleonora; Ilott, Andrew J; Klokkernes, Torunn; Kehlet, Cindie; Jerschow, Alexej

    2015-04-01

    The study of arctic or subarctic indigenous skin clothing material, known for its design and ability to keep the body warm, provides information about the tanning materials and techniques. The study also provides clues about the culture that created it, since tanning processes are often specific to certain indigenous groups. Untreated skin samples and samples treated with willow (Salix sp) bark extract and cod liver oil are compared in this study using both MRI and unilateral NMR techniques. The two types of samples show different proton spatial distributions and different relaxation times, which may also provide information about the tanning technique and aging behavior.

  6. MRI and unilateral NMR study of reindeer skin tanning processes.

    PubMed

    Zhu, Lizheng; Del Federico, Eleonora; Ilott, Andrew J; Klokkernes, Torunn; Kehlet, Cindie; Jerschow, Alexej

    2015-04-01

    The study of arctic or subarctic indigenous skin clothing material, known for its design and ability to keep the body warm, provides information about the tanning materials and techniques. The study also provides clues about the culture that created it, since tanning processes are often specific to certain indigenous groups. Untreated skin samples and samples treated with willow (Salix sp) bark extract and cod liver oil are compared in this study using both MRI and unilateral NMR techniques. The two types of samples show different proton spatial distributions and different relaxation times, which may also provide information about the tanning technique and aging behavior. PMID:25719858

  7. NMR spectroscopic study of organic phosphate esters coprecipitated with calcite

    NASA Astrophysics Data System (ADS)

    Phillips, Brian L.; Zhang, Zelong; Kubista, Laura; Frisia, Silvia; Borsato, Andrea

    2016-06-01

    Organic phosphorus incorporated in calcite during laboratory precipitation experiments and in natural cave deposits was investigated by solid-state NMR spectroscopy. For calcite precipitated in the presence of organic phosphoesters of varying size and functionality, solid-state 31P{1H} CP/MAS NMR shows that the phosphoesters were incorporated intact into the solid. Systematic changes in the 31P NMR chemical shift of the phosphate group were observed between the solid phosphoester and that incorporated in the solid precipitate, yielding 31P NMR chemical shifts of the coprecipitates in the range of +1.8 to -2.2 ppm. These chemical shifts are distinct from that of similarly prepared calcite coprecipitated with inorganic phosphate, 3.5 ppm. Only minor changes were noted in the phosphoester 31P chemical shift anisotropy (CSA) which suggests no significant change in the local structure of the phosphate group, which is dominated by C-O-P bonding. Close spatial proximity of the organic phosphate group to calcite structural components was revealed by 31P/13C rotational echo double resonance (REDOR) experiments for coprecipitates prepared with 13C-labeled carbonate. All coprecipitates showed significant 31P dephasing effects upon 13C-irradiation, signaling atomic-scale proximity to carbonate carbon. The dephasing rate for smaller organophosphate molecules is similar to that observed for inorganic phosphate, whereas much slower dephasing was observed for larger molecules having long and/or bulky side-chains. This result suggests that small organic molecules can be tightly enclosed within the calcite structure, whereas significant structural disruption required to accommodate the larger organic molecules leads to longer phosphate-carbonate distances. Comparison of 31P NMR spectroscopic data from the synthetic coprecipitates with those from calcite moonmilk speleothems indicates that phosphorus occurs mainly as inorganic orthophosphate in the natural deposits, although small

  8. NMR Studies of 3He Films on Boron Nitride

    NASA Astrophysics Data System (ADS)

    Tang, Y.; Sullivan, N. S.

    2014-12-01

    We report the results of NMR studies of the dynamics of 3He adsorbed on hexagonal boron nitride. These studies can identify the phase transitions of the 2D films as a function of temperature. A thermally activated temperature dependence is observed for 2.6 < T < 8 K compared to a linear temperature dependence for 0.7 < T < 2.6 K. This linear dependence is consistent with that expected for thermal diffusion in a fluid for coverages of 0.4 - 0.6 of a monolayer.

  9. Dynamic 1H NMR Studies of Schiff Base Derivatives

    NASA Astrophysics Data System (ADS)

    Köylü, M. Z.; Ekinci, A.; Böyükata, M.; Temel, H.

    2016-01-01

    The spin-lattice relaxation time T 1 and the spin-spin relaxation time T 2 of two Schiff base derivatives, N,N'-ethylenebis(salicylidene)-1,2-diaminoethane (H2L1) and N,N'-ethylenebis (salicylidene)-1,3-diaminopropane (H2L2), in DMSO-d6 solvent were studied as a function of temperature in the range of 20-50°C using a Bruker Avance 400.132 MHz 1H NMR spectrometer. Based on the activation energy ( E a) and correlation time (τc), we believe that the Schiff base derivatives perform a molecular tumbling motion.

  10. Solid-State NMR Studies of Chemically Lithiated CFx

    PubMed Central

    Leifer, N. D.; Johnson, V. S.; Ben-Ari, R.; Gan, H.; Lehnes, J. M.; Guo, R.; Lu, W.; Muffoletto, B. C.; Reddy, T.; Stallworth, P. E.; Greenbaum, S. G.

    2010-01-01

    Three types of fluorinated carbon, all in their original form and upon sequential chemical lithiations via n-butyllithium, were investigated by 13C and 19F solid-state NMR methods. The three starting CFx materials [where x = 1 (nominally)] were fiber based, graphite based, and petroleum coke based. The aim of the current study was to identify, at the atomic/molecular structural level, factors that might account for differences in electrochemical performance among the different kinds of CFx. Differences were noted in the covalent F character among the starting compounds and in the details of LiF production among the lithiated samples. PMID:20676233

  11. Solid-State NMR Studies of Chemically Lithiated CF.

    PubMed

    Leifer, N D; Johnson, V S; Ben-Ari, R; Gan, H; Lehnes, J M; Guo, R; Lu, W; Muffoletto, B C; Reddy, T; Stallworth, P E; Greenbaum, S G

    2010-01-01

    Three types of fluorinated carbon, all in their original form and upon sequential chemical lithiations via n-butyllithium, were investigated by (13)C and (19)F solid-state NMR methods. The three starting CF(x) materials [where x = 1 (nominally)] were fiber based, graphite based, and petroleum coke based. The aim of the current study was to identify, at the atomic/molecular structural level, factors that might account for differences in electrochemical performance among the different kinds of CF(x). Differences were noted in the covalent F character among the starting compounds and in the details of LiF production among the lithiated samples.

  12. ADVANCED SOLIDS NMR STUDIES OF COAL STRUCTURE AND CHEMISTRY

    SciTech Connect

    1997-09-01

    This report covers the progress made on the title project for the project period. The study of coal chemical structure is a vital component of research efforts to develop better chemical utilization of coals, and for furthering our basic understanding of coal geochemistry. In this grant we are addressing several structural questions pertaining to coals with advances in state of the art solids NMR methods. The main activity during this granting period was a completion of a detailed comparative analysis of the suite of spectral editing techniques developed in our laboratory for this purpose. The appended report is a manuscript being submitted to the Journal of Magnetic Resonance on this subject.

  13. ADVANCED SOLIDS NMR STUDIES OF COAL STRUCTURE AND CHEMISTRY

    SciTech Connect

    1998-03-01

    This report covers the progress made on the title project for the project period. The study of coal chemical structure is a vital component of research efforts to develop better chemical utilization of coals, and for furthering our basic understanding of coal geochemistry. In this grant we are addressing several structural questions pertaining to coals with advances in state of the art solids NMR methods. The main activity during this granting period was a detailed comparative analysis of the suite of spectral editing results obtained on the Argonne coals. We have extended our fitting procedure to include carbons of all types in the analysis.

  14. Studies of magnetism using nuclear orientation and related NMR techniques

    NASA Astrophysics Data System (ADS)

    Pond, James F.

    2001-09-01

    Nuclear Orientation and related NMR techniques have been used to study three magnetic insulators: Mn(COOCH3)2·4H2O, MnCl2·4H2O and CoCl2·6H 2O. Continuous wave NMR thermally detected by Nuclear Orientation has been used to investigate the magnetic properties and spin dynamics of the quasi-2-dimensional ferromagnet 54Mn-Mn(COOCH3)2·4H 2O. The system exhibits a frequency pulling effect due to the indirect Suhl-Nakamura interaction between nuclear spins and the electronic spin excitation spectrum is related to the coupling strength of the nuclear spins. The temperature dependence of the frequency pulling effect was measured for the two crystalline sublattices Mn1 and Mn2 in low magnetic field. The spectra show a structure not predicted theoretically. The current theory is valid only for I = 1/2 with uniaxial crystalline anisotropy fields. The theory of frequency pulling has been extended here to the case of I ≥ 1/2 and non-uniaxial crystalline anisotropy fields and the resonant frequencies and linewidths have been calculated as a function of temperature. The new theory and data agree well in terms of the magnitude and temperature dependence of the frequency pulling. Discrepancies are likely due to simplifying assumptions when calculating the electronic magnon spectrum. Classical and quantum numerical simulations confirm qualitatively the predictions of the model. The first Low Temperature Nuclear Orientation experiments on isotopes implanted into insulators is reported. Radioactive 56Mn ions have been implanted into insulating, antiferromagnetic crystals of MnCl 2·4H2O and CoCl2·6H2O. In MnCl2·4H2O, comparison of the gamma-ray anisotropy of the 56Mn nuclei with that of 54Mn, doped into the sample during growth, showed that both the 56Mn and 54Mn spins felt a very similar hyperfine field. The site occupancy factor in a simple, two site model was deduced to be 0.96+0.04-0.07 . In CoCl2·6H2O, the average hyperfine field for the implanted 56Mn was significantly

  15. NMR studies of copper speciation in the bovine rumen environment.

    PubMed

    Reid, R S; Attaelmannan, M A

    1998-02-01

    Dietary copper supplements containing complexed copper have been asserted to be more bioavailable than 'inorganic' supplements. Since bioavailability is intimately related to the particular metal ion species that exist in any given environment, studies of solution speciation can be used to examine this assertion. In a previous study, our computer modeling of copper speciation in bovine saliva indicated that when a lysine-complexed copper supplement is used, the complex will not persist. In the present study, these conclusions are supplemented and extended using 1H NMR experiments. Lysine and the copper(II)-lysine system are characterized, and chemical shifts of the individual species obtained. Chemical shift values for the copper(II)-lysine-bovine saliva system can then be predicted. Results show good agreement with experimental values. The scope of the computer modeling is then expanded to include the major low molar mass ligands present in the rumen. Implications of the results are discussed. The validity of this rumen model is further evaluated by NMR investigations on biological samples. The study provides further evidence that complexes such as copper(II)-lysine would disintegrate in the gastrointestinal tract, and are unlikely to be absorbed intact.

  16. On the potential of hyperpolarized water in biomolecular NMR studies

    PubMed Central

    Harris, Talia; Szekely, Or; Frydman, Lucio

    2016-01-01

    A main obstacle arising when using ex-situ hyperpolarization to increase the sensitivity of biomolecular NMR, is the fast relaxation that macromolecular spins undergo upon being transferred from the polarizer to the spectrometer where their observation takes place. To cope with this limitation the present study explores the use of hyperpolarized water, as a means to enhance the sensitivity of nuclei in biomolecules. Methods to achieve proton polarizations in excess of 5% in water transferred into the NMR spectrometer were devised, as were methods enabling this polarization to last for up to 30 sec. Upon dissolving aminoacids and polypeptides sited at the spectrometer into such hyperpolarized water, a substantial enhancement of certain biomolecular amide and amine proton resonances was observed. This exchange driven 1H enhancement was further passed on to sidechain and to backbone nitrogens, owing to spontaneous one-bond Overhauser processes. 15N signal enhancements >500 over 11.7 T thermal counterparts could thus be imparted, in a kinetic process that enabled multi-scan signal averaging. Besides potential bioanalytical uses, this approach opens interesting possibilities in the monitoring of dynamic biomolecular processes -including solvent accessibility and exchange process. PMID:24417324

  17. NMR Studies of Quantum Tunneling in Monolayers of Helium Three

    NASA Astrophysics Data System (ADS)

    Parks, Charles; Stachowiak, Piotr; Sullivan, Neil

    2002-03-01

    The results of NMR studies of the nuclear spin-spin relaxation are reported for commensurate monolayers of helium three adsorbed on hexagonal boron nitride. The measurements were made using pulsed NMR techniques for low temperatures, 0.01 < T < 5.0 K, and for moderately high magnetic fields (up to 6 T). The relaxation rate is independent of temperature at low temperatures, 0.12 < T < 0.85 K, and this behavior is interpreted in terms of particle-particle exchange motions of the adsorbed helium atoms. The effective exchange rates were observed to change significantly on replacing a fraction of the helium atoms with relatively immobile neon atoms. This is understood if there is a significant 3-particle exchange in addition to 2-particle exchange. The analyses of the experimental results indicate that the 3-spin exchange term in the exchange Hamiltonian is of opposite sign to that of the 2-spin exchange and also has a larger amplitude. At high temperatures, 0.8 < T < 5.0 K, an exponential temperature dependence of the rate is observed that is attributed to the thermal activation of vacancies.

  18. NMR at cryogenic temperatures: A {sup 13}C NMR study of ferrocene

    SciTech Connect

    Orendt, A.M.; Facelli, J.C.; Jiang, Y.J.; Grant, D.M.

    1998-09-24

    A new cryogenic apparatus is described that can be used to obtain NMR spectra at temperatures down to 8--10 K. The static solid {sup 13}C NMR spectrum of ferrocene is recorded at that temperature. Spectra recorded at higher temperatures show that ferrocene is still freely rotating about its 5-fold symmetry axis on the {sup 13}C NMR time scale at 45--50 K. A comparison of the principal values of the {sup 13}C chemical-shift tensor obtained from the room- and low-temperature spectra of ferrocene indicates that the lowest frequency chemical shift principal component, {delta}{sub 33}, is tilted off this symmetry axis by approximately 12{degree}. Quantum chemical calculations of the chemical-shift tensor, completed on structures of ferrocene from the literature as well as on optimized structures with the cyclopentadienyl rings locked in both the staggered and eclipsed arrangements, predict the angle between the {delta}{sub 33} direction and the rotation axis to be between 11 and 15{degree}, depending upon the geometry used in the calculation. The calculations also predict the sign of the angular perturbation, information not obtained from the experiment. An explanation of this angular change in the {delta}{sub 33} direction is provided by the composition of the molecular orbitals.

  19. NMR Studies on the Aqueous Phase Photochemical Degradation of TNT

    SciTech Connect

    Thorn, Kevin A.; Cox, Larry G.

    2008-04-06

    Aqueous phase photochemical degradation of 2,4,6-trinitrotoluene (TNT) is an important pathway in several environments, including washout lagoon soils, impact craters from partially detonated munitions that fill with rain or groundwater, and shallow marine environments containing unexploded munitions that have corroded. Knowledge of the degradation products is necessary for compliance issues on military firing ranges and formerly used defense sites. Previous laboratory studies have indicated that UV irradiation of aqueous TNT solutions results in a multicomponent product mixture, including polymerization compounds, that has been only partially resolved by mass spectrometric analyses. This study illustrates how a combination of solid and liquid state 1H, 13C, and 15N NMR spectroscopy, including two dimensional analyses, provides complementary information on the total product mixture from aqueous photolysis of TNT, and the effect of reaction conditions. Among the degradation products detected were amine, amide, azoxy, azo, and carboxylic acid compounds.

  20. Amphiphile diffusion in model membrane systems studied by pulsed NMR.

    PubMed

    Lindblom, G; Wennerström, H

    1977-01-01

    The translational diffusion of the amphiphilic molecules in a number of lyotropic liquid crystalline phases has been measured with the pulsed NMR pulsed magnetic field gradient method. The amphiphiles studied were soaps, monoglycerids and lecithins. Measurements were performed both for oriented lamellar and for cubic phases. The order of magnitude of the diffusion coefficients was found to be the same as in neat liquids of analogous compounds. It was also found that the difussion coefficient depend markedly on the amphiphile end group in a way that parallels the area per polar head group as determined in X-ray studies. When corrections for geometrical factors has been made the diffusion rate is approximately equal in cubic and lamellar phases containing the same amphiphile.

  1. NMR relaxation studies in doped poly-3-methylthiophene

    NASA Astrophysics Data System (ADS)

    Singh, K. Jugeshwar; Clark, W. G.; Gaidos, G.; Reyes, A. P.; Kuhns, P.; Thompson, J. D.; Menon, R.; Ramesh, K. P.

    2015-05-01

    NMR relaxation rates (1 /T1 ), magnetic susceptibility, and electrical conductivity studies in doped poly-3-methylthiophene are reported in this paper. The magnetic susceptibility data show the contributions from both Pauli and Curie spins, with the size of the Pauli term depending strongly on the doping level. Proton and fluorine NMR relaxation rates have been studied as a function of temperature (3-300 K) and field (for protons at 0.9, 9.0, 16.4, and 23.4 T, and for fluorine at 9.0 T). The temperature dependence of T1 is classified into three regimes: (a) For T <(g μBB /2 kB ) , the relaxation mechanism follows a modified Korringa relation due to electron-electron interactions and disorder. 1H - T1 is due to the electron-nuclear dipolar interaction in addition to the contact term. (b) For the intermediate temperature range (g μBB /2 kB ) study. Fluorine relaxation data have been analyzed and attributed to the P F6 reorientation. The cross relaxation among the 1H and 19F nuclei has been observed in the entire temperature range suggesting the role of magnetic dipolar interaction modulated by the reorientation of the symmetric molecular subgroups. The data analysis shows that the enhancement in the Korringa ratio is greater in a less conducting sample. Intra- and interchain hopping of charge carriers is found to be a dominant relaxation mechanism at low temperature. Frequency dependence of T1-1 on temperature shows that at low temperature [T <(g μBB /2 kB ) ] the system shows three dimensions and changes to quasi one dimension at

  2. NMR studies of two spliced leader RNAs using isotope labeling

    SciTech Connect

    Lapham, J.; Crothers, D.M.

    1994-12-01

    Spliced leader RNAs are a class of RNA molecules (<200 nts) involved in the trans splicing of messenger RNA found in trypanosomes, nematodes, and other lower eukaryotes. The spliced leader RNA from the trypanosome Leptomonas Collosoma exists in two alternate structural forms with similar thermal stabilities. The 54 nucleotides on the 5{prime} end of the SL molecule is structurally independent from the 3{prime} half of the RNA, and displays the two structural forms. Furthermore, the favored of the two structures was shown to contain anomalous nuclease sensitivity and thermal stability features, which suggests that there may be tertiary interactions between the splice site and other nucleotides in the 5{prime} end. Multidimensional NMR studies are underway to elucidate the structural elements present in the SL RNAs that give rise to their physical properties. Two spliced leader sequences have been studied. The first, the 54 nucleotides on the 5{prime} end of the L. Collosoma sequence, was selected because of earlier studies in our laboratory. The second sequence is the 5{prime} end of the trypanosome Crithidia Fasciculata, which was chosen because of its greater sequence homology to other SL sequences. Given the complexity of the NMR spectra for RNA molecules of this size, we have incorporated {sup 15}N/{sup 13}C-labeled nucleotides into the RNA. One of the techniques we have developed to simplify the spectra of these RNA molecules is isotope labeling of specific regions of the RNA. This has been especially helpful in assigning the secondary structure of molecules that may be able to adopt multiple conformations. Using this technique one can examine a part of the molecule without spectral interference from the unlabeled portion. We hope this approach will promote an avenue for studying the structure of larger RNAs in their native surroundings.

  3. NMR and molecular mechanics study of pyrethrins I and II.

    PubMed

    Rugutt, J K; Henry, C W; Franzblau, S G; Warner, I M

    1999-08-01

    Bioassay-directed fractionation of the organic extract of the Kenyan pyrethrum flowers (Chrysanthemum cinerariaefolium Vissiani) resulted in the isolation of two natural pyrethrin esters, pyrethrin I (PI) and pyrethrin II (PII) as the major constituents. These esters elicited inhibition of the multiple drug resistant (MDR) Mycobacterium tuberculosis. The high-field (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of PI and PII were unequivocally assigned using modern two-dimensional (2D) proton-detected heteronuclear multiple-quantum coherence (HMQC) and heteronuclear multiple-bond correlation (HMBC) experiments. The conformations of both esters were deduced from (1)H-(1)H vicinal coupling constants and confirmed by 2D nuclear Overhauser effect spectroscopy (NOESY). Computer molecular modeling (MM) studies revealed that PI and PII molecules adopt a "love-seat" conformation in chloroform (CDCl(3)) solution.

  4. Study of aqueous humour by 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Tkadlecová, Marcela; Havlíček, Jaroslav; Volka, Karel; Souček, Petr; Karel, Ivan

    1999-05-01

    The aim of this work was to study the composition of the samples of human aqueous humour including the protein content. Using 1H NMR spectroscopy many compounds (proteins, glucose, lactate, citrate and other metabolites) can be identified and their concentrations evaluated using the internal standard. While the concentrations of non-proteins in aqueous humour were relatively stable, the amount of proteins differed much more. In most of the spectra, the signals of proteins were hardly distinguishable from the baseline. For some samples a significantly higher protein content (more than 1 mg/ml) was found. The total protein concentration expressed in albumin equivalents can be determined by comparing the spectra measured by S2PUL (standard measurement) and CPMG (protein suppression) pulse sequentions. For comparison, the spectra of rabbit and bovine aqueous humour are also given.

  5. Ultra-broadband NMR probe: numerical and experimental study of transmission line NMR probe.

    PubMed

    Kubo, Atsushi; Ichikawa, Shinji

    2003-06-01

    We have reinvestigated a transmission line NMR probe first published by Lowe and co-workers in 1970s [Rev. Sci. Instrum. 45 (1974) 631; 48 (1977) 268] numerically and experimentally. The probe is expected to be ultra-broadband, thus might enable new types of solid-state NMR experiments. The NMR probe consists of a coil and capacitors which are connected to the coil at regular intervals. The circuit is the same as a cascaded LC low-pass filter, except there are nonzero mutual inductances between different coil sections. We evaluated the mutual inductances by Neumann's formula and calculated the electrical characteristics of the probe as a function of a carrier frequency. We found that they were almost the same as those of a cascaded LC low-pass filter, when the inductance L of a section was estimated from the inductance of the whole coil divided by the number of the sections, and if C was set to the capacitance in a section. For example, the characteristic impedance of a transmission line coil is given by Z=(L/C)(1/2). We also calculated the magnitude and the distribution of RF magnetic field inside the probe. The magnitude of RF field decreases when the carrier frequency is increased because the phase delay between neighboring sections is proportional to the carrier frequency. For cylindrical coils, the RF field is proportional to (pinu/2nu(d))(1/2)exp(-nu/nu(d)), where the decay frequency nu(d) is determined by the dimensions of the coil. The observed carrier frequency thus must be much smaller than the decay frequency. This condition restricts the size of transmission line coils. We made a cylindrical coil for a 1H NMR probe operating below 400 MHz. It had a diameter 2.3mm and a pitch 1.2mm. Five capacitors of 6pF were connected at every three turns. The RF field strength was 40 and 60 kHz at the input RF power 100 W by a calculation and by experiments, respectively. The calculations showed that the RF field inhomogeneity along the coil axis was caused by a

  6. Solid-State NMR Studies of Amyloid Fibril Structure

    NASA Astrophysics Data System (ADS)

    Tycko, Robert

    2011-05-01

    Current interest in amyloid fibrils stems from their involvement in neurodegenerative and other diseases and from their role as an alternative structural state for many peptides and proteins. Solid-state nuclear magnetic resonance (NMR) methods have the unique capability of providing detailed structural constraints for amyloid fibrils, sufficient for the development of full molecular models. In this article, recent progress in the application of solid-state NMR to fibrils associated with Alzheimer's disease, prion fibrils, and related systems is reviewed, along with relevant developments in solid-state NMR techniques and technology.

  7. Dynamic NMR of low-sensitivity fast-relaxing nuclei: (17)O NMR and DFT study of acetoxysilanes.

    PubMed

    Fusaro, Luca; Mameli, Giulia; Mocci, Francesca; Luhmer, Michel; Cerioni, Giovanni

    2012-02-01

    (17)O NMR is not routinely used for structure characterization, and kinetic studies of fluxional organic compounds are seldom undertaken because poor sensitivity and fast quadrupole relaxation are frequently regarded as intractable issues. This work shows how, nowadays, quantitative (17)O dynamic NMR studies on small organic molecules are feasible without enrichment being needed. It reports on acetoxysilanes, a class of fluxional compounds whose structure and dynamics were to be clarified. Natural abundance (17)O NMR spectra were recorded over a wide range of temperatures using standard instrumentation. The analysis relies on simple linewidth measurements and directly provides the activation parameters. The activation enthalpy is found to decrease with increasing number of acetoxy groups bound to silicon. Density functional theory calculations properly predict this trend and show that a single oxygen atom of the acetoxy group is bound to silicon, excluding chelation as binding mode, and that the dynamic process involves the shift of the silicon atom between the two oxygen atoms of the acetoxy group.

  8. Diffusion NMR methods applied to xenon gas for materials study.

    PubMed

    Mair, R W; Rosen, M S; Wang, R; Cory, D G; Walsworth, R L

    2002-12-01

    We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack. PMID:12807139

  9. Diffusion NMR methods applied to xenon gas for materials study

    NASA Technical Reports Server (NTRS)

    Mair, R. W.; Rosen, M. S.; Wang, R.; Cory, D. G.; Walsworth, R. L.

    2002-01-01

    We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack. c2002 John Wiley & Sons, Ltd.

  10. Fundamental studies of supported bimetallic catalysts by NMR spectroscopy

    SciTech Connect

    Savargaonkar, N.

    1996-10-17

    Various hydrogenation reactions on transition metals are important commercially whereas certain hydrogenolysis reactions are useful from fundamental point of view. Understanding the hydrogen mobility and kinetics of adsorption-desorption of hydrogen is important in understanding the mechanisms of such reactions involving hydrogen. The kinetics of hydrogen chemisorption was studied by means of selective excitation NMR on silica supported Pt, Rh and Pt-Rh catalysts. The activation energy of hydrogen desorption was found to be lower on silica supported Pt catalysts as compared to Rh and Pt-Rh catalysts. It was found that the rates of hydrogen adsorption and desorption on Pt-Rh catalyst were similar to those on Rh catalyst and much higher as compared to Pt catalyst. The Ru-Ag bimetallic system is much simpler to study than the Pt-Rh system and serves as a model system to characterize more complicated systems such as the K/Ru system. Ag was found to decrease the amounts of adsorbed hydrogen and the hydrogen-to-ruthenium stoichiometry. Ag reduced the populations of states with low and intermediate binding energies of hydrogen on silica supported Ru catalyst. The rates of hydrogen adsorption and desorption were also lower on silica supported Ru-Ag catalyst as compared to Ru catalyst. This report contains introductory information, the literature review, general conclusions, and four appendices. An additional four chapters and one appendix have been processed separately for inclusion on the data base.

  11. NMR Study of Strontium Binding by a Micaceous Mineral

    SciTech Connect

    Bowers, Geoffrey M.; Ravella, Ramesh; Komarneni, S.; Mueller, Karl T.

    2006-04-13

    The nature of strontium binding by soil minerals directly affects the transport and sequestration/remediation of radioactive strontium species released from leaking high-level nuclear waste storage tanks. However, the molecular-level structure of strontium binding sites has seldom been explored in phyllosilicate minerals by direct spectroscopic means and is not well-understood. In this work, we use solid-state NMR to analyze strontium directly and indirectly in a fully strontium-exchanged synthetic mica of nominal composition Na4Mg6Al4Si4O20F4. Thermogravimetric analysis, X-ray diffraction analysis, and NMR evidence supports that heat treatment at 500 °C for 4 h fully dehydrates the mica, creating a hydrogen-free interlayer. Analysis of the strontium NMR spectrum of the heat-treated mica shows a single strontium environment with a quadrupolar coupling constant of 9.02 MHz and a quadrupolar asymmetry parameter of 1.0. These quadrupolar parameters are consistent with a highly distorted and asymmetric coordination environment that would be produced by strontium cations without water in the coordination sphere bound deep within the ditrigonal holes. Evidence for at least one additional strontium environment, where proton-strontium couplings may occur, was found via a 1H-87Sr transfer of populations by double resonance NMR experiment. We conclude that the strontium cations in the proton-free interlayer are observable by 87Sr NMR and bound through electrostatic interactions as nine coordinate inner-sphere complexes sitting in the ditrigonal holes. Partially hydrated strontium cations invisible to direct 87Sr NMR are also present and located on the external mica surfaces, which are known to hydrate upon exposure to atmospheric moisture. These results demonstrate that modern pulsed NMR techniques and high fields can be used effectively to provide structural details of strontium binding by phyllosilicate minerals.

  12. NMR study of strontium binding by a micaceous mineral.

    PubMed

    Bowers, Geoffrey M; Ravella, Ramesh; Komarneni, Sridhar; Mueller, Karl T

    2006-04-13

    The nature of strontium binding by soil minerals directly affects the transport and sequestration/remediation of radioactive strontium species released from leaking high-level nuclear waste storage tanks. However, the molecular-level structure of strontium binding sites has seldom been explored in phyllosilicate minerals by direct spectroscopic means and is not well-understood. In this work, we use solid-state NMR to analyze strontium directly and indirectly in a fully strontium-exchanged synthetic mica of nominal composition Na(4)Mg(6)Al(4)Si(4)O(20)F(4). Thermogravimetric analysis, X-ray diffraction analysis, and NMR evidence supports that heat treatment at 500 degrees C for 4 h fully dehydrates the mica, creating a hydrogen-free interlayer. Analysis of the strontium NMR spectrum of the heat-treated mica shows a single strontium environment with a quadrupolar coupling constant of 9.02 MHz and a quadrupolar asymmetry parameter of 1.0. These quadrupolar parameters are consistent with a highly distorted and asymmetric coordination environment that would be produced by strontium cations without water in the coordination sphere bound deep within the ditrigonal holes. Evidence for at least one additional strontium environment, where proton-strontium couplings may occur, was found via a (1)H-(87)Sr transfer of populations by double resonance NMR experiment. We conclude that the strontium cations in the proton-free interlayer are observable by (87)Sr NMR and bound through electrostatic interactions as nine coordinate inner-sphere complexes sitting in the ditrigonal holes. Partially hydrated strontium cations invisible to direct (87)Sr NMR are also present and located on the external mica surfaces, which are known to hydrate upon exposure to atmospheric moisture. These results demonstrate that modern pulsed NMR techniques and high fields can be used effectively to provide structural details of strontium binding by phyllosilicate minerals. PMID:16599480

  13. NMR Spectroscopy to Study MAP Kinase Binding to MAP Kinase Phosphatases.

    PubMed

    Peti, Wolfgang; Page, Rebecca

    2016-01-01

    NMR spectroscopy and other solution methods are increasingly being used to obtain novel insights into the mechanisms by which MAPK regulatory proteins bind and direct the activity of MAPKs. Here, we describe how interactions between the MAPK p38α and its regulatory proteins are studied using NMR spectroscopy, isothermal titration calorimetry, and small angle X-ray scattering (SAXS). PMID:27514807

  14. High resolution deuterium NMR studies of bacterial metabolism

    SciTech Connect

    Aguayo, J.B.; Gamcsik, M.P.; Dick, J.D.

    1988-12-25

    High resolution deuterium NMR spectra were obtained from suspensions of five bacterial strains: Escherichia coli, Clostridium perfringens, Klebsiella pneumoniae, Proteus mirabilis, and Staphylococcus aureus. Deuterium-labeled D-glucose at C-1, C-2, and C-6 was used to monitor dynamically anaerobic metabolism. The flux of glucose through the various bacterial metabolic pathways could be determined by following the disappearance of glucose and the appearance of the major end products in the 2H NMR spectrum. The presence of both labeled and unlabeled metabolites could be detected using 1H NMR spectroscopy since the proton resonances in the labeled species are shifted upfield due to an isotopic chemical shift effect. The 1H-1H scalar coupling observed in both the 2H and 1H NMR spectra was used to assign definitively the resonances of labeled species. An increase in the intensity of natural abundance deuterium signal of water can be used to monitor pathways in which a deuteron is lost from the labeled metabolite. The steps in which label loss can occur are outlined, and the influence these processes have on the ability of 2H NMR spectroscopy to monitor metabolism are assessed.

  15. Internal dynamics of DNA - a solid state deuterium NMR study

    SciTech Connect

    Huang, Wen-Chang.

    1989-01-01

    In this dissertation, solid state {sup 2}H NMR spectroscopy has been used to investigate the dynamics of the sodium salt oligonucleotide, (d(CGCGAATTCGCG)){sub 2}, which contains the Eco R1 binding site. Deuterium quadrupole echo line shape and spin-lattice relaxation times were obtained as a function of hydration on three different deuterated samples. In the first sample, (d{sub 12}-(d(CG*CG*A*A*TTCG*CG*)){sub 2}), the C8 proton of all purine in the self-complementary dodecamer were exchanged for deuterons. Specifically labeled thymidine (C6 deuterated) was also synthetically incorporated at the seventh position (counting 5{prime} to 3{prime}) in the sequence (d{sub 2}-(d(CGCGAAT*TCGCG)){sub 2}). In the third sample the C2{double prime} position of the furanose ring of adenosine at the fifth and sixth positions in the same sequence (d{sub 4}-(d(CGCGA*A*TTCGCG)){sub 2}) was deuterium labeled. The static quadrupole coupling constant (e{sup 2}qQ/h) and asymmetry parameter ({eta}) were obtained through the analysis of appropriative motional models from the corresponding monomers studies.

  16. Comprehensive multiphase NMR: a promising technology to study plants in their native state.

    PubMed

    Wheeler, Heather L; Soong, Ronald; Courtier-Murias, Denis; Botana, Adolfo; Fortier-Mcgill, Blythe; Maas, Werner E; Fey, Michael; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J; Campbell, Malcolm M; Simpson, Andre

    2015-09-01

    Nuclear magnetic resonance (NMR) spectroscopy is arguably one the most powerful tools to study the interactions and molecular structure within plants. Traditionally, however, NMR has developed as two separate fields, one dealing with liquids and the other dealing with solids. Plants in their native state contain components that are soluble, swollen, and true solids. Here, a new form of NMR spectroscopy, developed in 2012, termed comprehensive multiphase (CMP)-NMR is applied for plant analysis. The technology composes all aspects of solution, gel, and solid-state NMR into a single NMR probe such that all components in all phases in native unaltered samples can be studied and differentiated in situ. The technology is evaluated using wild-type Arabidopsis thaliana and the cellulose-deficient mutant ectopic lignification1 (eli1) as examples. Using CMP-NMR to study intact samples eliminated the bias introduced by extraction methods and enabled the acquisition of a more complete structural and metabolic profile; thus, CMP-NMR revealed molecular differences between wild type (WT) and eli1 that could be overlooked by conventional methods. Methanol, fatty acids and/or lipids, glutamine, phenylalanine, starch, and nucleic acids were more abundant in eli1 than in WT. Pentaglycine was present in A. thaliana seedlings and more abundant in eli1 than in WT. PMID:25855560

  17. Study of aging of silicone rubber biomaterials with NMR.

    PubMed

    Pfleiderer, B; Xu, P; Ackerman, J L; Garrido, L

    1995-09-01

    Multinuclear nuclear magnetic resonance (NMR) spectroscopy (29Si, 13C, 1H) is used to characterize the aging process of silicone rubber-based biomaterials in a rat model. 1H NMR relaxation measurements (spin-lattice, T1, and spin-spin, T2, relaxation times) were performed to better understand the molecular dynamics of polysiloxane chains in implants. After 1 year of implantation in animals, changes in the 1H T2 relaxation times and the NMR spectra were observed in polydimethylsiloxane, Silastic sheets and chin implants, while these measurements remain unchanged in finger joints. Very small amounts of fat were detected in all types of silicone rubber implants at the end of the implantation period. This work shows that free silicone migrates from the implants to adjacent tissues and distant sites, such as spleen or liver, and is chemically modified.

  18. Solid state NMR studies of gels derived from low molecular mass gelators.

    PubMed

    Nonappa; Kolehmainen, E

    2016-07-13

    Since its invention more than six decades ago, nuclear magnetic resonance (NMR) spectroscopy has evolved as an inevitable part of chemical as well as structural analysis of small molecules, polymers, biomaterials and hybrid materials. In the solution state, due to the increased viscosity of complex viscoelastic fluids such as gels, liquid crystals and other soft materials, the rate of molecular tumbling is reduced, which in turn affects the chemical shift anisotropy, dipolar and quadrupolar interactions. As a consequence the solution state NMR spectra show broad lines, and therefore, extracting detailed structural information is a challenging task. In this context, solid state (SS) NMR has the ability to distinguish between a minute amount of polymorphic forms, conformational changes, and the number of non-equivalent molecules in an asymmetric unit of a crystal lattice, and to provide both qualitative as well as quantitative analytical data with a short-range order. Therefore, SS NMR has continued to evolve as an indispensable tool for structural analysis and gave birth to a new field called NMR crystallography. Solid state cross polarization (CP) and high resolution (HR) magic angle spinning (MAS) NMR spectroscopy has been used to study weak interactions in polymer gels. However, the application of SS NMR spectroscopy to study gels derived from low molecular weight gelators has been limited until recently. In this review, we will focus on the importance of solid state NMR spectroscopy in understanding and elucidating the structure of supramolecular gels derived from low molecular weight gelators with selected examples. PMID:27374054

  19. Solid state NMR studies of gels derived from low molecular mass gelators.

    PubMed

    Nonappa; Kolehmainen, E

    2016-07-13

    Since its invention more than six decades ago, nuclear magnetic resonance (NMR) spectroscopy has evolved as an inevitable part of chemical as well as structural analysis of small molecules, polymers, biomaterials and hybrid materials. In the solution state, due to the increased viscosity of complex viscoelastic fluids such as gels, liquid crystals and other soft materials, the rate of molecular tumbling is reduced, which in turn affects the chemical shift anisotropy, dipolar and quadrupolar interactions. As a consequence the solution state NMR spectra show broad lines, and therefore, extracting detailed structural information is a challenging task. In this context, solid state (SS) NMR has the ability to distinguish between a minute amount of polymorphic forms, conformational changes, and the number of non-equivalent molecules in an asymmetric unit of a crystal lattice, and to provide both qualitative as well as quantitative analytical data with a short-range order. Therefore, SS NMR has continued to evolve as an indispensable tool for structural analysis and gave birth to a new field called NMR crystallography. Solid state cross polarization (CP) and high resolution (HR) magic angle spinning (MAS) NMR spectroscopy has been used to study weak interactions in polymer gels. However, the application of SS NMR spectroscopy to study gels derived from low molecular weight gelators has been limited until recently. In this review, we will focus on the importance of solid state NMR spectroscopy in understanding and elucidating the structure of supramolecular gels derived from low molecular weight gelators with selected examples.

  20. Study of the New Pulse NMR System for the Jefferson Lab Helium-3 Polarized Target

    NASA Astrophysics Data System (ADS)

    Newton, Joseph

    2013-10-01

    At Jefferson Lab, a polarized Helium-3 target is used to study the neutron. The Helium-3 target is undergoing an upgrade to improve its polarization. Measuring it involved a new technique known as pulse Nuclear Magnetic Resonance (NMR). The focus of this project was to find noise in the Pulse NMR signal and to compute the calibration constant to make the polarization easier to deduce. Pulse NMR calibration tests were performed by doing AFP NMR measurements followed by Pulse NMR measurements while varying certain conditions. These included the convection heater, the operation of the oven, and the operation of the laser. Data analysis was done by fitting the pulse NMR signal from the oscilloscope and utilizing the Fourier Transform. Noise was analyzed in the fitting and the Fourier Transform. The calibration constants were affected by the convection heater. The values deviated between the pumping and target chambers of the cell when there was no convection but the values were closer when convection was induced. As far as the noise, it was found to be significant. These results will enable the calculation of the polarization with pulse NMR. In addition, the signal analysis provided insight into the influence of background noise on the pulse NMR measurement. This research was done though the SULI program of the Department of Energy.

  1. Novel application of NMR relaxometry in studies of diffusion in virgin rape oil.

    PubMed

    Rachocki, A; Tritt-Goc, J

    2014-01-01

    Field cycling (FC) proton nuclear magnetic resonance ((1)H NMR) relaxometry was applied to study the dynamics of rape oil molecules. The spin-lattice relaxation data, measured in the frequency range from 0.01 to 30 MHz, were analysed by applying relaxation theory combined with the force-free-hard-sphere (FFHS) diffusion model. In the low frequency range, the relaxation was dominated by the translational diffusion contribution. Therefore, the diffusion coefficient of rape oil was determined from a linear dependence of the (1)H NMR relaxation dispersion drawn as a function of the square root of Larmor frequency. The results are consistent with those obtained from the pulse gradient spin echo (PGSE) NMR method. To estimate the density of oil protons, a parameter required to derive the diffusion coefficient from NMR relaxometry, a single point imaging (SPI) NMR experiment was proposed.

  2. NMR and NQR study of the thermodynamically stable quasicrystals

    SciTech Connect

    Shastri, A.

    1995-02-10

    {sup 27}Al and {sup 61,65}Cu NMR measurements are reported for powder samples of stable AlCuFe and AlCuRu icosahedral quasicrystals and their crystalline approximants, and for a AlPdMn single grain quasicrystal. Furthermore, {sup 27}Al NQR spectra at 4.2 K have been observed in the AlCuFe and AlCuRu samples. From the quadrupole perturbed NMR spectra at different magnetic fields, and from the zero field NQR spectra, a wide distribution of local electric field gradient (EFG) tensor components and principal axis system orientations was found at the Al site. A model EFG calculation based on a 1/1 AlCuFe approximant was successful in explaining the observed NQR spectra. It is concluded that the average local gradient is largely determined by the p-electron wave function at the Al site, while the width of the distribution is due to the lattice contribution to the EFG. Comparison of {sup 63}Cu NMR with {sup 27}Al NMR shows that the EFG distribution at the two sites is similar, but that the electronic contribution to the EFG is considerably smaller at the Cu site, in agreement with a more s-type wave function of the conduction electrons.

  3. NMR Studies of Biomass and its Reaction Products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biomass refers to biological material derived from living or recently living organisms, such as wood, agricultural products and wastes, and alcohol fuels. An increasingly popular R&D approach is to convert biomass into industrial polymers or chemicals. NMR is an excellent technique for the character...

  4. 129Xe NMR studies of biochar made from biobased materials

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biochar is created by pyrolysis of biobased materials under controlled oxidative environments. The product is charcoal-like and can be used as filtration medium, sequestrant for metallic ions, soil conditioner, and other applications. In our work we have found 129Xe NMR to be an excellent technique...

  5. Selectively Labeling the Heterologous Protein in Escherichia coli for NMR Studies: A Strategy to Speed Up NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    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.

  6. High pressure NMR study of a small protein, gurmarin.

    PubMed

    Inoue, K; Yamada, H; Imoto, T; Akasaka, K

    1998-11-01

    The effect of pressure on the structure of gurmarin, a globular, 35-residue protein from Gymnema sylvestre, was studied in aqueous environment (95% 1H2O/5% 2H2O, pH 2.0) with an on-line variable pressure NMR system operating at 750 MHz. Two-dimensional TOCSY and NOESY spectra were measured as functions of pressure between 1 and 2000 bar at 40 degrees C. Practically all the proton signals of gurmarin underwent some shifts with pressure, showing that the entire protein structure responds to, and is altered by, pressure. Most amide protons showed different degrees of low field shifts with pressure, namely 0-0.2 ppm with an average of 0.051 ppm at 2000 bar, showing that they are involved in hydrogen bonding and that these hydrogen bonds are shortened by pressure by different degrees. The tendency was also confirmed that the chemical shifts of the amide protons exposed to the solvent (water) are more sensitive to pressure than those internally hydrogen bonded with carbonyls. The pressure-induced shifts of the H alpha signals of the residues in the beta-sheet showed a negative correlation with the 'folding' shifts (difference between the shift at 1 bar and that of a random coil), suggesting that the main-chain torsion angles of the beta-sheet are slightly altered by pressure. Significant pressure-induced shifts were also observed for the side-chain protons (but no larger than 10% of the 'folding' shifts), demonstrating that the tertiary structure of gurmarin is also affected by pressure. Finally, the linearity of the pressure-induced shifts suggest that the compressibility of gurmarin is invariant in the pressure range between 1 and 2000 bar. PMID:9862129

  7. Distal and proximal ligand interactions in heme proteins: Correlations between C-O and Fe-C vibrational frequencies, oxygen-17 and carbon-13 nuclear magnetic resonance chemical shifts, and oxygen-17 nuclear quadrupole coupling constants in C sup 17 O- and sup 13 CO-labeled species

    SciTech Connect

    Ki Deok Park; Guo, K.; Adebodun, F.; Chiu, M.L.; Sligar, S.G.; Oldfield, E. )

    1991-03-05

    The authors have obtained the oxygen-17 nuclear magnetic resonance (NMR) spectra of a variety of C{sup 17}O-labeled heme proteins, including sperm whale (Physeter catodon) myoglobin, two synthetic sperm whale myoglobin mutants (His E7 {yields} Val E7; His E7 {yields} Phe E7), adult human hemoglobin, rabbit (Oryctolagus cuniculus) hemoglobin, horseradish (Cochlearia armoracia) peroxidase isoenzymes A and C, and Caldariomyces fumago chloroperoxidase, in some cases as a function of pH, and have determined their isotropic {sup 17}O NMR chemical shifts, {delta}{sub i}, and spin-lattice relaxation times, T{sub 1}. They have also obtained similar results on a picket fence prophyrin. The results show an excellent correlation between the infrared C-O vibrational frequencies, {nu}(C-O), and {delta}{sub i}, between {nu}(C-O) and the {sup 17}O nuclear quadrupole coupling constant, and as expected between e{sup 2}qQ/h and {delta}{sub i}. The results suggest the IR and NMR measurements reflect the same interaction, which is thought to be primarily the degree of {pi}-back-bonding from Fe d to CO {pi}* orbitals, as outlined previously.

  8. Interaction of lafutidine in binding to human serum albumin in gastric ulcer therapy: STD-NMR, WaterLOGSY-NMR, NMR relaxation times, Tr-NOESY, molecule docking, and spectroscopic studies.

    PubMed

    Yang, Hongqin; Huang, Yanmei; He, Jiawei; Li, Shanshan; Tang, Bin; Li, Hui

    2016-09-15

    In this study, lafutidine (LAF) was used as a model compound to investigate the binding mechanism between antiulcer drugs and human serum albumin (HSA) through various techniques, including STD-NMR, WaterLOGSY-NMR, (1)H NMR relaxation times, tr-NOESY, molecule docking calculation, FT-IR spectroscopy, and CD spectroscopy. The analyses of STD-NMR, which derived relative STD (%) intensities, and WaterLOGSY-NMR, determined that LAF bound to HSA. In particular, the pyridyl group of LAF was in close contact with HSA binding pocket, whereas furyl group had a secondary binding. Competitive STD-NMR and WaterLOGSY-NMR experiments, with warifarin and ibuprofen as site-selective probes, indicated that LAF preferentially bound to site II in the hydrophobic subdomains IIIA of HSA. The bound conformation of LAF at the HSA binding site was further elucidated by transferred NOE effect (tr-NOESY) experiment. Relaxation experiments provided quantitative information about the relationship between the affinity and structure of LAF. The molecule docking simulations conducted with AutoDock and the restraints derived from STD results led to three-dimensional models that were consistent with the NMR spectroscopic data. The presence of hydrophobic forces and hydrogen interactions was also determined. Additionally, FT-IR and CD spectroscopies showed that LAF induced secondary structure changes of HSA.

  9. Affect intensity and negative mood regulation (NMR) expectancies: a preliminary Indian study.

    PubMed

    Mehrotra, Seema; Tripathi, Ravikesh

    2012-06-01

    Individuals differ in the intensity with which they typically experience affect as well as in their beliefs regarding their ability to alleviate negative mood states. These variables have been implicated in a range of clinical problems. Most studies utilize a single index of affect intensity. The differential correlates of positive and negative affect intensity, their association with negative mood regulation expectancy and their role as predictors of psychological outcomes have been insufficiently explored. This study aimed at exploring the relationship of affect intensity variables with negative mood regulation (NMR) expectancy, their association with age and gender and examining the role of affect intensity and NMR expectancy as predictors of stress and well being in a community sample of Indian adults. The sample consisted of 206 participants aged between 20 and 60 years. Higher age was associated with higher NMR expectancy but lower positive affect intensity. Positive and negative affect intensity showed differential patterns of association with NMR expectancy. Higher negative affect intensity was associated with lower NMR expectancy whereas higher positive affect intensity was associated with higher NMR expectancy. Affect intensity and NMR expectancy variables jointly predicted 30-39% of variance in perceived stress and well being. Implications for further research are discussed.

  10. NMR studies of selective population inversion and spin clustering

    SciTech Connect

    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.

  11. Studies of electrolyte penetration in carbon anodes by NMR techniques.

    SciTech Connect

    Sandi, G.

    1998-12-09

    A toroid cavity nuclear magnetic resonance (NMR) detector capable of recording radial concentration profiles, diffusion constants, and displacements of charge carriers was employed to investigate the lithium ion distribution in an electrochemical cell containing a carbonaceous material synthesized from pyrene and pillared clays as inorganic templates. A carbon rod was used in a control experiment to assign the Li{sup +} spectrum and to calibrate the one dimensional radial images.

  12. Solid State NMR Studies of the Aluminum Hydride Phases

    NASA Technical Reports Server (NTRS)

    Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.

    2006-01-01

    Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.

  13. NMR studies of molecules in liquid crystals and graphite

    SciTech Connect

    Rosen, M.E.

    1992-06-01

    NMR experiments to measure proton dipole couplings were performed on a series of n-alkanes (n-hexane through n-decane) dissolved in nematic liquid crystals. Computer modeling of the experimental NMR-spectra was done using several different models for intermolecular interactions in these systems. The model of Photinos et al. was found to be best in describing the intermolecular interactions in these systems and can provide a statistical picture of the conformation and orientation of the alkane molecules in their partially-oriented environment. Order parameters and conformational distributions for the alkanes can be calculated from the modeling. The alkanes are found to have conformational distributions very much like those found in liquid alkanes. Proton NMR spectra of tetrahydrofuran (THF) intercalated in two graphite intercalation compounds were also measured. Computer simulations of these spectra provide a picture of THF in the constrained environment between the graphene layers where the THF is oriented at a particular angle, can translate and rotate freely, but does not appear to pseudorotate.

  14. NMR study of ferroelastic phase transition of tetramethylammonium tetrabromocobaltate

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran; Kim, Sun Ha

    2016-09-01

    Static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) experiments were carried out on 1H, 13C, and 14N nuclei in order to understand the structural changes of the N(CH3)4 groups in [N(CH3)4]2CoBr4 near the ferroelastic phase transition temperature TC. The two chemically inequivalent N(CH3)4 groups were distinguished using 13C cross-polarization/(CP)MAS and 14N static NMR. The changes in chemical shifts, line intensities, and the spin-lattice relaxation time near TC can be correlated with the changing structural geometry, which underlies the phase transition. The 14N NMR spectra indicated a crystal symmetry change at TC, which is related to the ferroelastic domain with different orientations of the N(CH3)4 groups. The ferroelastic domain walls were confirmed by optical polarizing microscopy, and the wall orientations were described by the Sapriel theory. The transition to the ferroelastic phase was found to be related to the orientational ordering of the N(CH3)4 groups.

  15. NMR methods for in-situ biofilm metabolism studies: spatial and temporal resolved measurements

    SciTech Connect

    Majors, Paul D.; Mclean, Jeffrey S.; Fredrickson, Jim K.; Wind, Robert A.

    2005-11-01

    We are developing nuclear magnetic resonance (NMR) microscopy, spectroscopy and combined NMR/optical techniques to the study of biofilms. Objectives include: time and depth-resolved metabolite concentrations with isotropic spatial resolution on the order of 10 microns, metabolic pathways and flux rates, mass transport and ultimately their correlation with gene expression by optical microscopy in biofilms. These methods are being developed with Shewanella oneidensis MR-1 as a model system, but are equally applicable to other biofilm systems of interest. Thus, spatially resolved NMR of biofilms is expected to contribute significantly to the understanding of adherent cell metabolism.

  16. Solid-state NMR studies of theophylline co-crystals with dicarboxylic acids.

    PubMed

    Pindelska, Edyta; Sokal, Agnieszka; Szeleszczuk, Lukasz; Pisklak, Dariusz Maciej; Kolodziejski, Waclaw

    2014-11-01

    In this work, three polycrystalline materials containing co-crystals of theophylline with malonic, maleic, and glutaric acids were studied using (13)C, (15)N and (1)H solid-state NMR and FT-IR spectroscopy. The NMR assignments were supported by gauge including projector augmented waves (GIPAW) calculations of chemical shielding, performed using X-ray determined geometry. The experimental (13)C cross polarization/magic angle spinning (CP/MAS) NMR results and the calculated isotropic chemical shifts were in excellent agreement. A rapid and convenient method for theophylline co-crystals crystal structure analysis has been proposed for co-crystals, which are potentially new APIs.

  17. Backbone dynamics of barstar: a (15)N NMR relaxation study.

    PubMed

    Sahu, S C; Bhuyan, A K; Majumdar, A; Udgaonkar, J B

    2000-12-01

    Backbone dynamics of uniformly (15)N-labeled barstar have been studied at 32 degrees C, pH 6.7, by using (15)N relaxation data obtained from proton-detected 2D (1)H-(15)N NMR spectroscopy. (15)N spin-lattice relaxation rate constants (R(1)), spin-spin relaxation rate constants (R(2)), and steady-state heteronuclear (1)H-(15)N NOEs have been determined for 69 of the 86 (excluding two prolines and the N-terminal residue) backbone amide (15)N at a magnetic field strength of 14.1 Tesla. The primary relaxation data have been analyzed by using the model-free formalism of molecular dynamics, using both isotropic and axially symmetric diffusion of the molecule, to determine the overall rotational correlation time (tau(m)), the generalized order parameter (S(2)), the effective correlation time for internal motions (tau(e)), and NH exchange broadening contributions (R(ex)) for each residue. As per the axially symmetric diffusion, the ratio of diffusion rates about the unique and perpendicular axes (D( parallel)/D( perpendicular)) is 0.82 +/- 0.03. The two results have only marginal differences. The relaxation data have also been used to map reduced spectral densities for the NH vectors of these residues at three frequencies: 0, omega(H), and omega(N), where omega(H),(N) are proton and nitrogen Larmor frequencies. The value of tau(m) obtained from model-free analysis of the relaxation data is 5.2 ns. The reduced spectral density analysis, however, yields a value of 5.7 ns. The tau(m) determined here is different from that calculated previously from time-resolved fluorescence data (4.1 ns). The order parameter ranges from 0.68 to 0.98, with an average value of 0.85 +/- 0.02. A comparison of the order parameters with the X-ray B-factors for the backbone nitrogens of wild-type barstar does not show any considerable correlation. Model-free analysis of the relaxation data for seven residues required the inclusion of an exchange broadening term, the magnitude of which ranges from 2

  18. Automated sample preparation station for studying self-diffusion in porous solids with NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Hedin, Niklas; DeMartin, Gregory J.; Reyes, Sebastián C.

    2006-03-01

    In studies of gas diffusion in porous solids with nuclear magnetic resonance (NMR) spectroscopy the sample preparation procedure becomes very important. An apparatus is presented here that pretreats the sample ex situ and accurately sets the desired pressure and temperature within the NMR tube prior to its introduction in the spectrometer. The gas manifold that supplies the NMR tube is also connected to a microbalance containing another portion of the same sample, which is kept at the same temperature as the sample in the NMR tube. This arrangement permits the simultaneous measurement of the adsorption loading on the sample, which is required for the interpretation of the NMR diffusion experiments. Furthermore, to ensure a good seal of the NMR tube, a hybrid valve design composed of titanium, a Teflon® seat, and Kalrez® O-rings is utilized. A computer controlled algorithm ensures the accuracy and reproducibility of all the procedures, enabling the NMR diffusion experiments to be performed at well controlled conditions of pressure, temperature, and amount of gas adsorbed on the porous sample.

  19. Multiple-quantum NMR studies of spin clusters in liquid crystals and zeolites

    SciTech Connect

    Pearson, J. . Dept. of Chemistry Lawrence Berkeley Lab., CA )

    1991-07-01

    This work will describe the use of MQ NMR to study spin clusters in anisotropic materials. A technique known as multiple-quantum spin counting was used to determine average spin cluster sizes liquid crystalline materials and in faujacitic zeolites containing aromatic hydrocarbons. The first half of the thesis will describe MQ NMR and the MQ spin counting technique, and the second half of the thesis will describe the actual experiments and their results.

  20. Longitudinal-relaxation-enhanced NMR experiments for the study of nucleic acids in solution.

    PubMed

    Farjon, Jonathan; Boisbouvier, Jérôme; Schanda, Paul; Pardi, Arthur; Simorre, Jean-Pierre; Brutscher, Bernhard

    2009-06-24

    Atomic-resolution information on the structure and dynamics of nucleic acids is essential for a better understanding of the mechanistic basis of many cellular processes. NMR spectroscopy is a powerful method for studying the structure and dynamics of nucleic acids; however, solution NMR studies are currently limited to relatively small nucleic acids at high concentrations. Thus, technological and methodological improvements that increase the experimental sensitivity and spectral resolution of NMR spectroscopy are required for studies of larger nucleic acids or protein-nucleic acid complexes. Here we introduce a series of imino-proton-detected NMR experiments that yield an over 2-fold increase in sensitivity compared to conventional pulse schemes. These methods can be applied to the detection of base pair interactions, RNA-ligand titration experiments, measurement of residual dipolar (15)N-(1)H couplings, and direct measurements of conformational transitions. These NMR experiments employ longitudinal spin relaxation enhancement techniques that have proven useful in protein NMR spectroscopy. The performance of these new experiments is demonstrated for a 10 kDa TAR-TAR*(GA) RNA kissing complex and a 26 kDa tRNA.

  1. Extrinsic Proton NMR Studies of Mg(OH)2 and Ca(OH)2

    NASA Astrophysics Data System (ADS)

    Itoh, Yutaka; Isobe, Masahiko

    2016-03-01

    We studied narrow 1H NMR spectra of Mg(OH)2 and Ca(OH)2 powders at 100-355 K and 42-59 MHz using pulsed NMR techniques. The Fourier transformed NMR spectra of the proton free-induction signals show the superposition of broad and narrow components, which can be assigned to immobile protons and extrinsic mobile protons, respectively. We found that a narrow spectrum develops on heating above about Tc = 260 K and widens above a Larmor frequency of about νc = 50 MHz for Mg(OH)2. The temperature-induced NMR spectrum and the characteristic frequency νc of 50 MHz are the noteworthy features of the nuclear spin fluctuation spectra of the extrinsic protons.

  2. 51V-NMR study of the Kagome staircase compound Co3V2O8

    NASA Astrophysics Data System (ADS)

    Ogloblichev, V.; Kumagai, K.; Yakubovsky, A.; Mikhalev, K.; Furukawa, Y.; Verkhovskii, S.; Gerashenko, A.; Barilo, S.; Bychkov, G.; Shiryaev, S.; Korolev, A.

    2009-03-01

    Kagome staircase compound Co3V2O8 (S = 3/2) has a structure very similar to multiferroic compound Ni3V2Og (S = 1), but their magnetic phase diagrams differ noticeably. We present the results of the first NMR study in Co3V2O8 single crystal. From 51V-NMR spectra, the components of electric field gradient (EFG) tensor and of magnetic shifts tensor, Ki, are obtained. The temperature dependences of NMR shifts 51Ki for each main crystal axis direction are well described by a spin contributions in the paramagnetic phase. In ferromagnetic phase the zero field 51V-NMR spectrum is observed in the temperature range of 1.5-6.3 K.

  3. Gas-phase NMR studies of alcohols. Intrinsic acidities

    NASA Astrophysics Data System (ADS)

    Chauvel, J. Paul; True, Nancy S.

    1985-05-01

    Gas-phase (≈100 Torr) 1H NMR spectra of eighteen simple aliphatic and unsaturated alcohols, four fluorinated alcohols, and two thiols were obtained at 148.6°C where hydrogen bonding has little effect on chemical shifts. For the methanol, ethanol, n-propanol, i-propanol, t-butanol, i- butanol, neopentanol, 2,2,2-trifluoroethanol and benzyl alcohol, the observed hydroxylic proton chemical shifts correlate with previously obtained relative gas-phase acidities from thermochemical analysis which employed equilibrium constants of proton transfer reactions measured via mass spectroscopic and ion cyclotron resonance techniques. The correlational dependence is 10.3(0.5) kcal/mol ppm with a correlation coefficient of 0.99. These results demonstrate that the trend of increasing acidity with increasing size of the alkyl substituent is also reflected in the neutral forms of the alcohols, indicating that the polarizability of the ionic forms is not the only determining factor in relative gas-phase acidities of alcohols. Although factors affecting the hydroxylic proton chemical shifts of the larger substituted and unsaturated alcohols are more complex, their observed 1H NMR spectra also reflect this trend. For methanol and ethanol observed gas-phase 1H chemical shifts are also compared with recent theoritical calculations. 3JHH coupling constants across CO bonds are ≈ 5.5 Hz, significantly smaller than typical 3JHH coupling across sp 3 hybrid C C bonds.

  4. Positional isotope exchange studies on enzyme using NMR spectroscopy

    SciTech Connect

    Matsunaga, T.O.

    1987-01-01

    The isotopically enriched compounds, /sup 18/O-..beta..,..gamma..-ATP and /sup 18/O bridge-labeled pyrophosphate, synthesized previously in this laboratory, were used to investigate and measure the exchange vs. turnover of substrates and products from their central complexes in four selected enzyme systems. Using hi-field /sup 31/P NMR, we were able to differentiate between /sup 18/O labeled in the bridge vs. the non-bridge positions by virtue of the isotope shift upon the phosphorus nuclei. The bridge to non-bridge scrambling of the label was quantitated and the exchange vs. turnover ratios under a variety of conditions was determined. Using the substrate inhibitor carboxycreatinine, PIX experiments with /sup 18/O-..beta..,..gamma..-ATP and creatine kinase were conducted. It was shown that carboxycreatinine and creatine kinase promoted exchange of the /sup 18/O label as determined by NMR. We have concluded that carboxycreatinine is either a substrate that catalyzes very slow turnover or it catalyzes exchange by a dissociative (SN/sub 1//sub P/) type of mechanism

  5. An NMR Study of Biomimetic Fluorapatite – Gelatine Mesocrystals

    PubMed Central

    Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, Rüdiger

    2015-01-01

    The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers, and with experimental observations of an amorphous cover layer in biominerals. PMID:26515127

  6. An NMR Study of Biomimetic Fluorapatite - Gelatine Mesocrystals

    NASA Astrophysics Data System (ADS)

    Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, Rüdiger

    2015-10-01

    The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43- groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers, and with experimental observations of an amorphous cover layer in biominerals.

  7. /sup 31/P NMR saturation-transfer and /sup 13/C NMR kinetic studies of glycolytic regulation during anaerobic and aerobic glycolysis

    SciTech Connect

    Campbell-Burk, S.L.; den Hollander, J.A.; Alger, J.R.; Shulman, R.G.

    1987-11-17

    /sup 31/P NMR saturation-transfer techniques have been employed in glucose-gown derepressed yeast to determine unidirectional fluxes in the upper part of the Embden-Meyerhof-Parnas pathway. The experiments were performed during anaerobic and aerobic glycolysis by saturating the ATP/sub ..gamma../ resonances and monitoring changes in the phosphomonoester signals from glucose 6-phosphate and fructose 1,6-bisphosphate. These experiments were supplemented with /sup 13/C NMR measurements of glucose utilization rates and /sup 13/C NMR label distribution studies. Combined with data obtained previously from radioisotope measurement, these /sup 31/P and /sup 13/C NMR kinetic studies allowed estimation of the net glycolytic flow in addition to relative flows through phosphofructokinase (PFK) and Fru-1,6-P/sub 2/ase during anaerobic and aerobic glycolysis. The /sup 31/P NMR saturation-transfer results are consistent with previous results obtained from measurements of metabolite levels, radioisotope data, and /sup 13/C NMR studies, providing additional support for in vivo measurement of the flows during glycolysis.

  8. Theoretical and experimental NMR studies on muscimol from fly agaric mushroom (Amanita muscaria)

    NASA Astrophysics Data System (ADS)

    Kupka, Teobald; Wieczorek, Piotr P.

    2016-01-01

    In this article we report results of combined theoretical and experimental NMR studies on muscimol, the bioactive alkaloid from fly agaric mushroom (Amanita muscaria). The assignment of 1H and 13C NMR spectra of muscimol in DMSO-d6 was supported by additional two-dimensional heteronuclear correlated spectra (2D NMR) and gauge independent atomic orbital (GIAO) NMR calculations using density functional theory (DFT). The effect of solvent in theoretical calculations was included via polarized continuum model (PCM) and the hybrid three-parameter B3LYP density functional in combination with 6-311++G(3df,2pd) basis set enabled calculation of reliable structures of non-ionized (neutral) molecule and its NH and zwitterionic forms in the gas phase, chloroform, DMSO and water. GIAO NMR calculations, using equilibrium and rovibrationally averaged geometry, at B3LYP/6-31G* and B3LYP/aug-cc-pVTZ-J levels of theory provided muscimol nuclear magnetic shieldings. The theoretical proton and carbon chemical shifts were critically compared with experimental NMR spectra measured in DMSO. Our results provide useful information on its structure in solution. We believe that such data could improve the understanding of basic features of muscimol at atomistic level and provide another tool in studies related to GABA analogs.

  9. Sedimentary constraints on the duration of the Marinoan Oxygen-17 Depletion (MOSD) event.

    PubMed

    Killingsworth, Bryan A; Hayles, Justin A; Zhou, Chuanming; Bao, Huiming

    2013-10-29

    The ~635 Ma Marinoan glaciation is marked by dramatic Earth system perturbations. Deposition of nonmass-dependently (17)O-depleted sulfate (SO4(2-)) in worldwide postglacial sediments is, thus far, unique to this glaciation. It is proposed that an extremely high-pCO2 atmosphere can result in highly (17)O-depleted atmospheric O2, or the Marinoan Oxygen-17 Depletion (MOSD) event. This anomalous (17)O signal was imparted to sulfate of oxidative weathering origin. However, (17)O-depleted sulfate occurs in limited sedimentary intervals, suggesting that Earth surface conditions conducive to the MOSD had a finite duration. An MOSD duration can, therefore, provide much needed constraint on modeling Earth system responses at that time. Unfortunately, the sulfate (17)O record is often sparse or lacks radiometric dates. Here, we report 11 barite layers from a post-Marinoan dolostone sequence at Wushanhu in the South China Block. The (17)O depletion fluctuates in magnitude in lower layers but is persistently absent up section, providing the most confident first and last sedimentary appearance of the anomaly. δ(13)C chemostratigraphy is used to correlate the Wushanhu section to two proximal sections on the same shallow platform that lack barite layers but have published U-Pb dates that occur in dolostone and shale. Assuming a similar pattern and rate for carbonate and shale deposition among the different sections, we estimate the MOSD duration at 0-0.99 My. This number can be further constrained by new radiometric dates from equivalent sequences worldwide, thus underpinning models on the nonsteady-state Earth system response in the immediate aftermath of the Marinoan meltdown. PMID:23386719

  10. Dynamic model constraints on oxygen-17 depletion in atmospheric O2 after a snowball Earth

    PubMed Central

    Cao, Xiaobin; Bao, Huiming

    2013-01-01

    A large perturbation in atmospheric CO2 and O2 or bioproductivity will result in a drastic pulse of 17O change in atmospheric O2, as seen in the Marinoan Oxygen-17 Depletion (MOSD) event in the immediate aftermath of a global deglaciation 635 Mya. The exact nature of the perturbation, however, is debated. Here we constructed a coupled, four-box, and quick-response biosphere–atmosphere model to examine both the steady state and dynamics of the MOSD event. Our model shows that the ultra-high CO2 concentrations proposed by the “snowball’ Earth hypothesis produce a typical MOSD duration of less than 106 y and a magnitude of 17O depletion reaching approximately −35‰. Both numbers are in remarkable agreement with geological constraints from South China and Svalbard. Moderate CO2 and low O2 concentration (e.g., 3,200 parts per million by volume and 0.01 bar, respectively) could produce distinct sulfate 17O depletion only if postglacial marine bioproductivity was impossibly low. Our dynamic model also suggests that a snowball in which the ocean is isolated from the atmosphere by a continuous ice cover may be distinguished from one in which cracks in the ice permit ocean–atmosphere exchange only if partial pressure of atmospheric O2 is larger than 0.02 bar during the snowball period and records of weathering-derived sulfate are available for the very first few tens of thousands of years after the onset of the meltdown. In any case, a snowball Earth is a precondition for the observed MOSD event. PMID:23898167

  11. Sedimentary constraints on the duration of the Marinoan Oxygen-17 Depletion (MOSD) event

    PubMed Central

    Killingsworth, Bryan A.; Hayles, Justin A.; Zhou, Chuanming; Bao, Huiming

    2013-01-01

    The ∼635 Ma Marinoan glaciation is marked by dramatic Earth system perturbations. Deposition of nonmass-dependently 17O-depleted sulfate (SO42−) in worldwide postglacial sediments is, thus far, unique to this glaciation. It is proposed that an extremely high-pCO2 atmosphere can result in highly 17O-depleted atmospheric O2, or the Marinoan Oxygen-17 Depletion (MOSD) event. This anomalous 17O signal was imparted to sulfate of oxidative weathering origin. However, 17O-depleted sulfate occurs in limited sedimentary intervals, suggesting that Earth surface conditions conducive to the MOSD had a finite duration. An MOSD duration can, therefore, provide much needed constraint on modeling Earth system responses at that time. Unfortunately, the sulfate 17O record is often sparse or lacks radiometric dates. Here, we report 11 barite layers from a post-Marinoan dolostone sequence at Wushanhu in the South China Block. The 17O depletion fluctuates in magnitude in lower layers but is persistently absent up section, providing the most confident first and last sedimentary appearance of the anomaly. δ13C chemostratigraphy is used to correlate the Wushanhu section to two proximal sections on the same shallow platform that lack barite layers but have published U-Pb dates that occur in dolostone and shale. Assuming a similar pattern and rate for carbonate and shale deposition among the different sections, we estimate the MOSD duration at 0–0.99 My. This number can be further constrained by new radiometric dates from equivalent sequences worldwide, thus underpinning models on the nonsteady-state Earth system response in the immediate aftermath of the Marinoan meltdown. PMID:23386719

  12. Sedimentary constraints on the duration of the Marinoan Oxygen-17 Depletion (MOSD) event

    NASA Astrophysics Data System (ADS)

    Killingsworth, Bryan A.; Hayles, Justin A.; Zhou, Chuanming; Bao, Huiming

    2013-10-01

    The ∼635 Ma Marinoan glaciation is marked by dramatic Earth system perturbations. Deposition of nonmass-dependently 17O-depleted sulfate (SO42-) in worldwide postglacial sediments is, thus far, unique to this glaciation. It is proposed that an extremely high-pCO2 atmosphere can result in highly 17O-depleted atmospheric O2, or the Marinoan Oxygen-17 Depletion (MOSD) event. This anomalous 17O signal was imparted to sulfate of oxidative weathering origin. However, 17O-depleted sulfate occurs in limited sedimentary intervals, suggesting that Earth surface conditions conducive to the MOSD had a finite duration. An MOSD duration can, therefore, provide much needed constraint on modeling Earth system responses at that time. Unfortunately, the sulfate 17O record is often sparse or lacks radiometric dates. Here, we report 11 barite layers from a post-Marinoan dolostone sequence at Wushanhu in the South China Block. The 17O depletion fluctuates in magnitude in lower layers but is persistently absent up section, providing the most confident first and last sedimentary appearance of the anomaly. δ13C chemostratigraphy is used to correlate the Wushanhu section to two proximal sections on the same shallow platform that lack barite layers but have published U-Pb dates that occur in dolostone and shale. Assuming a similar pattern and rate for carbonate and shale deposition among the different sections, we estimate the MOSD duration at 0-0.99 My. This number can be further constrained by new radiometric dates from equivalent sequences worldwide, thus underpinning models on the nonsteady-state Earth system response in the immediate aftermath of the Marinoan meltdown.

  13. Sedimentary constraints on the duration of the Marinoan Oxygen-17 Depletion (MOSD) event.

    PubMed

    Killingsworth, Bryan A; Hayles, Justin A; Zhou, Chuanming; Bao, Huiming

    2013-10-29

    The ~635 Ma Marinoan glaciation is marked by dramatic Earth system perturbations. Deposition of nonmass-dependently (17)O-depleted sulfate (SO4(2-)) in worldwide postglacial sediments is, thus far, unique to this glaciation. It is proposed that an extremely high-pCO2 atmosphere can result in highly (17)O-depleted atmospheric O2, or the Marinoan Oxygen-17 Depletion (MOSD) event. This anomalous (17)O signal was imparted to sulfate of oxidative weathering origin. However, (17)O-depleted sulfate occurs in limited sedimentary intervals, suggesting that Earth surface conditions conducive to the MOSD had a finite duration. An MOSD duration can, therefore, provide much needed constraint on modeling Earth system responses at that time. Unfortunately, the sulfate (17)O record is often sparse or lacks radiometric dates. Here, we report 11 barite layers from a post-Marinoan dolostone sequence at Wushanhu in the South China Block. The (17)O depletion fluctuates in magnitude in lower layers but is persistently absent up section, providing the most confident first and last sedimentary appearance of the anomaly. δ(13)C chemostratigraphy is used to correlate the Wushanhu section to two proximal sections on the same shallow platform that lack barite layers but have published U-Pb dates that occur in dolostone and shale. Assuming a similar pattern and rate for carbonate and shale deposition among the different sections, we estimate the MOSD duration at 0-0.99 My. This number can be further constrained by new radiometric dates from equivalent sequences worldwide, thus underpinning models on the nonsteady-state Earth system response in the immediate aftermath of the Marinoan meltdown.

  14. Dynamic model constraints on oxygen-17 depletion in atmospheric O2 after a snowball Earth.

    PubMed

    Cao, Xiaobin; Bao, Huiming

    2013-09-01

    A large perturbation in atmospheric CO2 and O2 or bioproductivity will result in a drastic pulse of (17)O change in atmospheric O2, as seen in the Marinoan Oxygen-17 Depletion (MOSD) event in the immediate aftermath of a global deglaciation 635 Mya. The exact nature of the perturbation, however, is debated. Here we constructed a coupled, four-box, and quick-response biosphere-atmosphere model to examine both the steady state and dynamics of the MOSD event. Our model shows that the ultra-high CO2 concentrations proposed by the "snowball' Earth hypothesis produce a typical MOSD duration of less than 10(6) y and a magnitude of (17)O depletion reaching approximately -35‰. Both numbers are in remarkable agreement with geological constraints from South China and Svalbard. Moderate CO2 and low O2 concentration (e.g., 3,200 parts per million by volume and 0.01 bar, respectively) could produce distinct sulfate (17)O depletion only if postglacial marine bioproductivity was impossibly low. Our dynamic model also suggests that a snowball in which the ocean is isolated from the atmosphere by a continuous ice cover may be distinguished from one in which cracks in the ice permit ocean-atmosphere exchange only if partial pressure of atmospheric O2 is larger than 0.02 bar during the snowball period and records of weathering-derived sulfate are available for the very first few tens of thousands of years after the onset of the meltdown. In any case, a snowball Earth is a precondition for the observed MOSD event. PMID:23898167

  15. Dynamic model constraints on oxygen-17 depletion in atmospheric O2 after a snowball Earth.

    PubMed

    Cao, Xiaobin; Bao, Huiming

    2013-09-01

    A large perturbation in atmospheric CO2 and O2 or bioproductivity will result in a drastic pulse of (17)O change in atmospheric O2, as seen in the Marinoan Oxygen-17 Depletion (MOSD) event in the immediate aftermath of a global deglaciation 635 Mya. The exact nature of the perturbation, however, is debated. Here we constructed a coupled, four-box, and quick-response biosphere-atmosphere model to examine both the steady state and dynamics of the MOSD event. Our model shows that the ultra-high CO2 concentrations proposed by the "snowball' Earth hypothesis produce a typical MOSD duration of less than 10(6) y and a magnitude of (17)O depletion reaching approximately -35‰. Both numbers are in remarkable agreement with geological constraints from South China and Svalbard. Moderate CO2 and low O2 concentration (e.g., 3,200 parts per million by volume and 0.01 bar, respectively) could produce distinct sulfate (17)O depletion only if postglacial marine bioproductivity was impossibly low. Our dynamic model also suggests that a snowball in which the ocean is isolated from the atmosphere by a continuous ice cover may be distinguished from one in which cracks in the ice permit ocean-atmosphere exchange only if partial pressure of atmospheric O2 is larger than 0.02 bar during the snowball period and records of weathering-derived sulfate are available for the very first few tens of thousands of years after the onset of the meltdown. In any case, a snowball Earth is a precondition for the observed MOSD event.

  16. Low-temperature NMR studies on inosine wobble base pairs.

    PubMed

    Janke, Eline M Basílio; Riechert-Krause, Fanny; Weisz, Klaus

    2011-07-01

    Base pairs formed by the inosine nucleoside (I) play an important role in many physiological processes as well as in various DNA technologies. Relative stabilities and favored base pair geometries of free inosine wobble base pairs in aprotic solvents have been determined through (1)H NMR measurements at room temperature and at very low temperatures in a freonic solvent. As indicated by its significantly deshielded imino proton, the Watson-Crick-type I·C base pair forms a remarkably strong NHN hydrogen bond. For the thermodynamically less stable I·A wobble base pair, two configurations of similar population coexist at 133 K in the slow hydrogen bond exchange regime, namely a Watson-Crick(I)-Watson-Crick(A) geometry and a Watson-Crick(I)-Hoogsteen(A) geometry. I·U base pairs are stabilized by two rather weak hydrogen bonds and are significantly disfavored over inosine self-associates in a low-temperature Freon solution. PMID:21644523

  17. Molecular dynamics of solid cortisol studied by NMR

    NASA Astrophysics Data System (ADS)

    Andrew, E. R.

    Polycrystalline cortisol (hydrocortisone; 11β,17α,21-trihydroxy-4-preg- nene-3,20-dione; C21H30O5) has been investigated by continuous and pulse proton NMR methods between 78 and 400 K at Larmor frequencies of 7, 25 and 60 MHz. A reduced value of second moment was found above 90 K and is ascribed to reorientation of two methyl groups. A single asymmetric minimum was found in the temperature dependence of the spin-lattice relaxation times and this also is attributed to reorientation of two methyl groups. The asymmetry suggests an asymmetric distribution of correlation times of the motion. Using the Cole-Davidson distribution, the best computer fit yields the following parameters characterizing the motion: Ea = 11ṡ8 ± 0ṡ1 kJ mol-1, τ0 = 4ṡ6 ± 0ṡ4) x 10-13s, distribution parameter δ = 0ṡ62.

  18. Multinuclear MAS NMR studies of sodalitic framework materials

    SciTech Connect

    Johnson, G.M.; Mead, P.J.; Dann, S.E.; Weller, M.T.

    2000-02-24

    A wide range of sodalite framework materials, M{sub 8}[TT{prime}O{sub 4}]{sub 6}X{sub 2} where T = Al, Ga, Si, T{prime} = Be, Al, Si, Ge, have been characterized using {sup 27}Al, {sup 29}Si, and {sup 71}Ga magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Structural parameters, such as functions of the framework T{single{underscore}bond}O{single{underscore}bond}T{prime} angle, correlate linearly with the determined chemical shift values and provide relationships, as a function of T{prime}, which will facilitate characterization of more complex zeolitic compounds containing such species. The effects of changing a particular neighboring framework cation on the resonance position is controlled by variations in both framework bond angles/distances and electrostatic effects; these contributions are resolved.

  19. NMR study of chloride ion interactions with thylakoid membranes

    PubMed Central

    Baianu, I. C.; Critchley, C.; Govindjee; Gutowsky, H. S.

    1984-01-01

    The role of Cl- in photosynthetic O2 evolution has been investigated by observing the 35Cl NMR linewidth under a variety of conditions in aqueous suspensions of chloroplasts, primarily for the halophytes Avicennia germinans, Avicennia marina, and Aster tripolium but also for spinach. The line broadening shows there is weak, ionic binding of Cl- to thylakoids, the bound Cl- exchanging rapidly (>>104 sec-1) with free Cl- in solution. The binding is necessary for O2 evolution to occur. Michaelis-Menten constants obtained from the Cl- dependence of the O2 evolution rate are ≈15-70 mM for the halophytes compared with 0.6 mM for spinach (0.5 mM with Br-). There appear to be two types of Cl- binding sites in halophytes, of which the stronger is the activator, at lower [Cl-], of O2 evolution. The 35Cl line broadening includes a nonspecific interaction, which becomes apparent at high Cl- concentrations (≥0.5 M). PMID:16593474

  20. NMR relaxometry study of plaster mortar with polymer additives

    SciTech Connect

    Jumate, E.; Manea, D.; Moldovan, D.; Fechete, R.

    2013-11-13

    The cement mixed with water forms a plastic paste or slurry which stiffness in time and finally hardens into a resistant stone. The addition of sand aggregates, polymers (Walocel) and/or calcium carbonate will modify dramatically the final mortar mechanic and thermal properties. The hydration processes can be observed using the 1D NMR measurements of transverse T{sub 2} relaxation times distributions analysed by a Laplace inversion algorithm. These distributions were obtained for mortar pasta measured at 2 hours after preparation then at 3, 7 and 28 days after preparation. Multiple components are identified in the T{sub 2} distributions. These can be associated with the proton bounded chemical or physical to the mortar minerals characterized by a short T{sub 2} relaxation time and to water protons in pores with three different pore sizes as observed from SEM images. The evaporation process is faster in the first hours after preparation, while the mortar hydration (bonding of water molecules to mortar minerals) can be still observed after days or months from preparation. Finally, the mechanic resistance was correlated with the transverse T{sub 2} relaxation rates corresponding to the bound water.

  1. NMR studies of molecular structure in fruit cuticle polyesters.

    PubMed

    Fang, X; Qiu, F; Yan, B; Wang, H; Mort, A J; Stark, R E

    2001-07-01

    The cuticle of higher plants functions primarily as a protective barrier for the leaves and fruits, controlling microbial attack as well as the diffusion of water and chemicals from the outside environment. Its major chemical constituents are waxes (for waterproofing) and cutin (a structural support polymer). However, the insolubility of cutin has hampered investigations of its covalent structure and domain architecture, which are viewed as essential for the design of crop protection strategies and the development of improved synthetic waterproofing materials. Recently developed strategies designed to meet these investigative challenges include partial depolymerization using enzymatic or chemical reagents and spectroscopic examination of the intact polyesters in a solvent-swelled form. The soluble oligomers from degradative treatments of lime fruit cutin are composed primarily of the expected 10,16-dihydroxyhexadecanoic and 16-hydroxy-10-oxo-hexadecanoic acids; low-temperature HF treatments also reveal sugar units that are covalently attached to the hydroxyfatty acids. Parallel investigations of solvent-swollen cutin using 2D NMR spectroscopy assisted by magic-angle spinning yield well-resolved spectra that permit detailed comparisons to be made among chemical moieties present in the intact biopolymer, the soluble degradation products, and the unreacted solid residue. PMID:11423150

  2. NMR studies in chemistry. I. Organometallic tin and geramanium compounds. II. The sorbitol pathway in intact lenses

    SciTech Connect

    Williams, W.F.

    1985-01-01

    Nuclear magnetic resonance spectroscopy has been utilized in the study of two very different chemical problems. The bonding and structure of various cyclopropyl derivatives of tin and germanium has been investigated by means of Sn-119, Ge-73, C-13, and H-1 NMR spectroscopy. Intact rabbit lenses have also been studied using NMR spectroscopy with regard to diabetic cataract formation. C-13 and P-31 NMR spectroscopies have been utilized in the study of the sorbitol pathway and aldose reductase inhibition.

  3. (1) H NMR analysis of O-methyl-inositol isomers: a joint experimental and theoretical study.

    PubMed

    De Almeida, Mauro V; Couri, Mara Rubia C; De Assis, João Vitor; Anconi, Cleber P A; Dos Santos, Hélio F; De Almeida, Wagner B

    2012-09-01

    Density functional theory (DFT) calculations of (1) H NMR chemical shifts for l-quebrachitol isomers were performed using the B3LYP functional employing the 6-31G(d,p) and 6-311 + G(2d,p) basis sets. The effect of the solvent on the B3LYP-calculated NMR spectrum was accounted for using the polarizable continuum model. Comparison is made with experimental (1) H NMR spectroscopic data, which shed light on the average uncertainty present in DFT calculations of chemical shifts and showed that the best match between experimental and theoretical B3LYP (1) H NMR profiles is a good strategy to assign the molecular structure present in the sample handled in the experimental measurements. Among four plausible O-methyl-inositol isomers, the l-quebrachitol 2a structure was unambiguously assigned based only on the comparative analysis of experimental and theoretical (1) H NMR chemical shift data. The B3LYP infrared (IR) spectrum was also calculated for the four isomers and compared with the experimental data, with analysis of the theoretical IR profiles corroborating assignment of the 2a structure. Therefore, it is confirmed in this study that a combined experimental/DFT spectroscopic investigation is a powerful tool in structural/conformational analysis studies. PMID:22865668

  4. A Solid-State NMR Study of Selenium Substitution into Nanocrystalline Hydroxyapatite

    PubMed Central

    Kolmas, Joanna; Kuras, Marzena; Oledzka, Ewa; Sobczak, Marcin

    2015-01-01

    The substitution of selenium oxyanions in the hydroxyapatite structure was examined using multinuclear solid-state resonance spectroscopy (ssNMR). The study was supported by powder X-ray diffractometry (PXRD) and wavelength dispersion X-ray fluorescence (WD-XRF). Samples of pure hydroxyapatite (HA300) and selenate (HA300-1.2SeO4) or selenite (HA300-1.2SeO3) substituted hydroxyapatites were synthesized using the standard wet method and heated at 300 °C to remove loosely bonded water. PXRD data showed that all samples are single-phase, nanocrystalline hydroxyapatite. The incorporation of selenite and selenate ions affected the lattice constants. In selenium-containing samples the concentration of Se was very similar and amounted to 9.55% and 9.64%, for HA300-1.2SeO4 and HA300-1.2SeO3, respectively. PXRD and ssNMR data showed that the selenite doping significantly decreases the crystallite size and crystallinity degree. 31P and 1H NMR experiments demonstrated the developed surface hydrated layer in all samples, especially in HA300-1.2SeO3. 1H NMR studies showed the dehydroxylation of HA during the selenium oxyanions substitution and the existence of hydrogen bonding in structural hydroxyl group channels. 1H→77Se cross polarization NMR experiments indicated that selenites and selenates are located in the crystal lattice and on the crystal surface. PMID:25997001

  5. (1) H NMR analysis of O-methyl-inositol isomers: a joint experimental and theoretical study.

    PubMed

    De Almeida, Mauro V; Couri, Mara Rubia C; De Assis, João Vitor; Anconi, Cleber P A; Dos Santos, Hélio F; De Almeida, Wagner B

    2012-09-01

    Density functional theory (DFT) calculations of (1) H NMR chemical shifts for l-quebrachitol isomers were performed using the B3LYP functional employing the 6-31G(d,p) and 6-311 + G(2d,p) basis sets. The effect of the solvent on the B3LYP-calculated NMR spectrum was accounted for using the polarizable continuum model. Comparison is made with experimental (1) H NMR spectroscopic data, which shed light on the average uncertainty present in DFT calculations of chemical shifts and showed that the best match between experimental and theoretical B3LYP (1) H NMR profiles is a good strategy to assign the molecular structure present in the sample handled in the experimental measurements. Among four plausible O-methyl-inositol isomers, the l-quebrachitol 2a structure was unambiguously assigned based only on the comparative analysis of experimental and theoretical (1) H NMR chemical shift data. The B3LYP infrared (IR) spectrum was also calculated for the four isomers and compared with the experimental data, with analysis of the theoretical IR profiles corroborating assignment of the 2a structure. Therefore, it is confirmed in this study that a combined experimental/DFT spectroscopic investigation is a powerful tool in structural/conformational analysis studies.

  6. Practical applications of hydrostatic pressure to refold proteins from inclusion bodies for NMR structural studies.

    PubMed

    Ogura, Kenji; Kobashigawa, Yoshihiro; Saio, Tomohide; Kumeta, Hiroyuki; Torikai, Shinnosuke; Inagaki, Fuyuhiko

    2013-06-01

    Recently, the hydrostatic pressure refolding method was reported as a practical tool for solubilizing and refolding proteins from inclusion bodies; however, there have been only a few applications for protein structural studies. Here, we report the successful applications of the hydrostatic pressure refolding method to refold proteins, including the MOE-2 tandem zinc-finger, the p62 PB1 domain, the GCN2 RWD domain, and the mTOR FRB domain. Moreover, the absence of aggregation and the correct folding of solubilized protein samples were evaluated with size exclusion chromatography and NMR experiments. The analyses of NMR spectra for MOE-2 tandem zinc-finger and GCN2 RWD further led to the determination of tertiary structures, which are consistent with those from soluble fractions. Overall, our results indicate that the hydrostatic pressure method is effective for preparing samples for NMR structural studies.

  7. Expression and Purification of Src-family Kinases for Solution NMR Studies

    PubMed Central

    Piserchio, Andrea; Cowburn, David; Ghose, Ranajeet

    2012-01-01

    Summary NMR analyses of the structure, dynamics and interactions of the Src family kinases (SFKs) have been hindered by the limited ability to obtain sufficient amounts of properly folded, soluble protein from bacterial expression systems, to allow these studies to be performed in an economically viable manner. In this chapter we detail our attempts to overcome these difficulties using the catalytic domain (SrcCD) of c-Src, the prototypical SFK, as an illustrative example. We describe in detail two general methods to express and purify SrcCD from E. coli expression systems in both fully active wild-type and kinase-deficient mutant forms, allowing the efficient and cost-effective labeling by NMR-active isotopes for solution NMR studies. PMID:22167671

  8. 2H NMR studies of glycerol dynamics in protein matrices.

    PubMed

    Herbers, C R; Sauer, D; Vogel, M

    2012-03-28

    We use (2)H NMR spectroscopy to investigate the rotational motion of glycerol molecules in matrices provided by the connective tissue proteins elastin and collagen. Analyzing spin-lattice relaxation, line-shape properties, and stimulated-echo decays, we determine the rates and geometries of the motion as a function of temperature and composition. It is found that embedding glycerol in an elastin matrix leads to a mild slowdown of glycerol reorientation at low temperatures and glycerol concentrations, while the effect vanishes at ambient temperatures or high solvent content. Furthermore, it is observed that the nonexponential character of the rotational correlation functions is much more prominent in the elastin matrix than in the bulk liquid. Results from spin-lattice relaxation and line shape measurements indicate that, in the mixed systems, the strong nonexponentiality is in large part due to the existence of distributions of correlation times, which are broader on the long-time flank and, hence, more symmetric than in the neat system. Stimulated-echo analysis of slow glycerol dynamics reveals that, when elastin is added, the mechanism for the reorientation crosses over from small-angle jump dynamics to large-angle jump dynamics and the geometry of the motion changes from isotropic to anisotropic. The results are discussed against the background of present and previous findings for glycerol and water dynamics in various protein matrices and compared with observations for other dynamically highly asymmetric mixtures so as to ascertain in which way the viscous freezing of a fast component in the matrix of a slow component differs from the glassy slowdown in neat supercooled liquids. PMID:22462878

  9. NMR Relaxation in Systems with Magnetic Nanoparticles: A Temperature Study

    PubMed Central

    Issa, Bashar; Obaidat, Ihab M.; Hejasee, Rola H.; Qadri, Shahnaz; Haik, Yousef

    2013-01-01

    Purpose To measure and model NMR relaxation enhancement due to the presence of Gd substituted Zn-Mn ferrite magnetic nanoparticles at different temperatures. Materials and Methods Relaxation rates were measured at 1.5 T using FSE sequences in samples of agarose gel doped with uncoated and polyethylene glycol (PEG) coated Mn0.5Zn0.5Gd0.02Fe1.98O4 nanoparticles over the temperature range 8 to 58°C. Physical characterization of the magnetic nanoparticles synthesized using chemical co-precipitation included scanning (SEM) and transmission (TEM) electron microscopy, inductively coupled plasma (ICP), dynamic light scattering (DLS), and magnetometry. Results Relaxivity (in s−1 mM−1 Fe) for the uncoated and coated particles, respectively, increased as follows: from 2.5 to 3.2 and 0.4 to 0.7 for T1, while for T2 it increased from 162.3 to 253.7 and 59.7 to 82.2 over the temperature range 8 to 58°C. T2 data was fitted to the echo limited motional regime using one fitting parameter that reflects the degree of agglomeration of particles into a cluster. This parameter was found to increase linearly with temperature and was larger for the PEG coated particles than the uncoated ones. Conclusion The increase of 1/T2 with temperature is modeled successfully using echo limited motional regime where both diffusion of the protons and nanoparticle cluster size increase with temperature. Both transverse and longitudinal relaxation efficiencies are reduced by PEG coating at all temperatures. If prediction of relaxation rates under different particle concentrations and operating temperatures is possible then the use of MNP in temperature monitoring and hyperthermia applications may be achieved. PMID:23720101

  10. 2H NMR studies of glycerol dynamics in protein matrices

    NASA Astrophysics Data System (ADS)

    Herbers, C. R.; Sauer, D.; Vogel, M.

    2012-03-01

    We use 2H NMR spectroscopy to investigate the rotational motion of glycerol molecules in matrices provided by the connective tissue proteins elastin and collagen. Analyzing spin-lattice relaxation, line-shape properties, and stimulated-echo decays, we determine the rates and geometries of the motion as a function of temperature and composition. It is found that embedding glycerol in an elastin matrix leads to a mild slowdown of glycerol reorientation at low temperatures and glycerol concentrations, while the effect vanishes at ambient temperatures or high solvent content. Furthermore, it is observed that the nonexponential character of the rotational correlation functions is much more prominent in the elastin matrix than in the bulk liquid. Results from spin-lattice relaxation and line shape measurements indicate that, in the mixed systems, the strong nonexponentiality is in large part due to the existence of distributions of correlation times, which are broader on the long-time flank and, hence, more symmetric than in the neat system. Stimulated-echo analysis of slow glycerol dynamics reveals that, when elastin is added, the mechanism for the reorientation crosses over from small-angle jump dynamics to large-angle jump dynamics and the geometry of the motion changes from isotropic to anisotropic. The results are discussed against the background of present and previous findings for glycerol and water dynamics in various protein matrices and compared with observations for other dynamically highly asymmetric mixtures so as to ascertain in which way the viscous freezing of a fast component in the matrix of a slow component differs from the glassy slowdown in neat supercooled liquids.

  11. NMR-BASED METABOLOMIC STUDIES OF ENDOCRINE DISRUPTION IN SMALL FISH MODELS

    EPA Science Inventory

    Metabolomics is now being widely used to obtain complementary information to genomic and proteomic studies. Among the various approaches used in metabolomics, NMR spectroscopy is particularly powerful, in part because it is relatively non-selective, and is amenable to the study o...

  12. TC and H NMR studies of PQQ and selected derivatives. [Pyrroloquinoline quinone

    SciTech Connect

    Houck, D.R.; Unkefer, C.J.

    1988-01-01

    The ortho-quinone structure of pyrroloquinoline quinone (PQQ) is famous for its reactivity with nucleophilic species of carbon, nitrogen, and oxygen(Duine et. al. 1987). In fact, the crystal structure of PQQ was solved in the form of the C-5 acetone adduct(Salisbury et. al 1979). The propensity of the ortho-quinone to accept nucleophiles is the chemical basis of the function of PQQ at enzyme active sites. The present study focuses on the NMR of PQQ and various derivatives formed with oxygen and nitrogen nucleophiles. Our goals are to assign the H, TC, and VN NMR spectra and to rigorously confirm the structures of the adducts. Once the NMR data of the relevant adducts are well defined, we will use TC and VN labeled substrates to probe the active sites of PQQ containing enzymes. 7 refs., 2 figs., 1 tab.

  13. Prediction of (19)F NMR Chemical Shifts in Labeled Proteins: Computational Protocol and Case Study.

    PubMed

    Isley, William C; Urick, Andrew K; Pomerantz, William C K; Cramer, Christopher J

    2016-07-01

    The structural analysis of ligand complexation in biomolecular systems is important in the design of new medicinal therapeutic agents; however, monitoring subtle structural changes in a protein's microenvironment is a challenging and complex problem. In this regard, the use of protein-based (19)F NMR for screening low-molecular-weight molecules (i.e., fragments) can be an especially powerful tool to aid in drug design. Resonance assignment of the protein's (19)F NMR spectrum is necessary for structural analysis. Here, a quantum chemical method has been developed as an initial approach to facilitate the assignment of a fluorinated protein's (19)F NMR spectrum. The epigenetic "reader" domain of protein Brd4 was taken as a case study to assess the strengths and limitations of the method. The overall modeling protocol predicts chemical shifts for residues in rigid proteins with good accuracy; proper accounting for explicit solvation of fluorinated residues by water is critical. PMID:27218275

  14. NMR and Infrared Study of Thermal Oxidation of cis-1, 4-Polybutadiene

    NASA Technical Reports Server (NTRS)

    Gemmer, Robert V.; Golub, Morton A.

    1978-01-01

    A study of the microstructural changes occuring in CB during thermal, uncatalyzed oxidation was carried out. Although the oxidation of CB is accompanied by extensive crosslinking with attendant insolubilization, it was found possible to follow the oxidation of solid CB directly with C-13 NMR spectroscopy. The predominant products appearing in the C-13 NMR spectra of oxidized CB are epoxides. The presence of lesser amounts of alcohols, peroxides, and carbonyl structures was adduced from complementary infrared and NMR spectra of soluble extracts obtained from the oxidized, crosslinked CB. This distribution of functional groups contrasts with that previously reported for the autooxidation of 1,4-polyisoprene. The difference was rationalized in terms of the relative stabilities of intermediate radical species involved in the autoxidation of CB and 1,4-polyisoprene.

  15. Single-file diffusion of confined water inside SWNTs: an NMR study.

    PubMed

    Das, Anindya; Jayanthi, Sundaresan; Deepak, Handiganadu Srinivasa Murthy Vinay; Ramanathan, Krishna Venkatachala; Kumar, Anil; Dasgupta, Chandan; Sood, Ajay K

    2010-03-23

    We report a nuclear magnetic resonance (NMR) study of confined water inside approximately 1.4 nm diameter single-walled carbon nanotubes (SWNTs). We show that the confined water does not freeze even up to 223 K. A pulse field gradient (PFG) NMR method is used to determine the mean squared displacement (MSD) of the water molecules inside the nanotubes at temperatures below 273 K, where the bulk water outside the nanotubes freezes and hence does not contribute to the proton NMR signal. We show that the mean squared displacement varies as the square root of time, predicted for single-file diffusion in a one-dimensional channel. We propose a qualitative understanding of our results based on available molecular dynamics simulations.

  16. NMR and dielectric studies of hydrated collagen and elastin: Evidence for a delocalized secondary relaxation

    NASA Astrophysics Data System (ADS)

    Lusceac, Sorin A.; Rosenstihl, Markus; Vogel, Michael; Gainaru, Catalin; Fillmer, Ariane; Böhmer, Roland

    2011-01-01

    Using a combination of dielectric spectroscopy and solid-state deuteron NMR, the hydration water dynamics of connective tissue proteins is studied at sub-ambient temperatures. In this range, the water dynamics follows an Arrhenius law. A scaling analysis of dielectric losses, 'two-phase' NMR spectra, and spin-lattice relaxation times consistently yield evidence for a Gaussian distribution of energy barriers. With the dielectric data as input, random-walk simulations of a large-angle, quasi-isotropic water reorientation provide an approximate description of stimulated-echo data on hydrated elastin. This secondary process takes place in an essentially rigid energy landscape, but in contrast to typical {\\beta}-relaxations it is quasi-isotropic and delocalized. The delocalization is inferred from previous NMR diffusometry experiments. To emphasize the distinction from conventional {\\beta}-processes, for aqueous systems such a matrix-decoupled relaxation was termed a {\

  17. Solid-state NMR studies of biomineralization peptides and proteins.

    PubMed

    Roehrich, Adrienne; Drobny, Gary

    2013-09-17

    unanswered. This is largely due to a lack of methods capable of providing high-resolution structural information for proteins adsorbed to material surfaces under physiologically relevant conditions. In this Account, we highlight recent work that is providing insight into the structure and crystal recognition mechanisms of a salivary protein model system, as well as the structure and interactions of a peptide that catalyzes the formation of biosilica composites. To develop a better understanding of the structure and interactions of proteins in biomaterials, we have used solid-state NMR techniques to determine the molecular structure and dynamics of proteins and peptides adsorbed onto inorganic crystal surfaces and embedded within biomineral composites. This work adds to the understanding of the structure and crystal recognition mechanisms of an acidic human salivary phosphoprotein, statherin.

  18. Variable temperature NMR studies on the conformations of tonalensin in solution

    NASA Astrophysics Data System (ADS)

    Ortega, Alfredo; Maldonado, Emma; Díaz, Eduardo; Reynolds, William F.

    1998-05-01

    NMR studies on tonalensin 1, a diterpene containing a ten membered ring, made evident the presence of three conformational isomers in solution. At room temperature compound 1 exists as a mixture of the conformers 1A and 1B in a ratio 1:1 in a CDC1 3 solution and 1.5:1 in a Me 2CO-d 6/DMSO-d 6 solution. At lower temperatures a third conformer, 1C, was detected. It was responsible for the line broadening observed for 1A. Temperature dependent 2D NMR experiments have been employed to elucidate the automerization of compound 1.

  19. An NMR study of the coexistence of nematic and "induced" smectic phases in mixtures of nematics

    NASA Astrophysics Data System (ADS)

    Diehl, P.; Wasser, H. R.; Gowda, G. A. Nagana; Suryaprakash, N.; Khetrapal, C. L.

    1989-07-01

    Deuteron NMR studies of mixtures of nematic liquid crystals such as N-( p-ethoxybenzylidene)- p-n-butylaniline and trans-4-pentyl-4-(4-cyanophenyl)cyclohexane and the molecules dissolved therein show the coexistence of up to three different spectra at certain concentrations and temperatures. This is attributed to the coexistence of nematic and "induced" smectic phases.

  20. Genetic analysis of 16 NMR-lipoprotein fractions in humans, the GOLDN study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sixteen nuclear magnetic resonance (NMR) spectroscopy lipoprotein measurements of more than 1,000 subjects of GOLDN study, at fasting and at 3.5 and 6 h after a postprandial fat (PPL) challenge at visits 2 and 4, before and after a 3 weeks Fenofibrate (FF) treatment, were included in 6 time-independ...

  1. Ultra-high field NMR studies of antibody binding and site-specific phosphorylation of {alpha}-synuclein

    SciTech Connect

    Sasakawa, Hiroaki |; Sakata, Eri; Yamaguchi, Yoshiki; Masuda, Masami |; Mori, Tetsuya; Kurimoto, Eiji; Iguchi, Takeshi; Hisanaga, Shin-ichi; Iwatsubo, Takeshi; Hasegawa, Masato; Kato, Koichi |

    2007-11-23

    Although biological importance of intrinsically disordered proteins is becoming recognized, NMR analyses of this class of proteins remain as tasks with more challenge because of poor chemical shift dispersion. It is expected that ultra-high field NMR spectroscopy offers improved resolution to cope with this difficulty. Here, we report an ultra-high field NMR study of {alpha}-synuclein, an intrinsically disordered protein identified as the major component of the Lewy bodies. Based on NMR spectral data collected at a 920 MHz proton frequency, we performed epitope mapping of an anti-{alpha}-synuclein monoclonal antibody, and furthermore, characterized conformational effects of phosphorylation at Ser129 of {alpha}-synuclein.

  2. Solid-state and unilateral NMR study of deterioration of a Dead Sea Scroll fragment.

    PubMed

    Masic, A; Chierotti, M R; Gobetto, R; Martra, G; Rabin, I; Coluccia, S

    2012-02-01

    Unilateral and solid-state nuclear magnetic resonance (NMR) analyses were performed on a parchment fragment of the Dead Sea Scroll (DSS). The analyzed sample belongs to the collection of non-inscribed and nontreated fragments of known archaeological provenance from the John Rylands University Library in Manchester. Therefore, it can be considered as original DSS material free from any contamination related to the post-discovery period. Considering the paramount significance of the DSS, noninvasive approaches and portable in situ nondestructive methods are of fundamental importance for the determination of composition, structure, and chemical-physical properties of the materials under study. NMR studies reveal low amounts of water content associated with very short proton relaxation times, T(1), indicating a high level of deterioration of collagen molecules within scroll fragments. In addition, (13)C cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy shows characteristic peaks of lipids whose presence we attribute to the production technology that did not involve liming. Extraction with chloroform led to the reduction of both lipid and protein signals in the (13)C CPMAS spectrum indicating probable involvement of lipids in parchment degradation processes. NMR absorption and relaxation measurements provide nondestructive, discriminative, and sensitive tools for studying the deterioration effects on the organization and properties of water and collagen within ancient manuscripts.

  3. A Method for Solution NMR Structural Studies of Large Integral Membrane Proteins: Reverse Micelle Encapsulation

    PubMed Central

    Kielec, Joseph M.; Valentine, Kathleen G.; Wand, A. Joshua

    2009-01-01

    The structural study of membrane proteins perhaps represents one of the greatest challenges of the post-genomic era. While membrane proteins comprise over 50% of current and potential drug targets, their structural characterization lags far behind that of soluble proteins. Nuclear magnetic resonance (NMR) offers great potential not only with respect to structural characterization of integral membrane proteins but may also provide the ability to study the details of small ligand interactions. However, the size limitations of solution NMR have restricted comprehensive structural characterization of membrane protein NMR structures to the relatively small β-barrel proteins or helical proteins of relatively simple topology. In an effort to escape the barriers presented by slow molecular reorientation of large integral membrane proteins solubilized by detergent micelles in water, we have adapted the reverse micelle encapsulation strategy originally developed for the study of large soluble proteins by solution NMR methods. Here we review a novel approach to the solubilization of large integral membrane proteins in reverse micelle surfactants dissolved in low viscosity alkane solvents. The procedure is illustrated with a 54 kDa construct of the homotetrameric KcsA potassium channel. PMID:19665988

  4. NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.

    PubMed

    Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  5. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    SciTech Connect

    Bevilaqua, Rochele C. A.; Miranda, Caetano R.; Rigo, Vagner A.; Veríssimo-Alves, Marcos

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  6. NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.

    PubMed

    Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated. PMID:25429955

  7. Development of an in Situ NMR Photoreactor To Study Environmental Photochemistry.

    PubMed

    Bliumkin, Liora; Dutta Majumdar, Rudraksha; Soong, Ronald; Adamo, Antonio; Abbatt, Jonathan P D; Zhao, Ran; Reiner, Eric; Simpson, André J

    2016-06-01

    Photochemistry is a key environmental process directly linked to the fate, source, and toxicity of pollutants in the environment. This study explores two approaches for integrating light sources with nuclear magnetic resonance (NMR) spectroscopy: sample irradiation using a "sunlight simulator" outside the magnet versus direct irradiation of the sample inside the magnet. To assess their applicability, the in situ NMR photoreactors were applied to a series of environmental systems: an atmospheric pollutant (p-nitrophenol), crude oil extracts, and groundwater. The study successfully illustrates that environmentally relevant aqueous photochemical processes can be monitored in situ and in real time using NMR spectroscopy. A range of intermediates and degradation products were identified and matched to the literature. Preliminary measurements of half-lives were also obtained from kinetic curves. The sunlight simulator was shown to be the most suitable model to explore environmental photolytic processes in situ. Other light sources with more intense UV output hold potential for evaluating UV as a remediation alternative in areas such as wastewater treatment plants or oil spills. Finally, the ability to analyze the photolytic fate of trace chemicals at natural abundance in groundwater, using a cryogenic probe, demonstrates the viability of NMR spectroscopy as a powerful and complementary technique for environmental applications in general.

  8. Development of an in Situ NMR Photoreactor To Study Environmental Photochemistry.

    PubMed

    Bliumkin, Liora; Dutta Majumdar, Rudraksha; Soong, Ronald; Adamo, Antonio; Abbatt, Jonathan P D; Zhao, Ran; Reiner, Eric; Simpson, André J

    2016-06-01

    Photochemistry is a key environmental process directly linked to the fate, source, and toxicity of pollutants in the environment. This study explores two approaches for integrating light sources with nuclear magnetic resonance (NMR) spectroscopy: sample irradiation using a "sunlight simulator" outside the magnet versus direct irradiation of the sample inside the magnet. To assess their applicability, the in situ NMR photoreactors were applied to a series of environmental systems: an atmospheric pollutant (p-nitrophenol), crude oil extracts, and groundwater. The study successfully illustrates that environmentally relevant aqueous photochemical processes can be monitored in situ and in real time using NMR spectroscopy. A range of intermediates and degradation products were identified and matched to the literature. Preliminary measurements of half-lives were also obtained from kinetic curves. The sunlight simulator was shown to be the most suitable model to explore environmental photolytic processes in situ. Other light sources with more intense UV output hold potential for evaluating UV as a remediation alternative in areas such as wastewater treatment plants or oil spills. Finally, the ability to analyze the photolytic fate of trace chemicals at natural abundance in groundwater, using a cryogenic probe, demonstrates the viability of NMR spectroscopy as a powerful and complementary technique for environmental applications in general. PMID:27172272

  9. Two dimensional NMR and NMR relaxation studies of coal structure. Progress report, April 1, 1992--June 30, 1992

    SciTech Connect

    Zilm, K.W.

    1992-09-01

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

  10. Two dimensional NMR and NMR relaxation studies of coal structure. Progress report, January 1, 1992--March 31, 1992

    SciTech Connect

    Zilm, K.W.

    1992-07-01

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

  11. In situ study of the magnetoelectrolysis phenomenon during copper electrodeposition using time domain NMR relaxometry.

    PubMed

    Gomes, Bruna Ferreira; Nunes, Luiza Maria Silva; Lobo, Carlos Manuel Silva; Cabeça, Luís Fernando; Colnago, Luiz Alberto

    2014-10-01

    Although the effect of magnetic field (B) on electrochemical reactions (magnetoelectrolysis phenomenon) has been long known, it has not been considered in electrochemical reactions analyzed in situ by magnetic resonance methods, such as nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and magnetic resonance imaging (MRI), which are intrinsically performed in the presence of B. In this report, the effect of B on the copper electrodeposition reaction, measured by a low-field (0.23 T) NMR spectrometer, was demonstrated. As expected, an enhancement in the reaction rate in comparison to the ex situ electrodeposition reaction was observed. Such enhancement was not dependent on electrodes/magnetic field orientations. Parallel and perpendicular orientations showed similar electrodeposition rates, which is explained by the cyclotron flows generated by distortions in electric and magnetic field lines near the electrode and the electrode edge. Therefore, NMR spectroscopy is not a passive analytical method, as assumed in preceding in situ spectroelectrochemical studies. Although the magnetoelectrolysis phenomenon demonstrated in this report used a paramagnetic ion, it can also be observed for diamagnetic species, since the magnetoelectrolysis phenomenon is independent of the nature of the species. Consequently, similar convection effects may occur in other electrochemical nuclear magnetic resonance (EC-NMR) experiments, such as the electrochemical reaction of organic molecules, as well as in electrocatalysis/fuel cells, lithium-ion batteries, and experiments that use electrochemical electron paramagnetic resonance (EC-EPR) and electrochemical magnetic resonance imaging (EC-MRI).

  12. Li NMR study of heavy-fermion LiV2O4 containing magnetic defects

    SciTech Connect

    Zong, X.; Das, S.; Borsa, F.; Vannette, M.; Prozorov, R.; Schmalian, J.; Johnston, D.

    2008-04-21

    We present a systematic study of the variations of the {sup 7}Li NMR properties versus magnetic defect concentration up to 0.83 mol% within the spinel structure of polycrystalline powder samples and a collection of small single crystals of LiV2O4 in the temperature range from 0.5 to 4.2 K. We also report static magnetization measurements and ac magnetic susceptibility measurements at 14 MHz on the samples at low temperatures. Both the NMR spectrum and nuclear spin-lattice relaxation rate are inhomogeneous in the presence of the magnetic defects. The NMR data for the powders are well explained by assuming that (i) there is a random distribution of magnetic point defects, (ii) the same heavy Fermi liquid is present in the samples containing the magnetic defects as in magnetically pure LiV2O4, and (iii) the influences of the magnetic defects and of the Fermi liquid on the magnetization and NMR properties are separable. In the single crystals, somewhat different behaviors are observed. Remarkably, the magnetic defects in the powder samples show evidence of spin freezing below T {approx} 1.0 K, whereas in the single crystals with similar magnetic defect concentration no spin freezing was found down to 0.5 K. Thus different types of magnetic defects and/or interactions between them appear to arise in the powders versus the crystals, possibly due to the substantially different synthesis conditions of the powders and crystals.

  13. In situ study of the magnetoelectrolysis phenomenon during copper electrodeposition using time domain NMR relaxometry.

    PubMed

    Gomes, Bruna Ferreira; Nunes, Luiza Maria Silva; Lobo, Carlos Manuel Silva; Cabeça, Luís Fernando; Colnago, Luiz Alberto

    2014-10-01

    Although the effect of magnetic field (B) on electrochemical reactions (magnetoelectrolysis phenomenon) has been long known, it has not been considered in electrochemical reactions analyzed in situ by magnetic resonance methods, such as nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and magnetic resonance imaging (MRI), which are intrinsically performed in the presence of B. In this report, the effect of B on the copper electrodeposition reaction, measured by a low-field (0.23 T) NMR spectrometer, was demonstrated. As expected, an enhancement in the reaction rate in comparison to the ex situ electrodeposition reaction was observed. Such enhancement was not dependent on electrodes/magnetic field orientations. Parallel and perpendicular orientations showed similar electrodeposition rates, which is explained by the cyclotron flows generated by distortions in electric and magnetic field lines near the electrode and the electrode edge. Therefore, NMR spectroscopy is not a passive analytical method, as assumed in preceding in situ spectroelectrochemical studies. Although the magnetoelectrolysis phenomenon demonstrated in this report used a paramagnetic ion, it can also be observed for diamagnetic species, since the magnetoelectrolysis phenomenon is independent of the nature of the species. Consequently, similar convection effects may occur in other electrochemical nuclear magnetic resonance (EC-NMR) experiments, such as the electrochemical reaction of organic molecules, as well as in electrocatalysis/fuel cells, lithium-ion batteries, and experiments that use electrochemical electron paramagnetic resonance (EC-EPR) and electrochemical magnetic resonance imaging (EC-MRI). PMID:25162751

  14. Comparative study of inversion methods of three-dimensional NMR and sensitivity to fluids

    NASA Astrophysics Data System (ADS)

    Tan, Maojin; Wang, Peng; Mao, Keyu

    2014-04-01

    Three-dimensional nuclear magnetic resonance (3D NMR) logging can simultaneously measure transverse relaxation time (T2), longitudinal relaxation time (T1), and diffusion coefficient (D). These parameters can be used to distinguish fluids in the porous reservoirs. For 3D NMR logging, the relaxation mechanism and mathematical model, Fredholm equation, are introduced, and the inversion methods including Singular Value Decomposition (SVD), Butler-Reeds-Dawson (BRD), and Global Inversion (GI) methods are studied in detail, respectively. During one simulation test, multi-echo CPMG sequence activation is designed firstly, echo trains of the ideal fluid models are synthesized, then an inversion algorithm is carried on these synthetic echo trains, and finally T2-T1-D map is built. Futhermore, SVD, BRD, and GI methods are respectively applied into a same fluid model, and the computing speed and inversion accuracy are compared and analyzed. When the optimal inversion method and matrix dimention are applied, the inversion results are in good aggreement with the supposed fluid model, which indicates that the inversion method of 3D NMR is applieable for fluid typing of oil and gas reservoirs. Additionally, the forward modeling and inversion tests are made in oil-water and gas-water models, respectively, the sensitivity to the fluids in different magnetic field gradients is also examined in detail. The effect of magnetic gradient on fluid typing in 3D NMR logging is stuied and the optimal manetic gradient is choosen.

  15. {sup 1}H NMR spectroscopic studies establish that heparanase is a retaining glycosidase

    SciTech Connect

    Wilson, Jennifer C.; Laloo, Andrew Elohim; Singh, Sanjesh; Ferro, Vito

    2014-01-03

    Highlights: •{sup 1}H and {sup 13}C NMR chemical shifts of fondaparinux were fully assigned by 1D and 2D NMR techniques. •Hydrolysis of fondaparinux by heparanase was monitored by {sup 1}H NMR spectroscopy. •Heparanase is established to be a retaining glycosidase. -- Abstract: Heparanase is an endo-β-glucuronidase that cleaves heparan sulfate side chains of proteoglycans in basement membranes and the extracellular matrix (ECM). Heparanase is implicated in several diverse pathological processes associated with ECM degradation such as metastasis, inflammation and angiogenesis and is thus an important target for anti-cancer and anti-inflammatory drug discovery. Heparanase has been classed as belonging to the clan A glycoside hydrolase family 79 based on sequence analysis, secondary structure predictions and mutagenic analysis, and thus it has been inferred that it is a retaining glycosidase. However, there has been no direct experimental evidence to support this conclusion. Herein we describe {sup 1}H NMR spectroscopic studies of the hydrolysis of the pentasaccharide substrate fondaparinux by heparanase, and provide conclusive evidence that heparanase hydrolyses its substrate with retention of configuration and is thus established as a retaining glycosidase. Knowledge of the mechanism of hydrolysis may have implications for future design of inhibitors for this important drug target.

  16. Layered structure of room-temperature ionic liquids in microemulsions by multinuclear NMR spectroscopic studies.

    PubMed

    Falcone, R Dario; Baruah, Bharat; Gaidamauskas, Ernestas; Rithner, Christopher D; Correa, N Mariano; Silber, Juana J; Crans, Debbie C; Levinger, Nancy E

    2011-06-01

    Microemulsions form in mixtures of polar, nonpolar, and amphiphilic molecules. Typical microemulsions employ water as the polar phase. However, microemulsions can form with a polar phase other than water, which hold promise to diversify the range of properties, and hence utility, of microemulsions. Here microemulsions formed by using a room-temperature ionic liquid (RTIL) as the polar phase were created and characterized by using multinuclear NMR spectroscopy. (1)H, (11)B, and (19)F NMR spectroscopy was applied to explore differences between microemulsions formed by using 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) as the polar phase with a cationic surfactant, benzylhexadecyldimethylammonium chloride (BHDC), and a nonionic surfactant, Triton X-100 (TX-100). NMR spectroscopy showed distinct differences in the behavior of the RTIL as the charge of the surfactant head group varies in the different microemulsion environments. Minor changes in the chemical shifts were observed for [bmim](+) and [BF(4)](-) in the presence of TX-100 suggesting that the surfactant and the ionic liquid are separated in the microemulsion. The large changes in spectroscopic parameters observed are consistent with microstructure formation with layering of [bmim](+) and [BF(4)](-) and migration of Cl(-) within the BHDC microemulsions. Comparisons with NMR results for related ionic compounds in organic and aqueous environments as well as literature studies assisted the development of a simple organizational model for these microstructures. PMID:21547960

  17. Ammonia fixation by humic substances: A nitrogen-15 and carbon-13 NMR study

    USGS Publications Warehouse

    Thorn, K.A.; Mikita, M.A.

    1992-01-01

    The process of ammonia fixation has been studied in three well characterized and structurally diverse fulvic and humic acid samples. The Suwannee River fulvic acid, and the IHSS peat and leonardite humic acids, were reacted with 15N-labelled ammonium hydroxide, and analyzed by liquid phase 15N NMR spectrometry. Elemental analyses and liquid phase 13C NMR spectra also were recorded on the samples before and after reaction with ammonium hydroxide. The largest increase in percent nitrogen occurred with the Suwannee River fulvic acid, which had a nitrogen content of 0.88% before fixation and 3.17% after fixation. The 15N NMR spectra revealed that ammonia reacted similarly with all three samples, indicating that the functional groups which react with ammonia exist in structural configurations common to all three samples. The majority of nitrogcn incorporated into the samples appears to be in the form of indole and pyrrole nitrogen, followed by pyridine, pyrazine, amide and aminohydroquinone nitrogen. Chemical changes in the individual samples upon fixation could not be discerned from the 13C NMR spectra.

  18. NMR study of the magnetization of superfluid helium-3-boron and NMR of superfluid helium-3 in aerogel

    NASA Astrophysics Data System (ADS)

    Haard, Thomas Michael

    Pulsed NMR measurements of superfluid 3He confined in 98.2% porosity silica aerogel are reported. The aerogel suppressed the superfluid transition temperature TC and the order parameter magnitude from their bulk values in qualitative agreement with impurity scattering models. Magnetization measurements showed that the superfluid is an equal spin pairing state (ESP). The superfluid exhibited positive NMR frequency shifts with similar temperature dependence to those of the bulk A-phase, only smaller. TC was independent of the magnetic field for H < 1.8 kOe to within the experimental error. At 2.18 kOe an increased suppression of TC and the order parameter was observed. Two layers of solid 3He were adsorbed to the aerogel strands. When these were replaced with solid 4He a non-ESP superfluid state was observed. An experimental cell for measuring the heat capacity of 3He in aerogel was designed and fabricated. It was tested without aerogel by measuring the heat capacity of liquid 3He over a range of temperatures from 1 to 25 mK and at pressures of 7.0, 14.0, and 28.0 bar. The measurements in both the normal and superfluid phases were consistent with the data of Greywall. The discrepancy between static and dynamic measurements of the magnetization of superfluid 3He-B was characterized over a region of the phase diagram by comparison of nuclear magnetic resonance (NMR) data and recent SQUID data from other researchers. At the B- to A-phase transition, TAB, the discrepancy was absent at low pressure, but increased to 20% at 26.6 bar and 1.2 kOe. The NMR data were consistent with the weak-coupling-plus (wcp) theory at TAB for most pressures and fields. The Ginzburg-Landau strong-coupling parameter gz/( gz)wcp was determined from NMR results to equal 1.00 +/- 0.03 for all pressures. Combinations of the Ginzburg-Landau beta-parameters are reported that are consistent with this observation.

  19. Solid state NMR study of SEI formation in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Dachun

    Recently, rechargeable lithium ion batteries, which offer high energy density and long cycle life, are in great demand as power sources for our mobile electronic society. The formation of a solid electrolyte interphase (SEI) on the surface of electrodes in lithium ion batteries plays an essential role in their performance. This thesis presents solid state NMR and MAS NMR results on the SEI, which contribute to our understanding of SEI formation on both cathodes and anodes. This thesis is organized as following: Chapter 1 surveys the history of batteries and the challenges to further development of the lithium ion battery. Fundamental aspects and SEI formation mechanisms are also included in Chapter l. Chapter 2 deals with the principles and experimental techniques of solid state NMR. Chapter 3 presents studies of SEI formation on anode and cathode in lithium ion batteries using electrochemical impedance spectroscopy (EIS) and NMR. The results provide EIS and NMR evidence that cells containing electrolytes with high EC content display less irreversible capacity after high temperature storage. The irreversible capacity is attributed to SEI growth on electrode surfaces. NMR results on cathodes, on the other hand, imply that the presence of Ni in the cathode may reduce cell performance due to the oxidation of Ni 3+ to Ni4+. Our simulations show that a lower EC/DMC ratio is associated with a smaller SEI intensity for the cathode and higher intensity for the anode. Chapter 4 discusses the effect of temperature on SEI formation on anodes and cathodes. NMR measurements show that MCMB graphite based anodes exhibit high stability no chemical shift is evident over a wide temperature range. On cathodes, however, NMR does reveal changes in SEI intensity as a function of temperature. These changes are believed to be the result of decomposition of the SEI. Evidently, then, changes in the performance of the cell as a factor of temperature are, at least in part, due to changes in

  20. In-situ NMR study of molecular and ionic processes inside carbon nanopores

    NASA Astrophysics Data System (ADS)

    Luo, Zhixiang

    Interactions of simple ions with water and interfaces play critical roles in many electrochemical and biological processes. They are especially significant in nanoconfined regions and have a profound impact in many applications, for instance nanofluidics and supercapacitors. This dissertation employs a nuclear magnetic resonance (NMR) technique to study their influence on the ionic processes inside carbon nanopores. To characterize the carbon micropore structure, a convenient NMR method is established by taking a 1H magic angle spinning (MAS) spectrum of the adsorbed water. A density functional theory (DFT) computation of the nucleus-independent chemical shift (NICS) yields a quantitative relationship between the NICS values and the micropore sizes. The carbon micropore size and distribution are derived from the chemical shift and the spectrum lineshape. For aqueous electrolytes inside uncharged carbon nanopores, the measurement of ion concentrations reveals a substantial electroneutrality breakdown. The specific ion effects and ion-ion correlations are shown to play crucial roles in determining the degree of electroneutrality breakdown. The importance of those interactions is further revealed by the asymmetric and nonlinear responses of ion concentrations to the charging of the confining carbon walls. Such information is obtained with a carbon supercapacitor built into the NMR probe. The NMR observations are validated by a numerical calculation of the ion distribution in the nanopores using the generalized Poisson-Boltzmann (PB) equation, demonstrating that the nonelectrostatic interfacial interactions can indeed dominate the electrostatic interactions and lead to the breakdown of electroneutrality inside nanoconfined regions. Interfacial ion hydration is an essential part of the specific ion effects. Using in-situ 23Na and 19F NMR on carbon supercapacitors with different carbon pore sizes, I provide a molecular-scale understanding of the permeation and

  1. The influence of oxygen-17 enriched oxygen-donor ligands on the electronic spin relaxation behaviour of paramagnetic metal ions

    NASA Astrophysics Data System (ADS)

    Wells, Gregg B.; Yim, Moon B.; Makinen, Marvin W.

    Continuous wave microwave power saturation of high-spin paramagnetic metalloprotein complexes of Co2+ and Fe3+ showed that the value of the saturation parameter P1/2 is influenced by the coordination of oxygen-17 enriched water to the metal ion. No change was observed for H218O or 2H2O. Pulse saturation and recovery of paramagnetic high-spin Fe3+ heme proteins identified a fast relaxation component sensitive to isotopic oxygen-17 composition that was assigned to the process of spectral diffusion. It is shown that the change in relaxation time for spectral diffusion can alter the (apparent) spin-lattice relaxation to account for the observed changes in continuous wave microwave power saturation experiments. These changes are shown to correlate with alterations in the extent of covalency between the metal ion and oxygen-donor ligand. The experimental results provide a basis for use of continuous wave microwave saturation to identify the presence of oxygen-donor ligands within the inner coordination shell of high-spin Co2+ or Fe3+ in metalloprotein and small molecule complexes and to qualitatively assess the extent of covalency between the metal ion and the oxygen-donor ligand.

  2. Preliminary 1H NMR study on archaeological waterlogged wood.

    PubMed

    Maccotta, Antonella; Fantazzini, Paola; Garavaglia, Carla; Donato, Ines D; Perzia, Patrizia; Brai, Maria; Morreale, Filippa

    2005-01-01

    Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood. PMID:16485652

  3. Preliminary 1H NMR study on archaeological waterlogged wood.

    PubMed

    Maccotta, Antonella; Fantazzini, Paola; Garavaglia, Carla; Donato, Ines D; Perzia, Patrizia; Brai, Maria; Morreale, Filippa

    2005-01-01

    Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood.

  4. NMR Studies of the original magnetic properties of the cuprates: influence of impurities and defects.

    NASA Astrophysics Data System (ADS)

    Alloul, Henri

    1998-03-01

    The cuprates display original magnetic properties, both in their insulating and metallic phases. In underdoped metallic systems, a pseudo gap in the density of magnetic q=3D0 excitations is observed from local susceptibility measurements, as well as from specific heat and transport properties. A pseudo spin-gap in the AF excitations at the AF wave vector is detected both by NMR and inelastic neutron scattering. From the NMR measurements it can be concluded that these magnetic anomalies are quite similar in single layer(J. Bobroff, H.. Alloul, P. Mendels, V. Viallet, J. F. Marucco and D. Colson, Phys. Rev. Letters 78, 3757 (1997).), bilayer and trilayer underdoped cuprates. The modifications of magnetic properties induced by substitutions or defects in the planes, which do not modify appreciably the charge transfer have been studied. The spatial dependence of the spin susceptibility \\chi ' (r) of the pure material can be directly probed through the study of the modifications of the NMR spectra of various nuclei (^89Y, ^17O, ^63Cu) induced by such localised magnetic impurities. Large qualitative differences between the underdoped and slightly overdoped YBCO are evidenced from ^17O NMR line broadening in Ni substituted YBCO. This allows us to propose a quite powerful method for studying the q and T dependence of the static magnetic susceptibility (J. Bobroff et al, Phys. Rev. Letters 78, 3757 (1997).). The impurity magnetic state also directly reflects the occurence of electronic correlations in the metallic state. The case of Zn will be examined in some detail. ^89Y NMR has revealed that the substitution of this 3d^10 non magnetic atom on a Cu site induces a Curie like contribution to the local susceptibility on the near neighbour coppers ( A. V. Mahajan, H. Alloul, G. Collin and J. F. Marucco, Physical Review Letters 72, 3100 (1994).). The effective induced moment decreases with hole doping and becomes rather weak, but is still present for optimal doping

  5. NMR study of hydrogen diffusion in zirconium hydride

    SciTech Connect

    Korn, C.; Goren, S.D.

    1986-01-01

    The nuclear-magnetic-resonance method was used to study the diffusion of hydrogen in zirconium hydride by measuring the temperature dependence of T/sub 1/ in a temperature range where the major relaxation mechanism was due to hydrogen diffusion. The samples investigated were ZrH/sub 1.588/, ZrH/sub 1.629/, ZrH/sub 1.684/, ZrH/sub 1.736/, ZrH/sub 1.815/, ZrH/sub 1.910/, and ZrH/sub 1.960/. These spanned both the cubic and tetragonal phases. The activation energy was found to be independent of hydrogen concentration in the cubic phase with E/sub a/ = 13.4 +- 0.4 kcal/mol and a preexponential factor given by A = (1/2)(2-x)(45 +- 10) x 10/sup 12/ Hz. In the tetragonal phase the activation energy of the bulk of the hydrogen increased modestly with concentration. In addition, it was discovered that a new very fast hydrogen channel was created by the tetragonality for approx.3% of the hydrogen. They jump with a preexponential factor that is about 2 orders of magnitude larger than that of the rest of the hydrogen. A comparison was also made between the Bloembergen-Purcell-Pound, the Barton-Sholl, and the Bustard theories for nuclear magnetic relaxation due to diffusion.

  6. NMR study of hydrogen diffusion in zirconium hydride

    NASA Astrophysics Data System (ADS)

    Korn, C.; Goren, S. D.

    1986-01-01

    The nuclear-magnetic-resonance method was used to study the diffusion of hydrogen in zirconium hydride by measuring the temperature dependence of T1 in a temperature range where the major relaxation mechanism was due to hydrogen diffusion. The samples investigated were ZrH1.588, ZrH1.629, ZrH1.684, ZrH1.736, ZrH1.815, ZrH1.910, and ZrH1.960. These spanned both the cubic and tetragonal phases. The activation energy was found to be independent of hydrogen concentration in the cubic phase with Ea=13.4+/-0.4 kcal/mol and a preexponential factor given by A=(1/2)(2-x)(45+/-10)×1012 Hz. In the tetragonal phase the activation energy of the bulk of the hydrogen increased modestly with concentration. In addition, it was discovered that a new very fast hydrogen channel was created by the tetragonality for ~3% of the hydrogen. They jump with a preexponential factor that is about 2 orders of magnitude larger than that of the rest of the hydrogen. A comparison was also made between the Bloembergen-Purcell-Pound, the Barton-Sholl, and the Bustard theories for nuclear magnetic relaxation due to diffusion.

  7. Proton NMR study of the state of water in fibrin gels, plasma, and blood clots

    SciTech Connect

    Blinc, A.; Lahajnar, G.; Blinc, R.; Zidansek, A.; Sepe, A. )

    1990-04-01

    A proton NMR relaxation and pulsed field gradient self-diffusion study of water in fibrin gels, plasma, and blood clots has been performed with special emphasis on the effect of the sol-gel and shrinkage transitions. Deuteron NMR in fibrin gels was also studied to supplement the proton data. It is shown that a measurement of the water proton or deuteron T1/T2 ratio allows for a determination of the bound water fraction in all these systems. The change in the T1/T2 ratio at the shrinkage transition further allows for a determination of the surface fractal dimension of the gel if the change in the volume of the gel is known. The self-diffusion coefficient of water in these systems, which determines the transport properties of the gel, is found to be proportional to the free water fraction in both the nonshrunken and shrunken state.

  8. Structural studies of pravastatin and simvastatin and their complexes with SDS micelles by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Rakhmatullin, I. Z.; Galiullina, L. F.; Klochkova, E. A.; Latfullin, I. A.; Aganov, A. V.; Klochkov, V. V.

    2016-02-01

    Conformational features of pravastatin and simvastatin molecules in solution and in their complexes with sodium dodecyl sulfate micelles (SDS) were studied by 2D NOESY NMR spectroscopy. On the basis of the nuclear magnetic resonance experiments it was established that pravastatin and simvastatin can form molecular complex with SDS micelles which were considered as the model of cell membrane. In addition, interatomic distances for studied compounds were calculated based on 2D NOESY NMR experiments. It was shown that pravastatin interacts only with a surface of model membrane. However, in contrast to pravastatin, simvastatin penetrates into the inner part of SDS micelles. Observed distinctions in the mechanisms of interaction of pravastatin and simvastatin with models of cell membranes could explain the differences in their pharmacological properties.

  9. Protein-Carbohydrate Interactions Studied by NMR: From Molecular Recognition to Drug Design

    PubMed Central

    Fernández-Alonso, María del Carmen; Díaz, Dolores; Berbis, Manuel Álvaro; Marcelo, Filipa; Cañada, Javier; Jiménez-Barbero, Jesús

    2012-01-01

    Diseases that result from infection are, in general, a consequence of specific interactions between a pathogenic organism and the cells. The study of host-pathogen interactions has provided insights for the design of drugs with therapeutic properties. One area that has proved to be promising for such studies is the constituted by carbohydrates which participate in biological processes of paramount importance. On the one hand, carbohydrates have shown to be information carriers with similar, if not higher, importance than traditionally considered carriers as amino acids and nucleic acids. On the other hand, the knowledge on molecular recognition of sugars by lectins and other carbohydrate-binding proteins has been employed for the development of new biomedical strategies. Biophysical techniques such as X-Ray crystallography and NMR spectroscopy lead currently the investigation on this field. In this review, a description of traditional and novel NMR methodologies employed in the study of sugar-protein interactions is briefly presented in combination with a palette of NMR-based studies related to biologically and/or pharmaceutically relevant applications. PMID:23305367

  10. Reduction of andrographolide and its stereostructure by NMR and X-ray study.

    PubMed

    Singh, Deepika; Chaudhuri, Prabir K

    2013-04-01

    Andrographolide (1) on asymmetric reduction with nickel boride in situ led to the identification of a product as 12,13 R-dihydroandrographolide (3) in de (>96%). The structure and stereochemistry of compound 3 were established by NMR study and confirmed by X-ray crystallographic analysis. β-Substituent of γ-butyrolactone in andrographolide exerted diastereomeric selectivity in reduction. Neoandrographolide (2) under similar condition yielded 5. PMID:22559743

  11. Study of aging in oil paintings by 1D and 2D NMR spectroscopy.

    PubMed

    Spyros, Apostolos; Anglos, Demetrios

    2004-09-01

    Nuclear magnetic resonance spectroscopy is proposed as an efficient analytical tool in the study of painted artworks. The binding medium from two original oil paintings, dated from the early 20th and the late 17th century, was studied via high-resolution 1D and 2D NMR, establishing the advanced state of hydrolysis and oxidation of the oil paint. Studies of the solvent-extractable component from model samples of various drying oils, raw oil paints, and aged oil paints allowed the definition of several markers based on the integral ratios of various chemical species present in the 1H and 13C NMR spectra. These markers are sensitive to hydrolytic and oxidative processes that reflect the extent of aging in oil paintings. The rapidity, simplicity, and nondestructive nature of the proposed analytical NMR methodology represents a great advantage, since the usually minute sample quantities available from original artwork can be subsequently analyzed further by other analytical techniques, if necessary. PMID:15373425

  12. Solid-state 29Si MAS NMR studies of diatoms: structural characterization of biosilica deposits.

    PubMed

    Bertermann, R; Kröger, N; Tacke, R

    2003-03-01

    Four different diatom species (Chaetoceros debilis, Chaetoceros didymum, Cylindrotheca fusiformis, Nitzschia angularis) were studied by solid-state (29)Si MAS NMR spectroscopy. To determine the Q(2):Q(3):Q(4) ratios in the biosilica deposits of the diatoms, quantitative (29)Si MAS NMR experiments were performed. This analysis did not reveal any differences regarding the molecular architecture of the silica (i.e. the degree of condensation of the SiOH units (2 identical with SiOH --> identical with Si-O-Si identical with + H(2)O)) from the different diatom species. However, complete cells showed significantly smaller Q(4):Q(3) ratios (1.8-1.9) than extracted cell walls (2.5-2.8), indicating the existence of intracellular pools of less condensed silica.

  13. NMR study of the ternary carbides M2 AlC (M=Ti,V,Cr)

    NASA Astrophysics Data System (ADS)

    Lue, C. S.; Lin, J. Y.; Xie, B. X.

    2006-01-01

    We have performed a systematic study of the layered ternary carbides Ti2AlC , V2AlC , and Cr2AlC using Al27 NMR spectroscopy. The quadrupole splittings, Knight shifts, as well as spin-lattice relaxation times on each material have been identified. The sign of the isotropic Knight shift varies from positive for Ti2AlC and V2AlC to negative for Cr2AlC , attributed to the enhancement of hybridization with increasing valence electron count in the transition metal. Universally long relaxation times are found for these alloys. Results provide a measure of Al-s Fermi-level density of states Ns(EF) for Ti2AlC and V2AlC . In addition, the evidence that Ns(EF) correlates with the transition metal d -electron count has been explored in the present NMR investigation.

  14. /sup 13/C NMR studies of the molecular flexibility of antidepressants

    SciTech Connect

    Munro, S.L.; Andrews, P.R.; Craik, D.J.; Gale, D.J.

    1986-02-01

    The solution dynamics of a series of clinically potent antidepressants have been investigated by measuring /sup 13/C NMR relaxation parameters. Correlation times and internal motional rates were calculated from spin-lattice relaxation times and nuclear Overhauser effects for the protonated carbons in mianserin, imipramine-like antidepressants, and amitriptyline-like antidepressants. These data were interpreted in terms of overall molecular tumbling, internal rotations, and inherent flexibility of these structures. Of particular interest was the conformational variability of the tricyclic nucleus of the tricyclic antidepressants, where the data indicated a fivefold difference in mobility of the dimethylene bridge of imipramine-like antidepressants relative to amitriptyline-like compounds. The implications of such a difference in internal motions is discussed in relation to previous NMR studies and to the reported differences in pharmacological activity of these antidepressants.

  15. NMR methods for studying the structure and dynamics of oncogenic and antihistaminic peptides in biomembranes.

    PubMed

    Sizun, Christina; Aussenac, Fabien; Grelard, Axelle; Dufourc, Erick J

    2004-02-01

    We present several applications of both wide-line and magic angle spinning (MAS) solid-state NMR of bicelles in which are embedded fragments of a tyrosine kinase receptor or enkephalins. The magnetically orientable bicelle membranes are shown to be of particular interest for studying the functional properties of lipids and proteins in a state that is very close to their natural environment. Quadrupolar, dipolar and chemical shielding interactions can be used to determine minute alterations of internal membrane dynamics and the orientation of peptides with respect to the membrane plane. MAS of bicelles can in turn lead to high-resolution proton spectra of hydrated membranes. Using deuterium-proton contrast methods one can then obtain pseudo-high-resolution proton spectra of peptides or proteins embedded in deuterated membranes and determine their atomic 3D structure using quasi-conventional liquid-state NMR methods. PMID:14745798

  16. Chiral Magnetism in an Itinerant Helical Magnet, MnSi - An Extended 29Si NMR Study

    NASA Astrophysics Data System (ADS)

    Yasuoka, Hiroshi; Motoya, Kiyoichiro; Majumder, Mayukh; Witt, Sebastian; Krellner, Cornelius; Baenitz, Michael

    2016-07-01

    The microscopic magnetism in the helical, conical and ferromagnetically polarized phases in an itinerant helical magnet, MnSi, has been studied by an extended 29Si NMR at zero field and under external magnetic fields. The temperature dependence of the staggered moment, MQ(T), determined by the 29Si NMR frequency, ν(T), and the nuclear relaxation rate, 1/T1(T), at zero field is in general accord with the SCR theory for weak itinerant ferromagnetic metals and its extension to helical magnets. The external field dependence of resonance frequency, ν(H), follows a vector sum of the contributions from the atomic hyperfine and macroscopic fields with a field induced moment characteristic to itinerant magnets. A discontinuous jump of the resonance frequency at the critical field, Hc, between the conical and the polarized phases has also been found, which suggests a first order like change of the electronic states at Hc.

  17. Comparative evaluation of NMR and nuclear medicine in disc space infection: A pilot study

    SciTech Connect

    Modic, M.; Feiglin, D.; Piraino, D.; O'Donnell, J.K.; Go, R.T.; Weinstein, M.; MacIntyre, W.J.

    1984-01-01

    Six patients with proven disc space infection underwent bone scanning with 975MB/sub q/ HDP together with NMR imaging on a 0.6T superconducting magnet to obtain weighted T1 30mSec (TE .3 Sec TR) and T2 (120mSec TE 3 Sec TR) images within a 48 hr. period. All patients had plain radiographic evaluation of the areas involved. Three pts. had Ga-67 Citrate scans using 222MBq activity following the bone scan and 1 patient had CT images of the involved area. All 6 bone scans showed increased bony uptake in at least the adjacent vertebral end plates but did not show any abnormal uptake in the region of the disc. Bony activity distribution was non-specific and could have been consistent with either degenerative or osteomyelitic change. Gallium imaging in one case supported the latter diagnosis but did not indicate presence of disc space involvement. Two other cases showed bony involvement to the extent of the bone scan; one showing minimal uptake due to antibiotic therapy. Plain radiographs were suggestive of disc space infection in all cases. NMR in all cases revealed marked disc space and adjacent bone involvement to the extent shown on bone scans. T1 and T2 weighted images appeared highly specific for either infection or degenerative change and were unaffected by antibiotic therapy. NMR appears to be more sensitive in evaluation of disc space infection than radionuclide studies. NMR is also able to provide significant anatomic information involving thecal sac and neural structures. Nuclear medicine studies appear equally sensitive though less specific in the evaluation of bone involvement except perhaps where antibiotic therapy has been used.

  18. NMR Studies of Polymer-Nanoparticle Interfaces in Biological and Synthetic Nanocomposites

    NASA Astrophysics Data System (ADS)

    Schmidt-Rohr, Klaus

    2010-03-01

    Nuclear magnetic resonance (NMR) provides unique capabilities for studying buried interfaces in organic-inorganic (specifically phosphate-based) nanocomposites, in terms of local composition as well as distances between, and mobility of, structural units near the interface. The organic-inorganic interface is crucial for the mechanical coupling between the polymer and the inorganic nanoparticles. We have studied the organic-inorganic nanocomposite in bone and characterized the interface between the organic matrix (the triple-helical fibrous polypeptide collagen) and the inorganic, reinforcing bioapatite (a calcium phosphate) that accounts for 45 vol% of the material and is present as ˜3-nm thick nanocrystals. By solid-state ^13C^31P NMR, we can obtain selective spectra of the collagen residues at the interface; ionic and hydroxyproline C-OH groups of significant mobility are dominant. ^1H-^31P and ^1H-^13C NMR prove that water with isotropic mobility, which accounts for about 7% of the total volume, forms a monomolecular interfacial layer between apatite and collagen. Its rotational correlation time is about five orders of magnitude longer than that of liquid water. We propose that this water layer can be considered as ``viscous glue'' that holds the components of the nanocomposite together. It would avoid stress concentration and, by virtue of its flexible H-bonding, reduce the requirement of matched lock-and-key binding sites for collagen sidegroups on the apatite surface. In nanocomposites of phosphate glass with polyamides, ^1H-^13C NMR reveals a reduced crystallinity of the polyamide near the inorganic particles.[4pt] Coauthors: Yan-Yan Hu, Aditya Rawal (Ames Laboratory), Joshua Otaigbe (University of Southern Mississippi)

  19. Interaction of antiaggregant molecule ajoene with membranes. An ESR and 1H, 2H, 31P-NMR study.

    PubMed

    Debouzy, J C; Neumann, J M; Hervé, M; Daveloose, D; Viret, J; Apitz-Castro, R

    1989-01-01

    The structure of ajoene, a molecule extracted from garlic, has been studied by 1H-NMR and its interaction with model membranes by 1H-, 2H-, 31-P-NMR and ESR experiments. This study clearly shows that the ajoene molecule is located deep in the layer and is close to the interlayer medium. Moreover while NMR experiments show that the membrane structure is only slightly affected by the presence of ajoene, ESR experiments reveal significant modifications in phospholipid dynamics. This interaction, observed before with the phenothiazine derivative, promazine, results in an increase of the membrane fluidity in its hydrophobic part and could be related to clinical properties of ajoene.

  20. Novel electrolytes for use in new and improved batteries: An NMR study

    NASA Astrophysics Data System (ADS)

    Berman, Marc B.

    This thesis focuses on the use of nuclear magnetic resonance (NMR) spectroscopy in order to study materials for use as electrolytes in batteries. The details of four projects are described in this thesis as well as a brief theoretical background of NMR. Structural and dynamics properties were determined using several NMR techniques such as static, MAS, PFG diffusion, and relaxation to understand microscopic and macroscopic properties of the materials described within. Nuclei investigate were 1H, 2H, 7Li, 13C, 19F, 23Na, and 27Al. The first project focuses on an exciting new material to be used as a solid electrolyte membrane. T. The second project focuses on the dynamics of ionic liquid-solvent mixtures and their comparison to molecular dynamics computer simulations. The third project involves a solvent-free film containing NaTFSI salt mixed in to PEO for use in sodium-ion batteries. This final project focuses on a composite electrolyte consisting of a ceramic and solid: LiI:PEO:LiAlO2.

  1. Structure and motion of phospholipids in human plasma lipoproteins. A sup 31 P NMR study

    SciTech Connect

    Fenske, D.B.; Chana, R.S.; Parmar, Y.I.; Treleaven, W.D.; Cushley, R.J. )

    1990-04-24

    The structure and motion of phospholipids in human plasma lipoproteins have been studied by using {sup 31}P NMR. Lateral diffusion coefficients, D{sub T}, obtained from the viscosity dependence of the {sup 31}P NMR line widths, were obtained for very low density lipoprotein (VLDL), low-density lipoprotein (LDL), high-density lipoproteins (HDL{sub 2}, HDL{sub 3}), and egg PC/TO microemulsions at 25{degree}C, for VLDL at 40{degree}C, and for LDL at 45{degree}C. In order to prove the orientation and/or order of the phospholipid head-group, estimates of the residual chemical shift anistropy, {Delta}{sigma}, have been obtained for all the lipoproteins and the microemulsions from the viscosity and field dependence for the {sup 31}P NMR line widths. These results suggest differences in the orientation and/or ordering of the head-group in the HDLs. The dynamic behavior of the phosphate moiety in LDL and HDL{sub 3} has been obtained from the temperature dependence of the {sup 31}P spin-lattice relaxation rates. Values of the correlation time for phosphate group reorientation and the activation energy for the motion are nearly identical in LDL and HDL{sub 3} and are similar to values obtained for phospholipid bilayers. This argues against long-lived protein-lipid interactions being the source of either the slow diffusion in LDL or the altered head-group orientation in the HDLs.

  2. Intrinsic Proton NMR Studies of Mg(OH)2 and Ca(OH)2

    NASA Astrophysics Data System (ADS)

    Itoh, Yutaka; Isobe, Masahiko

    2016-09-01

    We studied the short proton free induction decay signals and the broad 1H NMR spectra of Mg(OH)2 and Ca(OH)2 powders at 77-355 K and 42 MHz using pulsed NMR techniques. Using a Gaussian-type back extrapolation procedure for the obscured data of the proton free induction decay signals, we obtained more precise values of the second moments of the Fourier-transformed broad NMR spectra than those in a previous report [Y. Itoh and M. Isobe, J. Phys. Soc. Jpn. 84, 113601 (2015)] and compared with the theoretical second moments. The decrease in the second moment could not account for the large decrease in the magnitude of the intrinsic proton spin-lattice relaxation rate 1/T1 from Mg(OH)2 to Ca(OH)2. The analysis of 1/T1 ∝ exp(-Eg/kBT) with Eg ˜ 0.01 eV points to a local hopping mechanism, and that of 1/T1 ∝ Tn with n ˜ 0.5 points to an anharmonic rattling mechanism.

  3. Nuclear Magnetic Resonance (NMR) as a tool for the study of the metabolism of Rickettsia slovaca.

    PubMed

    García-Álvarez, Lara; Busto, Jesús H; Peregrina, Jesús M; Santibáñez, Sonia; Portillo, Aránzazu; Avenoza, Alberto; Oteo, José A

    2015-01-01

    Rickettsial infections are caused by intracellular bacteria. They do not grow in standard culture media so there are limitations in routine practice to study their metabolism. Nuclear Magnetic Resonance (NMR) spectroscopy is used for identification of metabolites in biological samples. Vero cells infected with Rickettsia slovaca as well as uninfected cells were monitored by (1)H NMR showing the presence of ethanol and lactic acid. As no differences were observed, labeled compounds were added into cultures. When D-[1-13C]glucose was monitored by (13)C NMR no differences among infected and uninfected cells were observed in metabolic profiles. Glucose was transformed into ethanol in all cultures. Monitored experiments carried out with [2-13C]glycine showed differences between infected and uninfected cell cultures spectra. Glycine was partially transformed into serine, but the amount of the serine formed was larger in those infected. Moreover, L-[2-13C]leucine, L-[1-13C]isoleucine and L-[15N]tyrosine were evaluated. No differences among infected and uninfected cells were observed in the metabolic profiles when tyrosine and leucine were monitored. The amino acid L-[1-13C]isoleucine exhibited different metabolism in presence of the R. slovaca, showing a promising behavior as biomarker. In this work we focused on finding one or more compounds that could be metabolized specifically by R. slovaca and could be used as an indicator of its activity.

  4. [sup 31]P NMR study of immobilized artificial membrane surfaces. Structure and dynamics of immobilized phospholipids

    SciTech Connect

    Qiu, X.; Pidgeon, C. )

    1993-11-25

    Chromatography surfaces were prepared by immobilizing a single-chain ether phospholipid at approximately a monolayer density on silica particles. The chromatography particles are denoted as [sup ether]IAM.PC[sup C10/C3], and they are stable to all solvents. The structure and dynamics of the interphase created by immobilizing phospholipids on silica particles were studied by [sup 31]P NMR methods. [sup ether]IAM.PC[sup C10/C3] spontaneously wets when suspended in both aqueous and organic solvents, and [sup 31]P NMR spectra were obtained in water, methanol, chloroform, acetonitrile, and acetone. [sup 31]P NMR spectra were subjected to line-shape analysis. From line-shape analysis, the correlation times for rapid internal motion ([tau]-PLL) and wobbling ([tau]-PRP) of the phospholipid headgroup were calculated for each solvent. Immobilized phospholipid headgroups comprising the IAM interfacial region undergo rapid reorientation similar to the case of the phospholipids forming liposome membranes with [tau]-PLL approximately 1 ns. Phospholipids in liposome membranes exhibit slower wobbling motion ([tau]-PRP approximately 1 ms) in the plane of the membrane. However, the immobilized phospholipids on [sup ether]IAM.PC[sup C10/C3] surfaces wobble with correlation times [tau]-PRP that depend on the solvent bathing the [sup ether]IAM.PC[sup C10/C3] surface. 41 refs., 9 figs., 2 tabs.

  5. Solid-State NMR Studies Reveal Native-like β-Sheet Structures in Transthyretin Amyloid.

    PubMed

    Lim, Kwang Hun; Dasari, Anvesh K R; Hung, Ivan; Gan, Zhehong; Kelly, Jeffery W; Wright, Peter E; Wemmer, David E

    2016-09-20

    Structural characterization of amyloid rich in cross-β structures is crucial for unraveling the molecular basis of protein misfolding and amyloid formation associated with a wide range of human disorders. Elucidation of the β-sheet structure in noncrystalline amyloid has, however, remained an enormous challenge. Here we report structural analyses of the β-sheet structure in a full-length transthyretin amyloid using solid-state NMR spectroscopy. Magic-angle-spinning (MAS) solid-state NMR was employed to investigate native-like β-sheet structures in the amyloid state using selective labeling schemes for more efficient solid-state NMR studies. Analyses of extensive long-range (13)C-(13)C correlation MAS spectra obtained with selectively (13)CO- and (13)Cα-labeled TTR reveal that the two main β-structures in the native state, the CBEF and DAGH β-sheets, remain intact after amyloid formation. The tertiary structural information would be of great use for examining the quaternary structure of TTR amyloid. PMID:27589034

  6. Intrinsic Proton NMR Studies of Mg(OH)2 and Ca(OH)2

    NASA Astrophysics Data System (ADS)

    Itoh, Yutaka; Isobe, Masahiko

    2016-09-01

    We studied the short proton free induction decay signals and the broad 1H NMR spectra of Mg(OH)2 and Ca(OH)2 powders at 77-355 K and 42 MHz using pulsed NMR techniques. Using a Gaussian-type back extrapolation procedure for the obscured data of the proton free induction decay signals, we obtained more precise values of the second moments of the Fourier-transformed broad NMR spectra than those in a previous report [Y. Itoh and M. Isobe, http://doi.org/10.7566/JPSJ.84.113601, J. Phys. Soc. Jpn. 84, 113601 (2015)] and compared with the theoretical second moments. The decrease in the second moment could not account for the large decrease in the magnitude of the intrinsic proton spin-lattice relaxation rate 1/T1 from Mg(OH)2 to Ca(OH)2. The analysis of 1/T1 ∝ exp(-Eg/kBT) with Eg ˜ 0.01 eV points to a local hopping mechanism, and that of 1/T1 ∝ Tn with n ˜ 0.5 points to an anharmonic rattling mechanism.

  7. Molecular ordering of mixed surfactants in mesoporous silicas: A solid-state NMR study

    SciTech Connect

    Kobayashi, Takeshi; Mao, Kanmi; Wang, Shy-Guey; Lin, Victor S.-Y.; Pruski, Marek

    2011-02-17

    The use of mixed surfactants in the synthesis of mesoporous silica nanoparticles (MSNs) is of importance in the context of adjusting pore structures, sizes and morphologies. In the present study, the arrangement of molecules in micelles produced from a mixture of two surfactants, cetyltrimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPB) was detailed by solid-state NMR spectroscopy. Proximities of methyl protons in the trimethylammonium headgroup of CTAB and protons in the pyridinium headgroup of CPB were observed under fast magic angle spinning (MAS) by {sup 1}H-{sup 1}H double quantum (DQ) MAS NMR and NOESY. This result suggested that CTAB and CPB co-exist in the pores without forming significant monocomponent domain structures. {sup 1}H-{sup 29}Si heteronuclear correlation (HETCOR) NMR showed that protons in the headgroups of CTAB are in closer proximity to the silica surface than those in the CPB headgroups. The structural information obtained in this investigation leads to better understanding of the mechanisms of self-assembly and their role in determining the structure and morphology of mesoporous materials.

  8. A 140 GHz Pulsed EPR/212 MHz NMR Spectrometer for DNP Studies

    PubMed Central

    Smith, Albert A.; Corzilius, Björn; Bryant, Jeffrey A.; DeRocher, Ronald; Woskov, Paul P.; Temkin, Richard J.; Griffin, Robert G.

    2012-01-01

    We described a versatile spectrometer designed for the study of dynamic nuclear polarization (DNP) at low temperatures and high fields. The instrument functions both as an NMR spectrometer operating at 212 MHz (1H frequency) with DNP capabilities, and as a pulsed-EPR operating at 140 GHz. A coiled TE011 resonator acts as both an NMR coil and microwave resonator, and a double balanced (1H, 13C) radio frequency circuit greatly stabilizes the NMR performance. A new 140 GHz microwave bridge has also been developed, which utilizes a four-phase network and ELDOR channel at 8.75 GHz, that is then multiplied and mixed to obtain 140 GHz microwave pulses with an output power of 120 mW. Nutation frequencies obtained are as follows: 6 MHz on S = ½ electron spins, 100 kHz on 1H, and 50 kHz on 13C. We demonstrate basic EPR, ELDOR, ENDOR, and DNP experiments here. Our solid effect DNP results demonstrate an enhancement of 144 and sensitivity gain of 310 using OX063 trityl at 80 K and an enhancement of 157 and maximum sensitivity gain of 234 using Gd-DOTA at 20 K, which is significantly better performance than previously reported at high fields (>3 T). PMID:22975246

  9. NMR studies of methanol transport in membranes for fuel cell applications.

    SciTech Connect

    Every, H. A.; Zawodzinski, T. A. , Jr.

    2001-01-01

    Characterization of the methanol diffusion process in Nafion 117 was achieved with the use of a modified pulsed field gradient NMR technique. To ensure that the concentration of methanol was constant throughout the entire experiment, the membrane was continually immersed in the methanol solution. When using the standard pulsed field gradient NMR method, the diffusion of the methanol in the membrane is strongly influenced by the diffusion of methanol in solution. Application of a filter gradient suppresses the signal from the methanol in solution, enabling the methanol diffusion in the membrane to be observed unambiguously. Complete suppression of the solution signal was achieved when a 60% filter gradient was employed. Under such circumstances, the coefficient for diffusion of methanol within the membrane was calculated to be 4x10-6cm2s-1, which is similar to the values reported in the literature. Consequently, the use of NMR filter gradient measurements is a valid method for studying the diffusion coefficient of methanol within fuel cell membranes.

  10. A 140 GHz pulsed EPR/212 MHz NMR spectrometer for DNP studies

    NASA Astrophysics Data System (ADS)

    Smith, Albert A.; Corzilius, Björn; Bryant, Jeffrey A.; DeRocher, Ronald; Woskov, Paul P.; Temkin, Richard J.; Griffin, Robert G.

    2012-10-01

    We described a versatile spectrometer designed for the study of dynamic nuclear polarization (DNP) at low temperatures and high fields. The instrument functions both as an NMR spectrometer operating at 212 MHz (1H frequency) with DNP capabilities, and as a pulsed-EPR operating at 140 GHz. A coiled TE011 resonator acts as both an NMR coil and microwave resonator, and a double balanced (1H, 13C) radio frequency circuit greatly stabilizes the NMR performance. A new 140 GHz microwave bridge has also been developed, which utilizes a four-phase network and ELDOR channel at 8.75 GHz, that is then multiplied and mixed to obtain 140 GHz microwave pulses with an output power of 120 mW. Nutation frequencies obtained are as follows: 6 MHz on S = 1/2 electron spins, 100 kHz on 1H, and 50 kHz on 13C. We demonstrate basic EPR, ELDOR, ENDOR, and DNP experiments here. Our solid effect DNP results demonstrate an enhancement of 144 and sensitivity gain of 310 using OX063 trityl at 80 K and an enhancement of 157 and maximum sensitivity gain of 234 using Gd-DOTA at 20 K, which is significantly better performance than previously reported at high fields (⩾3 T).

  11. Topotecan dynamics, tautomerism and reactivity--1H/13C NMR and ESI MS study.

    PubMed

    Hyz, Karolina; Kawecki, Robert; Bednarek, Elzbieta; Bocian, Wojciech; Sitkowski, Jerzy; Kozerski, Lech

    2010-08-01

    Topotecan (TPT) is in clinical use as an antitumor agent, hycamtin. Because of this, it requires both biologically and chemically useful information to be available. TPT acts by binding to the covalent complex formed by nicked DNA and topoisomerase I. This has a poisonous effect since inserted into the single-strand nick and TPT inhibits its religation. We used NMR to trace TPT dynamics, tautomerism and solvolysis products in various solvents and conditions. Chemical stability was assessed in methanol and DMSO as compared to water, and the regioselectivity of the N- and O-methylation was studied using various alkylating agents. The reaction products of quaternization of the nitrogen atom and methylation of the oxygen atom were characterized by means of ESI MS, (1)H/(13)C-HMBC and -HSQCAD NMR. We have focused on the NMR characterization of TPT with an anticipation that its aggregation, tumbling properties and the intramolecular dipolar interactions will be a common feature for other compounds described in this article. These features can also be useful in tracing the interactions of this class of topoisomerase I (TopoI) poisons with DNA. Moreover, the results explained shed light on the recently disclosed problem of lack of stability of TPT in the heart tissue homogenate samples using the analytical assays developed for this class of compounds carried out in the presence of methanol. PMID:20623719

  12. Solid-state NMR study and assignments of the KcsA potassium ion channel of S. lividans.

    PubMed

    Varga, Krisztina; Tian, Lin; McDermott, Ann E

    2007-12-01

    The extraordinary efficiency and selectivity of potassium channels have made them ideal systems for biophysical and functional studies of ion conduction. We carried out solid-state NMR studies of the selectivity filter region of the protein. Partial site-specific assignments of the NMR signals were obtained based on high field multidimensional solid-state NMR spectra of uniformly (13)C, (15)N enriched KcsA potassium channel from Streptomyces lividans. Both backbone and sidechain atoms were assigned for residues V76-D80 and P83-L90, in and near the selectivity filter region of the protein; this region exhibits good dispersion and useful chemical shift fingerprints. This study will enable structure, dynamic and mechanistic studies of ion conduction by NMR.

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

    PubMed

    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.

  14. Heteronuclear NMR studies of cobalamins. 11. sup 15 N NMR studies of the axial nucleotide and amide side chains of cyanocobalamin and dicyanocobamides

    SciTech Connect

    Brown, K.; Brooks, H.B.; Xiang, Zou ); Victor, M.; Ray, A. ); Timkovich, R. )

    1990-11-28

    Spectroscopic and thermodynamic evidence for the structure of cobalamines and dicyanocobalamin (CN){sub 2}Cbl have been previously reported. The structure indicated the occurrence of the so-called tuck-in species. Further observations and characterization of the tuck-in species of (CN){sub 2}Cbl by {sup 15}N NMR spectroscopy are presented herein. These results represent the first observation of the {sup 15}N NMR spectrum of benzimidazole nucleotide of cobalamins. The first NMR observation of the amide protons of cobalamins and their connectivity to the amide nitrogens are also reported. 50 refs., 2 figs., 2 tabs.

  15. Xenon NMR of liquid crystals confined to cylindrical nanocavities: a simulation study.

    PubMed

    Karjalainen, Jouni; Vaara, Juha; Straka, Michal; Lantto, Perttu

    2015-03-21

    independent of temperature. Our results show that the combination of CG simulations and a QC pre-parameterised (129)Xe NMR shielding allows efficient studies of the phase behaviour and structure of complex systems containing thousands of molecules, and brings us closer to the simulation of NMR experiments. PMID:25690809

  16. NQR-NMR studies of higher alcohol synthesis Cu-Co catalysts. Final technical progress report

    SciTech Connect

    Murty, A.N.

    1995-03-10

    In recent years, due to the many technical advantages of using alcohol-gasoline blends, various processes for the production of higher alcohols from synthesis gas have been studied. The intent of this project is to conduct a comprehensive investigation into the nature of the electronic charge distribution in the vicinity of copper and cobalt nuclei in selected higher alcohol synthesis catalyst systems. Any strong perturbation in the orbital electronic charge distribution of Cu and Co is expected to sensitively influence both their catalytic properties and magnetic characteristics. The NMR and magnetic characterization studies undertaken in this investigation attempt to provide a better understanding of the correlation between magnetic and catalytic properties.

  17. The aluminium effect on the structure of silico-phosphate glasses studied by NMR and FTIR

    NASA Astrophysics Data System (ADS)

    Sitarz, Maciej; Fojud, Zbigniew; Olejniczak, Zbigniew

    2009-04-01

    Silico-phosphate glasses of NaCaPO 4-SiO 2 and NaCaPO 4-AlPO 4-SiO 2 system have been the subject of the presented investigations. Glasses of these systems are the basis for the preparation of glassy-crystalline biomaterials [R.D. Rawlings, Clin. Mater. 14 (1993) 155]. Detailed knowledge of the precursor glass structure is necessary for proper design of the glassy-crystalline biomaterials preparation procedure. Since there is no long-range ordering in glasses, spectroscopic methods which make it possible to study the short range ordering should be applied. MIR studies carried out in the work have allowed to establish that the glasses of the systems studied show domain composition [L.L. Hench, R.J. Splinter, T.K. Greenlee, W.C. Allen, J. Biol. Res. Symp. 2 (1971) 117; L.L. Hench, R.J. Splinter, W.C. Allen, T.K. Greenlee, J. Biol. Res. 5 (1972) 117]. Domain structure is close to that of the corresponding crystalline phases. It has been shown that even small amount of aluminium in the glass (5 mol.% of AlPO 4) significantly influences both, its texture (microscopic and EDX studies) and its structure (spectroscopic studies). 27Al NMR investigations have made it possible to establish unequivocally that aluminium occurs exclusively in tetrahedral coordination, i.e. it is involved in the formation of glass framework. Presence of aluminium results in significant changes in the [SiO 4] 4- and [PO 4] 3- tetrahedra environment which is reflected in 23Na, 31P and 29Si NMR spectra. Changes in the shapes and positions of the bands in the NMR spectra of glasses belonging to the NaCaPO 4-AlPO 4-SiO 2 system confirm great influence of aluminium on silico-phosphate glasses structure.

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

    PubMed

    Avram, Liat; Goldbourt, Amir; Cohen, Yoram

    2016-01-18

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

  19. Applications of carbon-13 and sodium-23 NMR in the study of plants, animal, and human cells

    SciTech Connect

    Sillerud, L.O.; Heyser, J.W.; Han, C.H.; Bitensky, M.W.

    1984-01-01

    Carbon-13 and sodium-23 NMR have been applied to the study of a variety of plant, animal and human cell types. Sodium NMR, in combination with dysprosium shift reagents, has been used to monitor sodium transport kinetics in salt-adapted, and non-adapted cells of P. milliaceum and whole D. spicata plants. The sodium content of human erythrocytes and leukemic macrophages was measured. Carbon-13 NMR was used to determine the structure and metabolism of rat epididymal fat pad adipocytes in real time. Insulin and isoproterenol-stimulated triacylglycerol turnover could be monitored in fat cell suspensions. (1-/sup 13/C) glucose was used as a substrate to demonstrate futile metabolic cycling from glucose to glycerol during lypolysis. Cell wall polysaccharide synthesis was followed in suspensions of P. milliaceum cells using (1-/sup 13/C) glucose as a precursor. These results illustrate the wide range of living systems which are amenable to study with NMR. 14 refs., 21 figs.

  20. Pulsed field gradient MAS-NMR studies of the mobility of carboplatin in cubic liquid-crystalline phases

    NASA Astrophysics Data System (ADS)

    Pampel, André; Michel, Dieter; Reszka, Regina

    2002-05-01

    A drug delivery system with cubic liquid-crystalline phase structure (cubic phase) containing the anti-cancer drug Carboplatin is studied. It is demonstrated that the combination of pulsed field gradient (PFG) NMR and MAS-NMR is a useful tool to study the biophysical properties of a cubic phase. The linewidth in 1H-NMR spectra is narrowed by MAS, which can be exploited to perform PFG diffusion NMR experiments under high-resolution conditions. Measurement of self-diffusion coefficients of all components of the cubic phase becomes possible. The influence of polyethylene glycol chains on the drug mobility is discussed. It is shown that polyethylene glycol chains interact with Carboplatin.

  1. NMR STUDIES OF LIQUID CRYSTALS AND MOLECULES DISSOLVED IN LIQUID CRYSTAL SOLVENTS

    SciTech Connect

    Drobny, G.P.

    1982-11-01

    This thesis describes several studies in which nuclear magnetic resonance (nmr) spectroscopy has been used to probe the structure, orientation and dynamics of liquid crystal mesogens and molecules dissolved in liquid crystalline phases. In addition, a modern high field nmr spectrometer is described which has been used to perform such nmr studies. Chapter 1 introduces the quantum mechanical formalisms used throughout this thesis and briefly reviews the fundamentals of nuclear spin physics and pulsed nmr spectroscopy. First the density operator is described and a specific form for the canonical ensemble is derived. Then Clebsch-Gordon coefficients, Wigner rotation matrices, and irreducible tensor operators are reviewed. An expression for the equilibrium (Curie) magnetization is obtained and the linear response of a spin system to a strong pulsed r.f. irradiation is described. Finally, the spin interaction Hamiltonians relevant to this work are reviewed together with their truncated forms. Chapter 2 is a deuterium magnetic resonance study of two 'nom' liquid crystals which possess several low temperature mesomorphic phases. Specifically, deuterium quadrupolar echo spectroscopy is used to determine the orientation of the liquid crystal molecules in smectic phases, the changes in molecular orientation and motion that occur at smectic-smectic phase transitions, and the order of the phase transitions. For both compounds, the phase sequence is determined to be isotropic, nematic, smectic A, smectic C, smectic B{sub A}, smectic B{sub C}, and crystalline. The structure of the smectic A phase is found to be consistent with the well-known model of a two dimensional liquid in which molecules are rapidly rotating about their long axes and oriented at right angles to the plane of the layers. Molecules in the smectic C phase are found to have their long axes tilted with respect to the layer normal, and the tilt angle is temperature dependent, increasing from zero at the smectic A

  2. Conformations of a model cyclic hexapeptide, CYIQNC: (1)H-NMR and molecular dynamics studies.

    PubMed

    Kulkarni, Ashok Kumar; Ojha, Rajendra Prasad

    2015-09-01

    Solution conformation of the cyclic hexapeptide sequence, [cyclo-S-Cys-Tyr-Ile-Gln-Asn-Cys-S] (CYIQNC) - a disulfide-linked fragment of a neurohypophyseal peptide hormone oxytocin (OT) - has been investigated by high-field one-dimensional (1D) and two-dimensional (2D) NMR spectroscopic methods and compared with the results obtained from computer simulation studies. (1)H-NMR results based on temperature dependence of amide proton chemical shifts and nuclear Overhauser effect indicate that peptide in solution populates different conformations, characterized by two fused β-turns. The segment Ile(3)-Gln(4)-Asn(5)-Cys(6) yields a preferred type-III β-turn at residues 4, 5 (HB, 3HN → 6CO), while the segment Cys(6), Cys(1)-Tyr(2)-Ile(3) exhibits inherently weaker, flexible β-turn either of type I/II'/III/half-turn at residues 1, 2 (HB, 6HN → 3CO). The computer simulation studies using a mixed protocol of distance geometry-simulated annealing followed by constrained minimization, restrained molecular dynamics, and energy minimization showed the possibility of existence of additional conformations with the hydrogen bonds, (a) 5HN → 3CO and (b) 2HN → 6CO. These results, therefore, indicate that the additional conformations obtained from both NMR and simulation studies can also be possible to the peptide. These additional conformations might have very small population in the solution and did not show their signatures in these conditions. These findings will be helpful in designing more analogs with modifications in the cyclic moiety of OT.

  3. Conformations of a model cyclic hexapeptide, CYIQNC: (1)H-NMR and molecular dynamics studies.

    PubMed

    Kulkarni, Ashok Kumar; Ojha, Rajendra Prasad

    2015-09-01

    Solution conformation of the cyclic hexapeptide sequence, [cyclo-S-Cys-Tyr-Ile-Gln-Asn-Cys-S] (CYIQNC) - a disulfide-linked fragment of a neurohypophyseal peptide hormone oxytocin (OT) - has been investigated by high-field one-dimensional (1D) and two-dimensional (2D) NMR spectroscopic methods and compared with the results obtained from computer simulation studies. (1)H-NMR results based on temperature dependence of amide proton chemical shifts and nuclear Overhauser effect indicate that peptide in solution populates different conformations, characterized by two fused β-turns. The segment Ile(3)-Gln(4)-Asn(5)-Cys(6) yields a preferred type-III β-turn at residues 4, 5 (HB, 3HN → 6CO), while the segment Cys(6), Cys(1)-Tyr(2)-Ile(3) exhibits inherently weaker, flexible β-turn either of type I/II'/III/half-turn at residues 1, 2 (HB, 6HN → 3CO). The computer simulation studies using a mixed protocol of distance geometry-simulated annealing followed by constrained minimization, restrained molecular dynamics, and energy minimization showed the possibility of existence of additional conformations with the hydrogen bonds, (a) 5HN → 3CO and (b) 2HN → 6CO. These results, therefore, indicate that the additional conformations obtained from both NMR and simulation studies can also be possible to the peptide. These additional conformations might have very small population in the solution and did not show their signatures in these conditions. These findings will be helpful in designing more analogs with modifications in the cyclic moiety of OT. PMID:25375824

  4. Study of comparative transmission capacity of C-N bond by /sup 19/F NMR method

    SciTech Connect

    Pombrik, S.I.; Polunkin, E.V.; Peregudov, A.S.; Kravtsov, D.N.; Fedin, E.I.

    1982-04-20

    A study was made of the /sup 19/F NMR spectra of a number of free and N-substituted benzylanilines ArCH/sub 2/NHC/sub 6/H/sub 4/F-4 and ArCH/sub 2/N(SO/sub 2/Ph)C/sub 6/H/sub 4/F, respectively. Results indicated that the binuclear bridge grouping CH/sub 2/-N has a high transmission capacity (TC). The addition of an acidic grouping the nitrogen atom has no effect on the TC of the C-N bond.

  5. The extracellular polysaccharide of Porphyridium sp.: an NMR study of lithium-resistant oligosaccharidic fragments.

    PubMed

    Gloaguen, Vincent; Ruiz, Gaël; Morvan, Henri; Mouradi-Givernaud, Aziza; Maes, Emmanuel; Krausz, Pierre; Strecker, Gérard

    2004-01-01

    This study deals with the chemical characterization of an extracellular polysaccharide produced by the unicellular red alga Porphyridium sp. The sugar moiety of this polymer is composed of three neutral monosaccharides (Xyl, Glc, and Gal) and one uronic acid (GlcA). Proteins represent 5.5% of the dry weight of the polymer. Uronic degradation of this exopolysaccharide with lithium in ethylenediamine yielded two different oligosaccharides. The absolute configuration of the constitutive monosaccharides was chemically determined and revealed the presence of D-Xyl, D-Glc, D-, and L-Gal. The following oligosaccharide structures were established by NMR spectroscopy: [carbohydrate structure: see text].

  6. Xenon-129 NMR study of the microporous structure of clays and pillared clays

    SciTech Connect

    Tsiao, C.; Carrado, K.A.

    1990-01-01

    {sup 129}Xe NMR studies have been carried out using xenon gas adsorbed in clays and pillared clays. Data from the measurements provide information on the pore structure of clays before and after pillaring. The results indicate that the effective pore diameter of montmorillonite increases, for example, from 5.4 {Angstrom} to 8.0 {Angstrom} after pillaring cheto-montmorillonite with aluminum polyoxohydroxy Keggin cations. The data are consistent with X-ray powder diffraction results, which show a corresponding increase in the interlamellar gallery height from 5.6 {Angstrom} to 8.4 {Angstrom}.

  7. Solid-state NMR studies of the dynamics and structure of mouse keratin intermediate filaments

    SciTech Connect

    Mack, J.W.; Torchia, D.A.; Steinert, P.M.

    1988-07-26

    The molecular dynamics and structural organization of mouse epidermal keratin intermediate filaments (IF) have been studied via solid-state nuclear magnetic resonance (NMR) experiments performed on IF labeled both in vivo and in vitro with isotopically enriched amino acids. As a probe of the organization of the peripheral glycine-rich end domains of the IF, carbon-13 NMR experiments have been performed on subfilamentous forms (prekeratin) and on IF reassembled in vitro that had been labeled with either (1-/sup 13/C)glycine or (2-/sup 13/C)glycine, as more than 90% of the glycines of the keratins are located in the end domains. Measurements of carbon relaxation times, nuclear Overhauser enhancements, and signal intensities show that the motions of the peptide backbone in the end domains are effectively isotropic. These results indicate that the end domains of IF are remarkably flexible and have little or no structural order. To probe the structural organization of the coiled-coil rod domains of the IF, separate samples of native keratin IF, raised in primary tissue culture, were labeled with L-(1-/sup 13/C)leucine, L-(/sup 2/H/sub 10/)leucine, or L-(2,3,3-/sup 2/H/sub 3/)leucine, as greater than 90% of the leucyl residues of the keratin IF types studied are located in the coiled coils which form the central core of IF. Deuterium NMR experiments performed on IF labeled with deuteriated leucines indeed reveal a marked degree of peptide backbone rigidity within the coiled coils, confirming the initial conclusions of the carbon-13 data. These data, demonstrating relative peptide backbone rigidity yet side-chain flexibility, are interpreted to mean that the coiled coils of these keratin IF are not tightly packed together but rather form a somewhat looser structure which permits a significant degree of side-chain mobility.

  8. A stable amorphous statin: solid-state NMR and dielectric studies on dynamic heterogeneity of simvastatin.

    PubMed

    Nunes, Teresa G; Viciosa, M Teresa; Correia, Natália T; Danède, F; Nunes, Rita G; Diogo, Hermínio P

    2014-03-01

    Statins have been widely used as cholesterol-lowering agents. However, low aqueous solubility of crystalline statins and, consequently, reduced biovailability require seeking for alternative forms and formulations to ensure an accurate therapeutic window. The objective of the present study was to evaluate the stability of amorphous simvastatin by probing molecular dynamics using two nondestructive techniques: solid-state NMR and dielectric relaxation spectroscopy. Glassy simvastatin was obtained by the melt quench technique. (13)C cross-polarization/magic-angle-spinning (CP/MAS) NMR spectra and (1)H MAS NMR spectra were obtained from 293 K up to 333 K (Tg ≈ 302 K). The (13)C spin-lattice relaxation times in the rotating frame, T1ρ, were measured as a function of temperature, and the correlation time and activation energy data obtained for local motions in different frequency scales revealed strong dynamic heterogeneity, which appears to be essential for the stability of the amorphous form of simvastatin. In addition, the (1)H MAS measurements presented evidence for mobility of the hydrogen atoms in hydroxyl groups which was assigned to noncooperative secondary relaxations. The complex dielectric permittivity of simvastatin was monitored in isochronal mode at five frequencies (from 0.1 to 1000 kHz), by carrying out a heating/cooling cycle allowing to obtain simvastatin in the supercooled and glassy states. The results showed that no dipolar moment was lost due to immobilization, thus confirming that no crystallization had taken place. Complementarily, the present study focused on the thermal stability of simvastatin using thermogravimetric analysis while the thermal events were followed up by differential scanning calorimetry and dielectric relaxation spectroscopy. Overall, the results confirm that the simvastatin in the glass form reveals a potential use in the solid phase formulation on the pharmaceutical industry.

  9. UV-visible and (1)H-(15)N NMR spectroscopic studies of colorimetric thiosemicarbazide anion sensors.

    PubMed

    Farrugia, Kristina N; Makuc, Damjan; Podborska, Agnieszka; Szaciłowski, Konrad; Plavec, Janez; Magri, David C

    2015-02-14

    Four model thiosemicarbazide anion chemosensors containing three N-H bonds, substituted with phenyl and/or 4-nitrophenyl units, were synthesised and studied for their anion binding abilities with hydroxide, fluoride, acetate, dihydrogen phosphate and chloride. The anion binding properties were studied in DMSO and 9 : 1 DMSO-H2O by UV-visible absorption and (1)H/(13)C/(15)N NMR spectroscopic techniques and corroborated with DFT studies. Significant changes were observed in the UV-visible absorption spectra with all anions, except for chloride, accompanied by dramatic colour changes visible to the naked eye. These changes were determined to be due to the deprotonation of the central N-H proton and not due to hydrogen bonding based on (1)H/(15)N NMR titration studies with acetate in DMSO-d6-0.5% water. Direct evidence for deprotonation was confirmed by the disappearance of the central thiourea proton and the formation of acetic acid. DFT and charge distribution calculations suggest that for all four compounds the central N-H proton is the most acidic. Hence, the anion chemosensors operate by a deprotonation mechanism of the central N-H proton rather than by hydrogen bonding as is often reported. PMID:25451865

  10. Solid-state NMR studies of proteins immobilized on inorganic surfaces

    DOE PAGES

    Shaw, Wendy J.

    2014-10-29

    Solid state NMR is the primary tool for studying the quantitative, site-specific structure, orientation, and dynamics of biomineralization proteins under biologically relevant conditions. Two calcium phosphate proteins, statherin and leucine rich amelogenin protein (LRAP), have been studied in depth and have different features, challenging our ability to extract design principles. More recent studies of the significantly larger full-length amelogenin represent a challenging but necessary step to ultimately investigate the full diversity of biomineralization proteins. Interactions of amino acids and silaffin peptide with silica are also being studied, along with qualitative studies of proteins interacting with calcium carbonate. Dipolar recoupling techniquesmore » have formed the core of the quantitative studies, yet, the need for isolated spin pairs makes this approach costly and time intensive. The use of multi-dimensional techniques is advancing, methodology which, despite its challenges with these difficult-to-study proteins, will continue to drive future advancements in this area.« less

  11. Solid-state NMR studies of proteins immobilized on inorganic surfaces

    SciTech Connect

    Shaw, Wendy J.

    2014-10-29

    Solid state NMR is the primary tool for studying the quantitative, site-specific structure, orientation, and dynamics of biomineralization proteins under biologically relevant conditions. Two calcium phosphate proteins, statherin and leucine rich amelogenin protein (LRAP), have been studied in depth and have different features, challenging our ability to extract design principles. More recent studies of the significantly larger full-length amelogenin represent a challenging but necessary step to ultimately investigate the full diversity of biomineralization proteins. Interactions of amino acids and silaffin peptide with silica are also being studied, along with qualitative studies of proteins interacting with calcium carbonate. Dipolar recoupling techniques have formed the core of the quantitative studies, yet, the need for isolated spin pairs makes this approach costly and time intensive. The use of multi-dimensional techniques is advancing, methodology which, despite its challenges with these difficult-to-study proteins, will continue to drive future advancements in this area.

  12. Intracellular water in Artemia cysts (brine shrimp): Investigations by deuterium and oxygen-17 nuclear magnetic resonance.

    PubMed

    Kasturi, S R; Seitz, P K; Chang, D C; Hazlewood, C F

    1990-08-01

    The dormant cysts of Artemia undergo cycles of hydration-dehydration without losing viability. Therefore, Artemia cysts serve as an excellent intact cellular system for studying the dynamics of water-protein interactions as a function of hydration. Deuterium spin-lattice (T(1)) and spin-spin (T(2)) relaxation times of water in cysts hydrated with D(2)O have been measured for hydrations between 1.5 and 0.1 g of D(2)O per gram of dry solids. When the relaxation rates (I/T(1), I/T(2)) of (2)H and (17)O are plotted as a function of the reciprocal of hydration (1/H), an abrupt change in slope is observed near 0.6 g of D(2)O (or H(2) (17)O)/gram of dry solids, the hydration at which conventional metabolism is activated in this system. The results have been discussed in terms of the two-site and multisite exchange models for the water-protein interaction as well as protein dynamics models. The (2)H and (17)O relaxation rates as a function of hydration show striking similarities to those observed for anisotropic motion of water molecules in protein crystals.It is suggested here that although the simple two-site exchange model or n-site exchange model could be used to explain our data at high hydration levels, such models are not adequate at low hydration levels (<0.6 g H(2)O/g) where several complex interactions between water and proteins play a predominant role in the relaxation of water nuclei. We further suggest that the abrupt change in the slope of I/T(1) as a function of hydration in the vicinity of 0.6 g H(2)O/g is due to a change in water-protein interactions resulting from a variation in the dynamics of protein motion. PMID:19431762

  13. Structural studies of bacterial transcriptional regulatory proteins by multidimensional heteronuclear NMR

    SciTech Connect

    Volkman, B.F.

    1995-02-01

    Nuclear magnetic resonance spectroscopy was used to elucidate detailed structural information for peptide and protein molecules. A small peptide was designed and synthesized, and its three-dimensional structure was calculated using distance information derived from two-dimensional NMR measurements. The peptide was used to induce antibodies in mice, and the cross-reactivity of the antibodies with a related protein was analyzed with enzyme-linked immunosorbent assays. Two proteins which are involved in regulation of transcription in bacteria were also studied. The ferric uptake regulation (Fur) protein is a metal-dependent repressor which controls iron uptake in bacteria. Two- and three-dimensional NMR techniques, coupled with uniform and selective isotope labeling allowed the nearly complete assignment of the resonances of the metal-binding domain of the Fur protein. NTRC is a transcriptional enhancer binding protein whose N-terminal domain is a {open_quote}receiver domain{close_quote} in the family of {open_quote}two-component{close_quote} regulatory systems. Phosphorylation of the N-terminal domain of NTRC activates the initiation of transcription of aeries encoding proteins involved in nitrogen regulation. Three- and four-dimensional NMR spectroscopy methods have been used to complete the resonance assignments and determine the solution structure of the N-terminal receiver domain of the NTRC protein. Comparison of the solution structure of the NTRC receiver domain with the crystal structures of the homologous protein CheY reveals a very similar fold, with the only significant difference being the position of helix 4 relative to the rest of the protein. The determination of the structure of the NTRC receiver domain is the first step toward understanding a mechanism of signal transduction which is common to many bacterial regulatory systems.

  14. Local electromagnetic properties of magnetic pnictides: a comparative study probed by NMR measurements.

    PubMed

    Majumder, M; Ghoshray, K; Ghoshray, A; Pal, A; Awana, V P S

    2013-05-15

    (75)As and (31)P NMR studies are performed in PrCoAsO and NdCoPO respectively. The Knight shift data in PrCoAsO indicate the presence of an antiferromagnetic interaction between the 4f moments along the c axis in the ferromagnetic state of Co 3d moments. We propose a possible spin structure in this system. The (75)As quadrupolar coupling constant, νQ, increases continuously with decrease of temperature and is found to vary linearly with the intrinsic spin susceptibility, K(iso). This indicates the possibility of the presence of a coupling between charge density and spin density fluctuations. Further, the (31)P NMR Knight shift and spin-lattice relaxation rate (1/T1) in the paramagnetic state of NdCoPO indicate that the differences of LaCoPO and NdCoPO from SmCoPO are due to the decrement of the interlayer separation and not due to the moments of the 4f electrons. The nuclear spin-lattice relaxation time (T1) in NdCoPO shows weak anisotropy at 300 K. Using the self-consistent renormalization (SCR) theory of itinerant ferromagnets, it is shown that in the ab plane, the spin fluctuations are three-dimensional ferromagnetic in nature. From SCR theory the important spin-fluctuation parameters (T0, TA, F¯1) are evaluated. The similarities and dissimilarities of the NMR results in As and P based systems with different rare earths are also discussed. PMID:23604391

  15. Optimizing nanodiscs and bicelles for solution NMR studies of two β-barrel membrane proteins

    PubMed Central

    Kucharska, Iga; Edrington, Thomas C.; Liang, Binyong

    2015-01-01

    Solution NMR spectroscopy has become a robust method to determine structures and explore the dynamics of integral membrane proteins. The vast majority of previous studies on membrane proteins by solution NMR have been conducted in lipid micelles. Contrary to the lipids that form a lipid bilayer in biological membranes, micellar lipids typically contain only a single hydrocarbon chain or two chains that are too short to form a bilayer. Therefore, there is a need to explore alternative more bilayer-like media to mimic the natural environment of membrane proteins. Lipid bicelles and lipid nanodiscs have emerged as two alternative membrane mimetics that are compatible with solution NMR spectroscopy. Here, we have conducted a comprehensive comparison of the physical and spectroscopic behavior of two outer membrane proteins from Pseudomonas aeruginosa, OprG and OprH, in lipid micelles, bicelles, and nanodiscs of five different sizes. Bicelles stabilized with a fraction of negatively charged lipids yielded spectra of almost comparable quality as in the best micellar solutions and the secondary structures were found to be almost indistinguishable in the two environments. Of the five nanodiscs tested, nanodiscs assembled from MSP1D1ΔH5 performed the best with both proteins in terms of sample stability and spectral resolution. Even in these optimal nanodiscs some broad signals from the membrane embedded barrel were severely overlapped with sharp signals from the flexible loops making their assignments difficult. A mutant OprH that had two of the flexible loops truncated yielded very promising spectra for further structural and dynamical analysis in MSP1D1ΔH5 nanodiscs. PMID:25869397

  16. Temperature-reversible eruptions of vesicles in model membranes studied by NMR.

    PubMed Central

    Nezil, F A; Bayerl, S; Bloom, M

    1992-01-01

    Deuterium (2H) and phosphorus (31P) nuclear magnetic resonance (NMR) and freeze-fracture electron microscopy were used to study spontaneous vesiculation in model membranes composed of POPC:POPS with or without cholesterol. The NMR spectra indicated the presence of a central isotropic line, the intensity of which is reversibly and linearly dependent upon temperature in the L alpha phase, with no hysteresis when cycling between higher and lower temperatures. Freeze-fracture microscopy showed small, apparently connected vesicles that were only present when the samples were frozen (for freeze-fracture) from an initial temperature of 40-60 degrees C, and absent when the samples are frozen from an initial temperature of 20 degrees C. Analysis of motional narrowing was consistent with the isotropic lines being due to lateral diffusion in (and tumbling of) small vesicles (diameters approximately 50 nm). These results were interpreted in terms of current theories of shape fluctuations in large unilamellar vesicles which predict that small daughter vesicles may spontaneously "erupt" from larger parent vesicles in order to expel the excess area created by thermal expansion of the bilayer surface at constant volume. Assuming that all the increased area due to increasing temperature is associated with the isotropic lines, the NMR results allowed a novel estimate of the coefficient of area expansion alpha A in multilamellar vesicles (MLVs) which is in good agreement with micromechanical measurements upon giant unilamellar vesicles of similar composition. Experiments performed on unilamellar vesicles, which had been placed upon glass beads, confirmed that alpha A determined in this way is unchanged compared with the MLV case. Addition of the highly positively charged (extrinsic) myelin basic protein (MBP) to a POPC:POPS system showed that membrane eruptions of the type described here occur in response to the presence of this protein. Images FIGURE 5 FIGURE 5 FIGURE 5 FIGURE 6

  17. Local electromagnetic properties of magnetic pnictides: a comparative study probed by NMR measurements.

    PubMed

    Majumder, M; Ghoshray, K; Ghoshray, A; Pal, A; Awana, V P S

    2013-05-15

    (75)As and (31)P NMR studies are performed in PrCoAsO and NdCoPO respectively. The Knight shift data in PrCoAsO indicate the presence of an antiferromagnetic interaction between the 4f moments along the c axis in the ferromagnetic state of Co 3d moments. We propose a possible spin structure in this system. The (75)As quadrupolar coupling constant, νQ, increases continuously with decrease of temperature and is found to vary linearly with the intrinsic spin susceptibility, K(iso). This indicates the possibility of the presence of a coupling between charge density and spin density fluctuations. Further, the (31)P NMR Knight shift and spin-lattice relaxation rate (1/T1) in the paramagnetic state of NdCoPO indicate that the differences of LaCoPO and NdCoPO from SmCoPO are due to the decrement of the interlayer separation and not due to the moments of the 4f electrons. The nuclear spin-lattice relaxation time (T1) in NdCoPO shows weak anisotropy at 300 K. Using the self-consistent renormalization (SCR) theory of itinerant ferromagnets, it is shown that in the ab plane, the spin fluctuations are three-dimensional ferromagnetic in nature. From SCR theory the important spin-fluctuation parameters (T0, TA, F¯1) are evaluated. The similarities and dissimilarities of the NMR results in As and P based systems with different rare earths are also discussed.

  18. Solid state NMR and LVSEM studies on the hardening of latex modified tile mortar systems

    SciTech Connect

    Rottstegge, J.; Arnold, M.; Herschke, L.; Glasser, G.; Wilhelm, M.; Spiess, H.W. . E-mail: spiess@mpip-mainz.mpg.de; Hergeth, W.D.

    2005-12-15

    Construction mortars contain a broad variety of both inorganic and organic additives beside the cement powder. Here we present a study of tile mortar systems based on portland cement, quartz, methyl cellulose and different latex additives. As known, the methyl cellulose stabilizes the freshly prepared cement paste, the latex additive enhances final hydrophobicity, flexibility and adhesion. Measurements were performed by solid state nuclear magnetic resonance (NMR) and low voltage scanning electron microscopy (LVSEM) to probe the influence of the latex additives on the hydration, hardening and the final tile mortar properties. While solid state NMR enables monitoring of the bulk composition, scanning electron microscopy affords visualization of particles and textures with respect to their shape and the distribution of the different phases. Within the alkaline cement paste, the poly(vinyl acetate) (VAc)-based latex dispersions stabilized by poly(vinyl alcohol) (PVA) were found to be relatively stable against hydrolysis. The influence of the combined organic additives methyl cellulose, poly(vinyl alcohol) and latexes stabilized by poly(vinyl alcohol) on the final silicate structure of the cement hydration products is small. But even small amounts of additives result in an increased ratio of ettringite to monosulfate within the final hydrated tile mortar as monitored by {sup 27}Al NMR. The latex was found to be adsorbed to the inorganic surfaces, acting as glue to the inorganic components. For similar latex water interfaces built up by poly(vinyl alcohol), a variation in the latex polymer composition results in modified organic textures. In addition to the networks of the inorganic cement and of the latex, there is a weak network build up by thin polymer fibers, most probably originating from poly(vinyl alcohol). Besides the weak network, polymer fibers form well-ordered textures covering inorganic crystals such as portlandite.

  19. Interaction of melittin with mixed phospholipid membranes composed of dimyristoylphosphatidylcholine and dimyristoylphosphatidylserine studied by deuterium NMR

    SciTech Connect

    Dempsey, C.; Bitbol, M.; Watts, A. )

    1989-08-08

    The interaction of bee venom melittin with mixed phospholipid bilayers composed of dimyristoylphosphatidylcholine deuterated in the {alpha}- and {beta}-methylenes of the choline head group (DMPC-d{sub 4}) and dimyristoylphosphatidylserine deuterated in the {alpha}-methylene and {beta}-CH positions of the serine head group (DMPS-d{sub 3}) was studied in ternary mixtures by using deuterium NMR spectroscopy. The changes in the deuterium quadrupole splittings of the head-group deuteriomethylenes of DMPC-d{sub 4} induced by DMPS in binary mixtures were systematically reversed by increasing concentrations of melittin, so that at a melittin concentration of 4 mol % relative to total lipid the deuterium NMR spectrum from DMPC-d{sub 4} in the ternary mixture was similar to the spectrum from pure DMPC-d{sub 4} bilayers. The absence of deuterium NMR signals arising from melittin-bound DMPS in ternary mixtures containing DMPS-d{sub 3} indicates that the reversal by melittin of the effects of DMPS on the quadrupole splittings of DMPC-d{sub 4} results from the response of the choline head group to the net surface charge rather than from phase separation of melittin-DMPS complexes. The similarity in the effects of the two cationic but otherwise dissimilar peptides indicates that the DMPS head group responds to the surface charge resulting from the presence in the bilayer of charged amphiphiles, in a manner analogous to the response of the choline head group of phosphatidylcholine to the bilayer surface charge. The presence of DMPS greatly stabilized DMPC bilayers with respect to melittin-induced micellization, indicating that the latter effect of melittin may not be important for the hemolytic activity of the peptide.

  20. Gas-phase NMR technique for studying the thermolysis of materials: thermal decomposition of ammonium perfluorooctanoate.

    PubMed

    Krusic, Paul J; Roe, D Christopher

    2004-07-01

    The kinetics of the thermal decomposition of ammonium perfluorooctanoate (APFO) has been studied by high-temperature gas-phase nuclear magnetic resonance spectroscopy over the temperature range 196-234 degrees C. We find that APFO cleanly decomposes by first-order kinetics to give the hydrofluorocarbon 1-H-perfluoroheptane and is completely decomposed (>99%) in a matter of minutes at the upper limit of this temperature range. Based on the temperature dependence of the measured rate constants, we find that the enthalpy and entropy of activation are DeltaH++ = 150 +/- 11 kJ mol(-1) and DeltaS++ = 3 +/- 23 J mol(-)(1) deg(-1). These activation parameters may be used to calculate the rate of APFO decomposition at the elevated temperatures (350-400 degrees C) at which fluoropolymers are processed; for example, at 350 degrees C the half-life for APFO is estimated to be less than 0.2 s. Our studies provide the fundamental parameters involved in the decomposition of the ammonium salt of perfluorooctanoic acid and indicate the utility of gas-phase NMR for thermolysis studies of a variety of materials that release compounds that are volatile at the temperature of decomposition and that contain an NMR-active nucleus.

  1. Electronic Properties and 13C NMR Structural Study of Y3N@C88

    PubMed Central

    Fu, Wujun; Zhang, Jianyuan; Champion, Hunter; Fuhrer, Tim; Azuremendi, Hugo; Zuo, Tianming; Zhang, Jianfei; Harich, Kim; Dorn, Harry C.

    2011-01-01

    In this paper we report the synthesis, purification, 13C NMR and other characterization studies of Y3N@C88. The 13C NMR, UV-vis and chromatographic data suggest an Y3N@C88 having IPR allowed cage with D2(35)-C88 symmetry. In earlier density functional theory (DFT) computational and X-ray crystallographic studies, it was reported that lanthanide (A3N)6+ clusters are stabilized in D2(35)-C88 symmetry cages and have reduced HOMO-LUMO gaps relative to other trimetallic nitride endohedral metallofullerene cage systems, for example, A3N@C80. In this paper, we report that the non-lanthanide (Y3N)6+ cluster in the D2(35)-C88 cage exhibits a HOMO-LUMO gap consistent with other lanthanide A3N@C88 molecules based on electrochemical measurements and DFT computational study. These results suggests that the reduced HOMO-LUMO gap of A3N@C88 systems is a property dominated by the D2(35)-C88 carbon cage and not f-orbital lanthanide electronic metal cluster (A3N)6+ orbital participation. PMID:21506556

  2. Solid-state NMR studies of collagen-based parchments and gelatin.

    PubMed

    Aliev, Abil E

    2005-03-01

    Historical collagen-based parchments have been studied by solid-state NMR. In addition, new parchment (produced according to traditional methods) and gelatin from bovine skin were also studied. Wideline 1H and MAS 13C measurements were carried out directly on intact parchments. A simple approach is proposed for evaluation of the extent of parchment degradation based on the linewidth changes in the 13C CPMAS spectra relative to new parchment and gelatin. Structural (bound) water content was estimated from wideline 1H NMR lineshape and relaxation time measurements. It was found that the relative water content in parchments correlates linearly with 13C MAS linewidths. Its decrease on parchment degradation indicates that structural water molecules are of primary importance in stabilizing higher order collagen structures. Backbone and side chain dynamics of collagen in parchments were compared to those of gelatin based on the 13C dipolar-dephased experiments. Carbonyl 13C chemical shift anisotropies were measured to deduce the geometry of the collagen backbone motion. Unlike previous studies, we found that the collagen backbone motion is similar to that found in other proteins and occurs primarily via small-angle librations about internal bond directions.

  3. NMR studies of p7 protein from hepatitis C virus

    PubMed Central

    Cook, Gabriel A.

    2009-01-01

    The p7 protein of hepatitis C virus (HCV) plays an important role in the viral lifecycle. Like other members of the viroporin family of small membrane proteins, the amino acid sequence of p7 is largely conserved over the entire range of genotypes, and it forms ion channels that can be blocked by a number of established channel-blocking compounds. Its characteristics as a membrane protein make it difficult to study by most structural techniques, since it requires the presence of lipids to fold and function properly. Purified p7 can be incorporated into phospholipid bilayers and micelles. Initial solid-state nuclear magnetic resonance (NMR) studies of p7 in 14-O-PC/6-O-PC bicelles indicate that the protein contains helical segments that are tilted approximately 10° and 25° relative to the bilayer normal. A truncated construct corresponding to the second transmembrane domain of p7 is shown to have properties similar to those of the full-length protein, and was used to determine that the helix segment tilted at 10° is in the C-terminal portion of the protein. The addition of the channel blocker amantadine to the full-length protein resulted in selective chemical shift changes, demonstrating that NMR has a potential role in the development of drugs targeted to p7. PMID:19727701

  4. Simulation studies of instrumental artifacts on spin I=1 double quantum filtered NMR spectroscopy

    PubMed Central

    Sun, Cheng; Boutis, Gregory S.

    2010-01-01

    We report on the results of a simulation based study of the effect of various experimental artifacts for spin I=1 double quantum filtered NMR. The simulation captures the effects of static field inhomogeneity, finite pulse widths, phase errors, transients and radio frequency inhomogeneity. We simulated the spectral distortions introduced under these errors for four, eight and sixteen step phase cycles that are well known in the NMR community. The dominating pulse errors are radio frequency field inhomogeneity and antisymmetric pulse transients. These errors result in the reduction of signal intensity as well as an introduction of distortions in the detected double quantum filtered spectrum. Using the simulation tool we studied the improvement one obtains when implementing a sixteen step phase cycle over a four step phase cycle. The results indicate that implementing a sixteen step phase cycle over an eight or four step phase cycle does not result in a significant reduction in the DQF intensity loss, or reduction in spectral distortions for antisymmetric transients. PMID:20451432

  5. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    SciTech Connect

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  6. Molecular docking and NMR binding studies to identify novel inhibitors of human phosphomevalonate kinase

    SciTech Connect

    Boonsri, Pornthip; Neumann, Terrence S.; Olson, Andrew L.; Cai, Sheng; Herdendorf, Timothy J.; Miziorko, Henry M.; Hannongbua, Supa; Sem, Daniel S.

    2013-01-04

    Highlights: Black-Right-Pointing-Pointer Natural and synthetic inhibitors of human phosphomevalonate kinase identified. Black-Right-Pointing-Pointer Virtual screening yielded a hit rate of 15%, with inhibitor K{sub d}'s of 10-60 {mu}M. Black-Right-Pointing-Pointer NMR studies indicate significant protein conformational changes upon binding. -- Abstract: Phosphomevalonate kinase (PMK) phosphorylates mevalonate-5-phosphate (M5P) in the mevalonate pathway, which is the sole source of isoprenoids and steroids in humans. We have identified new PMK inhibitors with virtual screening, using autodock. Promising hits were verified and their affinity measured using NMR-based {sup 1}H-{sup 15}N heteronuclear single quantum coherence (HSQC) chemical shift perturbation and fluorescence titrations. Chemical shift changes were monitored, plotted, and fitted to obtain dissociation constants (K{sub d}). Tight binding compounds with K{sub d}'s ranging from 6-60 {mu}M were identified. These compounds tended to have significant polarity and negative charge, similar to the natural substrates (M5P and ATP). HSQC cross peak changes suggest that binding induces a global conformational change, such as domain closure. Compounds identified in this study serve as chemical genetic probes of human PMK, to explore pharmacology of the mevalonate pathway, as well as starting points for further drug development.

  7. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    DOE PAGES

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulkmore » IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.« less

  8. Membrane lipids protected from oxidation by red wine tannins: a proton NMR study.

    PubMed

    Furlan, Aurélien L; Jobin, Marie-Lise; Buchoux, Sébastien; Grélard, Axelle; Dufourc, Erick J; Géan, Julie

    2014-12-01

    Dietary polyphenols widespread in vegetables and beverages like red wine and tea have been reported to possess antioxidant properties that could have positive effects on human health. In this study, we propose a new in situ and non-invasive method based on proton liquid-state nuclear magnetic resonance (NMR) to determine the antioxidant efficiency of red wine tannins on a twice-unsaturated phospholipid, 1,2-dilinoleoyl-sn-glycero-3-phosphocholine (DLiPC), embedded in a membrane model. Four tannins were studied: (+)-catechin (C), (-)-epicatechin (EC), (-)-epicatechin gallate (ECG), and (-)-epigallocatechin gallate (EGCG). The lipid degradation kinetics was determined by measuring the loss of the bis-allylic protons during oxidation induced by a radical initiator, 2,2'-Azobis(2-methylpropionamidine) dihydrochloride (AAPH). The antioxidant efficiency, i.e. the ability of tannins to slow down the lipid oxidation rate, was shown to be higher for galloylated tannins, ECG and EGCG. Furthermore, the mixture of four tannins was more efficient than the most effective tannin, EGCG, demonstrating a synergistic effect. To better understand the antioxidant action mechanism of polyphenols on lipid membranes, the tannin location was investigated by NMR and molecular dynamics. A correlation between antioxidant action of tannins and their location at the membrane interface (inserted at the glycerol backbone level) could thus be established.

  9. NMR study of the interactions of polymyxin B, gramicidin S, and valinomycin with dimyristoyllecithin bilayers

    SciTech Connect

    Zidovetzki, R.; Banerjee, U.; Harrington, D.W.; Chan, S.I.

    1988-07-26

    The interactions of three polypeptide antibiotics (polymyxin B, gramicidin S, and valinomycin) with artificial lecithin membranes were studied by nuclear magnetic resonance (NMR). Combination of /sup 31/P and /sup 2/H NMR allowed observation of perturbations of the bilayer membrane structure induced by each of the antibiotics in the regions of the polar headgroups and acyl side chains of the phospholipids. The comparative study of the effects of these membrane-active antibiotics and the lipid bilayer structure demonstrated distinct types of antibiotic-membrane interactions in each case. Thus, the results showed the absence of interaction of polymyxin B with the dimyristoyllecithin membranes. In contrast, gramicidin S exhibited strong interaction with the lipid above the gel to liquid-crystalline phase transition temperature: disordering of the acyl side chains was evident. Increasing the concentration of gramicidin S led to disintegration of the bilayer membrane structure. At a molar ratio of 1:16 of gramicidin S to lecithin, the results are consistent with coexistence of gel and liquid-crystalline phases of the phospholipids near the phase transition temperature. Valinomycin decreased the phase transition temperature of the lipids and increased the order parameters of the lipid side chains. Such behavior is consistent with penetration of the valinomycin molecule into the interior of the lipid bilayers.

  10. A strategy for co-translational folding studies of ribosome-bound nascent chain complexes using NMR spectroscopy.

    PubMed

    Cassaignau, Anaïs M E; Launay, Hélène M M; Karyadi, Maria-Evangelia; Wang, Xiaolin; Waudby, Christopher A; Deckert, Annika; Robertson, Amy L; Christodoulou, John; Cabrita, Lisa D

    2016-08-01

    During biosynthesis on the ribosome, an elongating nascent polypeptide chain can begin to fold, in a process that is central to all living systems. Detailed structural studies of co-translational protein folding are now beginning to emerge; such studies were previously limited, at least in part, by the inherently dynamic nature of emerging nascent chains, which precluded most structural techniques. NMR spectroscopy is able to provide atomic-resolution information for ribosome-nascent chain complexes (RNCs), but it requires large quantities (≥10 mg) of homogeneous, isotopically labeled RNCs. Further challenges include limited sample working concentration and stability of the RNC sample (which contribute to weak NMR signals) and resonance broadening caused by attachment to the large (2.4-MDa) ribosomal complex. Here, we present a strategy to generate isotopically labeled RNCs in Escherichia coli that are suitable for NMR studies. Uniform translational arrest of the nascent chains is achieved using a stalling motif, and isotopically labeled RNCs are produced at high yield using high-cell-density E. coli growth conditions. Homogeneous RNCs are isolated by combining metal affinity chromatography (to isolate ribosome-bound species) with sucrose density centrifugation (to recover intact 70S monosomes). Sensitivity-optimized NMR spectroscopy is then applied to the RNCs, combined with a suite of parallel NMR and biochemical analyses to cross-validate their integrity, including RNC-optimized NMR diffusion measurements to report on ribosome attachment in situ. Comparative NMR studies of RNCs with the analogous isolated proteins permit a high-resolution description of the structure and dynamics of a nascent chain during its progressive biosynthesis on the ribosome. PMID:27466710

  11. Low temperature FTIR, Raman, NMR spectroscopic and theoretical study of hydroxyethylammonium picrate

    NASA Astrophysics Data System (ADS)

    Sudharsana, N.; Sharma, A.; Kuş, N.; Fausto, R.; Luísa Ramos, M.; Krishnakumar, V.; Pal, R.; Guru Row, T. N.; Nagalakshmi, R.

    2016-01-01

    A combined experimental (infrared, Raman and NMR) and theoretical quantum chemical study is performed on the charge-transfer complex hydroxyethylammonium picrate (HEAP). The infrared (IR) spectra for HEAP were recorded at various temperatures, ranging from 16 K to 299 K, and the Raman spectrum was recorded at room temperature. A comparison of the experimental IR and Raman spectra with the corresponding calculated spectra was done, in order to facilitate interpretation of the experimental data. Formation of the HEAP complex is evidenced by the presence of the most prominent characteristic bands of the constituting groups of the charge-transfer complex [e.g., NH3+, CO- and NO2]. Vibrational spectroscopic analysis, together with natural bond orbital (NBO) and theoretical charge density analysis in the crystalline phase, was used to shed light on relevant structural details of HEAP resulting from deprotonation of picric acid followed by formation of a hydrogen bond of the N-H⋯OC type between the hydroxyethylammonium cation and the picrate. 13C and 1H NMR spectroscopic analysis are also presented for the DMSO-d6 solution of the compound revealing that in that medium the HEAP crystal dissolves forming the free picrate and hydroxyethylammonium ions. Finally, the electron excitation analysis of HEAP was performed in an attempt to determine the nature of the most important excited states responsible for the NLO properties exhibited by the compound.

  12. Cannibalism Affects Core Metabolic Processes in Helicoverpa armigera Larvae—A 2D NMR Metabolomics Study

    PubMed Central

    Vergara, Fredd; Shino, Amiu; Kikuchi, Jun

    2016-01-01

    Cannibalism is known in many insect species, yet its impact on insect metabolism has not been investigated in detail. This study assessed the effects of cannibalism on the metabolism of fourth-instar larvae of the non-predatory insect Helicoverpa armigera (Lepidotera: Noctuidea). Two groups of larvae were analyzed: one group fed with fourth-instar larvae of H. armigera (cannibal), the other group fed with an artificial plant diet. Water-soluble small organic compounds present in the larvae were analyzed using two-dimensional nuclear magnetic resonance (NMR) and principal component analysis (PCA). Cannibalism negatively affected larval growth. PCA of NMR spectra showed that the metabolic profiles of cannibal and herbivore larvae were statistically different with monomeric sugars, fatty acid- and amino acid-related metabolites as the most variable compounds. Quantitation of 1H-13C HSQC (Heteronuclear Single Quantum Coherence) signals revealed that the concentrations of glucose, glucono-1,5-lactone, glycerol phosphate, glutamine, glycine, leucine, isoleucine, lysine, ornithine, proline, threonine and valine were higher in the herbivore larvae. PMID:27598144

  13. Rheo-NMR Studies of an Enzymatic Reaction: Evidence of a Shear-Stable Macromolecular System

    PubMed Central

    Edwards, Patrick J.B.; Kakubayashi, Motoko; Dykstra, Robin; Pascal, Steven M.; Williams, Martin A.K.

    2010-01-01

    Abstract Understanding the effects of shear forces on biopolymers is key to understanding how biological systems function. Although currently there is good agreement between theoretical predictions and experimental measurements of the behavior of DNA and large multimeric proteins under shear flow, applying the same arguments to globular proteins leads to the prediction that they should only exhibit shear-induced conformational changes at extremely large shear rates. Nevertheless, contradictory experimental evidence continues to appear, and the effect of shear on these biopolymers remains contentious. Here, a custom-built rheo-NMR cell was used to investigate whether shear flow modifies enzyme action compared with that observed quiescently. Specifically, 1H NMR was used to follow the kinetics of the liberation of methanol from the methylesterified polysaccharide pectin by pectinmethylesterase enzymes. Two different demethylesterifying enzymes, known to have different action patterns, were used. In all experiments performed, Couette flows with shear rates of up to 1570 s−1 did not generate detectable differences in the rate of methanol liberation compared to unsheared samples. This study provides evidence for a shear-stable macromolecular system consisting of a largely β-sheet protein and a polysaccharide, in line with current theoretical predictions, but in contrast to some other experimental work on other proteins. PMID:20441763

  14. FTIR, Raman and NMR spectroscopic and DFT theoretical studies on poly(N-vinylimidazole).

    PubMed

    Talu, Muzaffer; Demiroğlu, Elif Uzluk; Yurdakul, Şenay; Badoğlu, Serdar

    2015-01-01

    In this study where the FTIR, Raman, (1)H NMR and (13)C NMR spectra of poly(N-vinylimidazole) which can be abbreviated as poly(NVIM) are first reported, a comparison of the experimental and theoretical vibrational spectral data of monomer NVIM and water-soluble poly(NVIM) has been given; such a comparison over the vibrational modes and associated spectral data calculated at B3LYP/6-31+G(d) level of theory for NVIM and its stable dimer forms provided significant contributions for getting a reliable interpretation of the observed vibrational spectra of poly(NVIM). The obtained results revealed that the change from NVIM to poly(NVIM) should be characterized by the disappearance of the CH₂CH bonds of the vinyl group and the appearance of the aliphatic CH and CH₂ bonds. Besides this, the thermal properties of poly(NVIM) were elucidated by thermogravimetric analyses such as TGA, DTA and DSC, while some electronic structure parameters of the most stable dimers of NVIM were investigated through the structure calculations performed by using B3LYP method and 6-31+G(d) basis set within the density functional theory (DFT) methodology. PMID:25022498

  15. The NMR studies on two new furostanol saponins from Agave sisalana leaves.

    PubMed

    Zou, Peng; Fu, Jing; Yu, He-shui; Zhang, Jie; Kang, Li-ping; Ma, Bai-ping; Yan, Xian-zhong

    2006-12-01

    The detailed NMR studies and full assignments of the 1H and 13C spectral data for two new furostanol saponins isolated from Agave sisalana leaves are described. Their structures were established using a combination of 1D and 2D NMR techniques including 1H, 13C, 1H-1H COSY, TOCSY, HSQC, HMBC and HSQC-TOCSY, and also FAB-MS spectrometry and chemical methods. The structures were established as (25S)-26-(beta-D-glucopyranosyl)-22 xi-hydroxyfurost-12-one-3beta-yl-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->3)-O-[O-beta-D-glucopyranosyl-(1-->2)]-O-beta-D-glucopyranosyl-(1-->4)-beta-D-galacto- pyranoside (1) and (25S)-26-(beta-D-glucopyranosyl)-22xi-hydroxyfurost-5-en-12-one-3beta-yl-O-alpha-L-rhamno- pyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->3)-O-[O-beta-D-glucopyranosyl-(1-->2)]-O-beta-D-glucopyranosyl- (1-->4)-beta-D-galactopyranoside (2).

  16. NMR Studies of Cu/zeolite SCR Catalysts Hydrothermally Aged with Urea

    SciTech Connect

    Cheng, Yisun; Hoard, John; Lambert, Christine; Kwak, Ja Hun; Peden, Charles HF

    2008-06-26

    The effects of hydrothermal aging of Cu/zeolite urea-SCR catalysts on their reactivity and material properties was assessed by performance tests and multiple characterization techniques that included 27Al NMR and XRD. Three aging protocols were used that consisted of varying temperature during hydrothermal aging with or without exposure to aqueous urea solution. Differences in behavior were even found for samples hydrothermally aged immediately following exposure to the urea solution or if the sample was dried overnight before hydrothermal aging. The combination of urea and high temperature exposure increased the deactivation of Cu/zeolite SCR catalysts beyond that observed by hydrothermal aging alone, with an immediate high temperature exposure following wetting of the catalyst core with aqueous urea causing the most significant deterioration in performance. The impact of urea on SCR catalyst durability was also found to increase with the aging temperature. NMR analysis suggested that aging with urea resulted in relatively more dealumination of the zeolite for the SCR catalysts in this study.

  17. The dynamic complex of cytochrome c6 and cytochrome f studied with paramagnetic NMR spectroscopy.

    PubMed

    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.

  18. Evidence of vintage effects on grape wines using 1H NMR-based metabolomic study.

    PubMed

    Lee, Jang-Eun; Hwang, Geum-Sook; Van Den Berg, Frans; Lee, Cherl-Ho; Hong, Young-Shick

    2009-08-19

    The chemical composition of grape wines varies with grape variety, environmental factors of climate and soil, and bacterial strains, which can each affect the wine quality. Using (1)H NMR analysis coupled with multivariate statistical data sets, we investigated the effects of grape vintage on metabolic profiles of wine and the relationship between wine metabolites and meteorological data. Principal component analysis (PCA) showed a clear differentiation between Meoru wines that were vinified with the same yeast strain and Meoru grapes harvested from the same vineyard but with a different vintage. The metabolites contributing to the differentiation were identified as 2,3-butandiol, lactic acid, alanine, proline, gamma-aminobutyric acid (GABA), choline, and polyphenols, by complementary PCA loading plot. Markedly higher levels of proline, lactic acid and polyphenols were observed in the 2006 vintage wines compared to those of 2007 vintage, showing excellent agreement with the meteorological data that the sun-exposed time and rainfall in 2006 were approximately two times more and four times less, respectively, than those in 2007. These results revealed the important role of climate during ripening period in the chemical compositions of the grape. This study highlights the reliability of NMR-based metabolomic data by integration with meteorological data in characterizing wine or grape.

  19. Solid-state NMR and density functional theory studies of ionization states of thiamin.

    PubMed

    Paramasivam, Sivakumar; Balakrishnan, Anand; Dmitrenko, Olga; Godert, Amy; Begley, Tadhg P; Jordan, Frank; Polenova, Tatyana

    2011-02-01

    Thiamin diphosphate (ThDP) is a key coenzyme in sugar metabolism. The 4'-aminopyrimidine ring of ThDP cycles through several ionization and tautomeric states during enzyme catalysis, but it is not fully understood which states are adopted during the individual steps of the catalytic cycle. Thiamin has been synthesized with labels selectively inserted into the C2 and C6' positions, as well as into the amino group, creating [C2, C6'-(13)C(2)] thiamin and [N4'-(15)N] thiamin. Magic-angle spinning (MAS) NMR spectroscopy has been employed to record the (13)C and (15)N chemical shift anisotropy (CSA) tensors for C2, C6', and N4' atoms. Our results indicate that the isotropic chemical shifts as well as the principal components of the (13)C and (15)N CSA tensors are very sensitive to the protonation states in these compounds and, therefore, permit differentiating between the two ionization states, 4-aminopyrimidine and 4-aminopyrimidinium. Using density functional theory (DFT), we have calculated the magnetic shielding anisotropy tensors of C2, C6', and N4' and found excellent agreement between the computed and the experimental tensors. Our findings indicate that MAS NMR spectroscopy in conjunction with DFT calculations is a sensitive probe of ionization states in the thiamin cofactor. The results of this study will serve as a guide for characterization of ionization and tautomeric states of thiamin in complexes with thiamin-dependent enzymes.

  20. Cannibalism Affects Core Metabolic Processes in Helicoverpa armigera Larvae-A 2D NMR Metabolomics Study.

    PubMed

    Vergara, Fredd; Shino, Amiu; Kikuchi, Jun

    2016-01-01

    Cannibalism is known in many insect species, yet its impact on insect metabolism has not been investigated in detail. This study assessed the effects of cannibalism on the metabolism of fourth-instar larvae of the non-predatory insect Helicoverpa armigera (Lepidotera: Noctuidea). Two groups of larvae were analyzed: one group fed with fourth-instar larvae of H. armigera (cannibal), the other group fed with an artificial plant diet. Water-soluble small organic compounds present in the larvae were analyzed using two-dimensional nuclear magnetic resonance (NMR) and principal component analysis (PCA). Cannibalism negatively affected larval growth. PCA of NMR spectra showed that the metabolic profiles of cannibal and herbivore larvae were statistically different with monomeric sugars, fatty acid- and amino acid-related metabolites as the most variable compounds. Quantitation of ¹H-(13)C HSQC (Heteronuclear Single Quantum Coherence) signals revealed that the concentrations of glucose, glucono-1,5-lactone, glycerol phosphate, glutamine, glycine, leucine, isoleucine, lysine, ornithine, proline, threonine and valine were higher in the herbivore larvae. PMID:27598144

  1. Hydrogen Bonds in Crystalline Imidazoles Studied by 15N NMR and ab initio MO Calculations

    NASA Astrophysics Data System (ADS)

    Ueda, Takahiro; Nagatomo, Shigenori; Masui, Hirotsugu; Nakamura, Nobuo; Hayashi, Shigenobu

    1999-07-01

    Intermolecular hydrogen bonds of the type N-H...N in crystals of imidazole and its 4-substituted and 4,5-disubstituted derivatives were studied by 15N CP/MAS NMR and an ab initio molecular orbital (MO) calculation. In the 15N CP/MAS NMR spectrum of each of the imidazole derivatives, two peaks due to the two different functional groups, >NH and =N-, were observed. The value of the 15N isotropic chemical shift for each nitrogen atom depends on both the length of the intermolecular hydrogen bond and the kind of the substituent or substituents. It was found that the difference between the experimen-tal chemical shifts of >NH and =N-varies predominantly with the hydrogen bond length but does not show any systematic dependence on the kind of substituent. The ab initio MO calculations suggest that the hydrogen bond formation influences the 15N isotropic chemical shift predominantly, and that the difference between the 15N isotropic chemical shift of >NH and =N-varies linearly with the hydrogen bond length.

  2. Probing NMR parameters, structure and dynamics of 5-nitroimidazole derivatives. Density functional study of prototypical radiosensitizers.

    PubMed

    Ramalho, Teodorico C; Bühl, Michael

    2005-02-01

    The 15N chemical shifts of metronidazole (1), secnidazole (2), nimorazole (3) and tinidazole (4), radiosensitizers based on the 5-nitroimidazole motif, are reported. A detailed computational study of 1 is presented, calling special attention to the performance of various theoretical methods in reproducing the 13C and 15N data observed in solution. The most sophisticated approach involves density functional-based Car-Parrinello molecular dynamics simulations (CPMD) of 1 in aqueous solution (BP86 level) and averaging chemical shifts over snapshots from the trajectory. In the NMR calculations for these snapshots (performed at the B3LYP level), a small number of discrete water molecules are retained, and the remaining bulk solution effects are included via a polarizable continuum model (PCM). A similarly good accord with experiment is obtained from much less involved, static geometry optimization and NMR computation of pristine 1 employing a PCM approach. Solvent effects on delta(15N), which are of the order of up to 20 ppm, are not due to changes in geometric parameters upon solvation, but arise from the direct response of the electronic wavefunction to the presence of the solvent, which can be represented by discrete molecules and/or the dielectric bulk. PMID:15558660

  3. Structural analysis of molybdo-zinc-phosphate glasses: Neutron scattering, FTIR, Raman scattering, MAS NMR studies

    NASA Astrophysics Data System (ADS)

    Renuka, C.; Shinde, A. B.; Krishna, P. S. R.; Reddy, C. Narayana

    2016-08-01

    Vitreous samples were prepared in the xMoO3-17ZnO-(83-x) NaPO3 with 35 ≥ x ≥ 55 glass forming system by energy efficient microwave heating method. Structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), Raman scattering, Magic Angle Spin Nuclear magnetic resonance (MAS NMR) and Neutron scattering. Addition of MoO3 to the ZnO-NaPO3 glass leads to a pronounced increase in glass transition temperature (Tg) suggesting a significant increase in network connectivity and strength. In order to analyze FTIR and Raman scattering, a simple structural model is presented to rationalize the experimental observations. A number of structural units are formed due to network modification, and the resulting glass may be characterized by a network polyhedral with different numbers of unshared corners. 31P MAS NMR confirms a clear distinction between structural species having 3, 2, 1, 0 bridging oxygens (BOs). Further, Neutron scattering studies were used to probe the structure of these glasses. The result suggests that all the investigated glasses have structures based on chains of four coordinated phosphate and six coordinated molybdate units, besides, two different lengths of P-O bonds in tetrahedral phosphate units that are assigned to bonds of the P-atom with terminal and bridging oxygen atoms.

  4. Interactions of Polyvinylpyrrolidone with Chlorin e6-Based Photosensitizers Studied by NMR and Electronic Absorption Spectroscopy.

    PubMed

    Hädener, Marianne; Gjuroski, Ilche; Furrer, Julien; Vermathen, Martina

    2015-09-10

    Polyvinylpyrrolidone (PVP) can act as potential drug delivery vehicle for porphyrin-based photosensitizers in photodynamic therapy (PDT) to enhance their stability and prevent porphyrin self-association. In the present study the interactions of PVP (MW 10 kDa) were probed with five different derivatives of chlorin e6 (CE6) bearing either one of the amino acids serine, lysine, tyrosine or arginine, or monoamino-hexanoic acid as substituent. All derivatives of CE6 (xCE) formed aggregates of a similar structure in aqueous buffer in the millimolar range. In the presence of PVP monomerization of all xCE aggregates could be proved by (1)H NMR spectroscopy. xCE-PVP complex formation was confirmed by (1)H NMR T2 relaxation and diffusion ordered spectroscopy (DOSY). (1)H(1)H-NOESY data suggested that the xCE uptake into the PVP polymer matrix is governed by hydrophobic interactions. UV-vis absorption and fluorescence emission bands of xCE in the micromolar range revealed characteristic PVP-induced bathochromic shifts. The presented data point out the potential of PVP as carrier system for amphiphilic derivatives of chlorin e6. The capacity of PVP to monomerize xCE aggregates may enhance their efficiency as possible photosensitizers in PDT.

  5. Solution NMR Studies of Antiamoebin, a Membrane Channel-Forming Polypeptide

    PubMed Central

    Galbraith, T. P.; Harris, R.; Driscoll, P. C.; Wallace, B. A.

    2003-01-01

    Antiamoebin I is a membrane-active peptaibol produced by fungi of the species Emericellopsis which is capable of forming ion channels in membranes. Previous structure determinations by x-ray crystallography have shown the molecule is mostly helical, with a deep bend in the center of the polypeptide, and that the backbone structure is independent of the solvent used for crystallization. In this study, the solution structure of antiamoebin was determined by NMR spectroscopy in methanol, a solvent from which one of the crystal structures was determined. The ensemble of structures produced exhibit a right-handed helical C terminus and a left-handed helical conformation toward the N-terminus, in contrast to the completely right-handed helices found in the crystal structures. The NMR results also suggest that a “hinge” region exists, which gives flexibility to the polypeptide in the central region, and which could have functional implications for the membrane insertion process. A model for the membrane insertion and assembly process is proposed based on the antiamoebin solution and crystal structures, and is contrasted with the assembly and insertion mechanism proposed for other ion channel-forming polypeptides. PMID:12524274

  6. The dynamic complex of cytochrome c6 and cytochrome f studied with paramagnetic NMR spectroscopy.

    PubMed

    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. PMID:24685428

  7. Morphological Characterization of DMPC/CHAPSO Bicellar Mixtures: A Combined SANS and NMR Study

    SciTech Connect

    Li, Ming; Morales, Hannah H; Katsaras, John; Kucerka, Norbert; Yang, Yongkun; Macdonald, P; Nieh, Mu-Ping

    2013-01-01

    Spontaneously forming structures of a system composed of dimyristoyl phosphatidylcholine (DMPC) and 3-[(3-cholamidopropyl)dimethylammonio]-2-hydroxy-1-propanesulfonate (CHAPSO) were studied by small-angle neutron scattering (SANS), 31P NMR, and stimulated echo (STE) pulsed field gradient (PFG) 1H NMR diffusion measurements. Charged lipid dimyristoyl phosphatidylglycerol (DMPG) was used to induce different surface charge densities. The structures adopted were investigated as a function of temperature and lipid concentration for samples with a constant molar ratio of long-chain to short-chain lipids (=3). In the absence of DMPG, zwitterionic bicellar mixtures exhibited a phase transition from discoidal bicelles, or ribbons, to multilamellar vesicles either upon dilution or with increased temperature. CHAPSO-containing mixtures showed a higher thermal stability in morphology than DHPC-containing mixtures at the corresponding lipid concentrations. In the presence of DMPG, discoidal bicelles (or ribbons) were also found at low temperature and lower lipid concentration mixtures. At high temperature, perforated lamellae were observed in high concentration mixtures ( 7.5 wt %) whereas uniform unilamellar vesicles and bicelles formed in low-concentration mixtures ( 2.5 wt %), respectively, when the mixtures were moderately and highly charged. From the results, spontaneous structural diagrams of the zwitterionic and charged systems were constructed.

  8. Improving NMR Protein Structure Quality by Rosetta Refinement: a Molecular Replacement Study

    SciTech Connect

    Ramelot, T.; Raman, S; Kuzin, A; Hunt, J; Baker, D; Kennedy, M

    2009-01-01

    The structure of human protein HSPC034 has been determined by both solution nuclear magnetic resonance (NMR) spectroscopy and X-ray crystallography. Refinement of the NMR structure ensemble, using a Rosetta protocol in the absence of NMR restraints, resulted in significant improvements not only in structure quality, but also in molecular replacement (MR) performance with the raw X-ray diffraction data using MOLREP and Phaser. This method has recently been shown to be generally applicable with improved MR performance demonstrated for eight NMR structures refined using Rosetta (Qian et al., Nature 2007;450:259-264). Additionally, NMR structures of HSPC034 calculated by standard methods that include NMR restraints have improvements in the RMSD to the crystal structure and MR performance in the order DYANA, CYANA, XPLOR-NIH, and CNS with explicit water refinement (CNSw). Further Rosetta refinement of the CNSw structures, perhaps due to more thorough conformational sampling and/or a superior force field, was capable of finding alternative low energy protein conformations that were equally consistent with the NMR data according to the Recall, Precision, and F-measure (RPF) scores. On further examination, the additional MR-performance shortfall for NMR refined structures as compared with the X-ray structure were attributed, in part, to crystal-packing effects, real structural differences, and inferior hydrogen bonding in the NMR structures. A good correlation between a decrease in the number of buried unsatisfied hydrogen-bond donors and improved MR performance demonstrates the importance of hydrogen-bond terms in the force field for improving NMR structures. The superior hydrogen-bond network in Rosetta-refined structures demonstrates that correct identification of hydrogen bonds should be a critical goal of NMR structure refinement. Inclusion of nonbivalent hydrogen bonds identified from Rosetta structures as additional restraints in the structure calculation results in

  9. Improving NMR Protein Structure Quality by Rosetta Refinement: A Molecular Replacement Study

    SciTech Connect

    Ramelot, Theresa A.; Raman, Srivatsan; Kuzin, Alexander P.; Xiao, Rong; Ma, LiChung; Acton, Thomas; Hunt, John F.; Montelione, Gaetano; Baker, David; Kennedy, Michael A.

    2009-04-01

    The structure of human protein HSPC034 has been determined by both solution nuclear magnetic resonance (NMR) spectroscopy and X-ray crystallography. Refinement of the NMR structure ensemble, using a Rosetta protocol in the absence of NMR restraints, resulted in significant improvements not only in structure quality, but also in molecular replacement (MR) performance with the raw X-ray diffraction data using MOLREP and Phaser. This method has recently been shown to be generally applicable with improved MR performance demonstrated for eight NMR structures refined using Rosetta (Qian et al., Nature 2007;450:259–264). Additionally, NMR structures of HSPC034 calculated by standard methods that include NMR restraints have improvements in the RMSD to the crystal structure and MR performance in the order DYANA, CYANA, XPLOR-NIH, and CNS with explicit water refinement (CNSw). Further Rosetta refinement of the CNSw structures, perhaps due to more thorough conformational sampling and/or a superior force field, was capable of finding alternative low energy protein conformations that were equally consistent with the NMR data according to the Recall, Precision, and F-measure (RPF) scores. On further examination, the additional MR-performance shortfall for NMR refined structures as compared with the X-ray structure were attributed, in part, to crystal-packing effects, real structural differences, and inferior hydrogen bonding in the NMR structures. A good correlation between a decrease in the number of buried unsatisfied hydrogen-bond donors and improved MR performance demonstrates the importance of hydrogen-bond terms in the force field for improving NMR structures. The superior hydrogen-bond network in Rosetta-refined structures demonstrates that correct identification of hydrogen bonds should be a critical goal of NMR structure refinement. Inclusion of nonbivalent hydrogen bonds identified from Rosetta structures as additional restraints in the structure calculation results

  10. Cloud point, fluorimetric and 1H NMR studies of ibuprofen-polymer systems

    NASA Astrophysics Data System (ADS)

    Khan, Iqrar Ahmad; Anjum, Kahkashan; Koya, P. Ajmal; Qadeer, Atiytul; Kabir-ud-Din

    2014-01-01

    Influence of six polymers viz. hydroxyethyl cellulose (HEC), hydroxypropyl methyl cellulose (HPMC), polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), sodium carboxy methyl cellulose (NaCMC) and dextran sulfate (DxS) on solution properties of amphiphilic drug ibuprofen (IBF) has been described in this work. As only HPMC showed the clouding behavior (among the polymers employed herein), its cloud point (CP) was studied in detail in presence of varying amounts of IBF containing different fixed concentrations of inorganic salts (NaCl, NaNO3, Na2SO4, KBr and KNO3). Presence of all these salts had CP reducing effect. By means of steady state fluorescence quenching studies, average aggregation number of IBF aggregates (Nagg) in the presence of varying amounts of the mentioned polymers were evaluated and discussed. 1H NMR studies show that the magnitude of chemical shifts (δ) varies with the nature of the polymer.

  11. Crowding versus molecular seeding: NMR studies of protein aggregation in hen egg white

    NASA Astrophysics Data System (ADS)

    Sanfelice, D.; Adrover, M.; Martorell, G.; Pastore, A.; Temussi, P. A.

    2012-06-01

    In living systems, proteins are surrounded by many other macromolecules of different nature, at high total concentrations. In the last few years, there has been an increasing effort to study biological macromolecules directly in natural crowded environments, such as in intact bacterial cells or by mimicking natural crowding by adding proteins, polysaccharides or even synthetic polymers. We have recently proposed hen egg white (HEW) as a suitable, natural medium to study macromolecules in crowding conditions. Here, we show that HEW can increase dramatically the aggregation kinetics of proteins with an in-built tendency to associate. By dissecting the mechanism we demonstrate that only part of this effect is due to crowding, while another factor playing an important role is the interaction with proteins from the milieu. High molecular weight glycoproteins present in HEW act as efficient molecular seeds for aggregation. Our results bear important consequences for in-cell NMR studies and suggest a role of glycosylated proteins in aggregation.

  12. Solid state NMR method development and studies of biological and biomimetic nanocomposites

    SciTech Connect

    Hu, Yanyan

    2011-01-01

    This thesis describes application and development of advanced solid-state nuclear magnetic resonance techniques for complex materials, in particular organic-inorganic nanocomposites and thermoelectric tellurides. The apatite-collagen interface, essential for understanding the biomineralization process in bone and engineering the interface for controlled bio-mimetic synthesis and optimized mechanical properties, is buried within the nanocomposite of bone. We used multinuclear solid-state NMR to study the composition and structure of the interface. Citrate has been identified as the main organic molecule strongly bound to the apatite surface with a density of 1/(2 nm)2, covering 1/6 of the total surface area in bovine bone. Citrate provides more carboxylate groups, one of the key functional groups found to affect apatite nucleation and growth, than all the non-collagenous proteins all together in bone; thus we propose that citrate stabilizes apatite crystals at a very small thickness of ~3 nm (4 unit cells) to increase bone fracture tolerance. The hypothesis has been confirmed in vitro by adding citrate in the bio-mimetic synthesis of polymerhydroxyapatite nanocomposites. The results have shown that the size of hydroxyapatite nanocrystals decreases as increasing citrate concentration. With citrate concentrations comparable to that in body fluids, similar-sized nanocrystals as in bone have been produced. Besides the dimensions of the apatite crystals, the composition of bone also affects its biofunctional and macroscopic mechanical properties; therefore, our team also extended its effort to enhance the inorganic portion in our bio-mimetic synthesis from originally 15 wt% to current 50 wt% compared to 65 wt% in bovine bone, by using Lysine-Leucine hydroxyapatite nucleating diblock co-polypeptide, which forms a gel at very low concentration. In this thesis, various advanced solid state NMR techniques have been employed to characterize nanocomposites

  13. Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds.

    PubMed

    Perić, Berislav; Gautier, Régis; Pickard, Chris J; Bosiočić, Marko; Grbić, Mihael S; Požek, Miroslav

    2014-01-01

    Two hexanuclear niobium halide cluster compounds with a [Nb6X12](2+) (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable Bo field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of (95)Mo nuclei in structurally related compounds containing [Mo6Br8](4+) cluster cores. Experimentally determined δiso((93)Nb) values are in the range from 2,400 to 3,000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (Vzz and δ33) coinciding with the molecular four-fold axis of the [Nb6X12](2+) unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (Vzz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (Vyy) and the largest CS principal axis (δ11) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by (79/81)Br NQR and (35)Cl solid-state NMR measurements.

  14. Purification and stable isotope labeling of the calcium- and integrin-binding protein 1 for structural and functional NMR studies.

    PubMed

    Huang, Hao; Vogel, Hans J

    2013-01-01

    The Calcium- and Integrin-Binding protein 1 (CIB1) has been identified as an important regulatory Ca(2+)-binding protein that is involved in various cellular functions. Nuclear Magnetic Resonance (NMR) spectroscopy provides a powerful approach to study the structure, dynamics, and interactions of CIB1 and related proteins. Multidimensional NMR spectroscopy combined with various selective isotope labeling strategies has proven to be successful in the structure determination of CIB1. Moreover, the same approach allowed the detection of conformational changes when the protein binds different metal ions, and it facilitated the study of the interaction of CIB1 with the cytoplasmic domain of the human integrin αIIb subunit. In this protocol, we describe the purification and isotope labeling strategies for productive NMR studies of CIB1. The same isotope labeling strategies can be implemented to study numerous related regulatory calcium-binding proteins.

  15. Phase Diagram for 3He Films on Boron Nitride: NMR Studies

    NASA Astrophysics Data System (ADS)

    Tang, Yibing; Sullivan, Neil

    2014-03-01

    Recent studies of the thermodynamic properties of 3He films on graphite have revealed the existence of a previously undetected self-bound liquid phase at low density coverages. We report the results of NMR relaxation time studies for 3He adsorbed on hexagonal boron nitride designed to explore the dynamics of the adsorbed 3He atoms in order to identify the phase boundaries as a function of temperature. A steep thermally activated temperature dependence is observed at high temperatures (T > 2 . 6) K, followed by a linear dependence for 0 . 77 < T < 2 . 6 K. The linear dependence is consistent with that expected for thermal diffusion in the self-bound liquid state. The research was supported in part by a grant from the National Science Foundation, DMR-1303599.

  16. The interaction of polyamines with DNA: a 23Na NMR study.

    PubMed Central

    Burton, D R; Forsén, S; Reimarsson, P

    1981-01-01

    The interaction between a variety of polyamines, both naturally occurring and synthetic, and calf thymus DNA has been studied using 23Na NMR. The relaxation behaviour of 23Na reflects the extent of interaction of Na+ with DNA phosphate groups and therefore the extent of charge neutralisation of DNA phosphate groups (P) by polyamine amino and imino groups (N) in solutions of DNa, polyamine and Na+. The studies reveal that whereas spermine and spermidine are capable of expelling nearly all of the Na+ ions from DNA at N/P approximately 1, diamines such as putrescine and homologues of spermine and spermidine are capable of neutralising only roughly 50% of DNA phosphates. The results provide a challenge to current models of DNA-polyamine interactions. PMID:7232215

  17. Dynamic NMR studies of restricted arene rotation in the chromiu tricarbonyl thiophene and selenophene complexes

    SciTech Connect

    Sanger, M.J.

    1994-05-27

    This thesis contains the results of organometallic studies of thiophene and selenophene coordination in transition metal complexes. Chromium tricarbonyl complexes of thiophene, selenophene, and their alkyl-substituted derivatives were prepared and variable-temperature {sup 13}C NMR spectra of these complexes were recorded in dimethyl ether. Bandshape analyses of these spectra yielded activation parameters for restricted rotation of the thiophene and selenophene ligands in these complexes. Extended Hueckel molecular orbital calculations (EHMO) of the free thiophene and selenophene ligands and selected chromium tricarbonyl thiophene complexes were performed to better explain the activation barriers of these complexes. The structure of Cr(CO){sub 3}({eta}{sup 5}-2,5-dimethylthiophene) was established by a single crystal X-ray diffraction study.

  18. High-pressure low-temperature locknut cell for both EPR and NMR studies to 10 kilobars and 77 K

    NASA Astrophysics Data System (ADS)

    Sinha, Shantanu; Srinivasan, R.

    1983-11-01

    A locked high-pressure cell with working pressure range up to 10 kbars suitable for low-temperature studies to 77 K has been described. It can be used for both EPR and NMR studies of single crystals (and other solid samples). The high-pressure seal and all other aspects of the cell remain the same for either application. Only a change of the bottom plug is required for a switch from a nuclear-magnetic-resonance (NMR) to an electron-paramagnetic-resonance (EPR) experiment. Details of the procedure for the calibration of pressure inside the cell at various temperatures are discussed. The performance of the cell in EPR (Cr3+ion) and NMR (27Al nucleus) studies is reported.

  19. Carbon-13 NMR studies of salt shock-induced carbohydrate turnover in the marine cyanobacterium Agmenellum quadruplicatum

    NASA Technical Reports Server (NTRS)

    Tel-Or, E.; Spath, S.; Packer, L.; Mehlhorn, R. J.

    1986-01-01

    Carbon turnover in response to abrupt changes in salinity, including the mobilization of glycogen for use in osmoregulation was studied with pulse-chase strategies utilizing nuclear magnetic resonance (NMR)-silent and NMR-detectable 12C and 13C isotopes, respectively. Growth of Agmenellum quadruplicatum in 30%-enriched 13C bicarbonate provided sufficient NMR-detectability of intracellular organic osmoregulants for these studies. A comparison of NMR spectra of intact cells and their ethanol extracts showed that the intact cell data were suitable for quantitative work, and, when combined with ESR measurements of cell volumes, yielded intracellular glucosylglycerol concentrations without disrupting the cells. NMR pulse-chase experiments were used to show that 13C-enriched glycogen, which had previously been accumulated by the cells under nitrogen-limited growth at low salinities, could be utilized for the synthesis of glucosylglycerol when the cells were abruptly transferred to hypersaline media, but only in the light. It was also shown that the accumulation of glucosylglycerol in the light occurred on a time scale similar to that of cell doubling. Depletion of glucosylglycerol when cells abruptly transferred to lower salinities appeared to be rapid--the intracellular pool of this osmoregulant was decreased 2-fold within 2 hours of hypotonic shock.

  20. NMR studies of the solution conformation and dynamics of the tyrocidine peptide antibiotics

    SciTech Connect

    Zhou, N.

    1985-01-01

    The tyrocidine B and tyrocidine C /sup 1/H NMR spectra in DMSO-d/sub 6/ were assigned by using 2D /sup 1/H-/sup 1/H correlation spectroscopy and 1D double resonance experiments. Based on the proton chemical shifts, /sup 3/J/sub NH-N..cap alpha../ coupling constants, the chemical shift temperature dependence, and 1D and 2D /sup 1/H-/sup 1/H NOE values, a backbone conformation consisting of an anti-parallel ..beta..-pleated sheet, a type I ..beta..-turn and a type II' ..beta..-turn was suggested for both tyrocidines B and C. Seven out of ten side chains were determined to exist predominantly in one classical Chi/sub 1/ rotamer; while the residues Val/sup 1/ and Leu/sup 3/ had two Chi/sub 1/ rotamers which were significantly populated. Chi/sub 2/ angles were determined for residues Phe/sup 4/, Trp/sup 6/, DPhe/sup 7/ (D Trp/sup 7/) and Asn/sup 8/. The natural abundance /sup 13/C spectra of tyrocidine B and tyrocidine C were assigned by using /sup 1/H-/sup 13/C correlation spectroscopy. A study of the effect of soluble paramagnetic nitroxide compounds on tyrocidine A proton T/sub 1/ values were performed which confirmed the proposed tyrocidine A conformation. It also proved that these nitroxide compounds are very useful in studying proton solvent exposure, and therefore in delineating hydrogen bonding. A proton NMR study of the opioid peptide dynorphin-(1-13) in aqueous solution was reported which was consistent with a non-ordered molecule in the solution.

  1. Real-time NMR studies of electrochemical double-layer capacitors.

    PubMed

    Wang, Hao; Köster, Thomas K-J; Trease, Nicole M; Ségalini, Julie; Taberna, Pierre-Louis; Simon, Patrice; Gogotsi, Yury; Grey, Clare P

    2011-12-01

    (11)B NMR spectroscopy has been used to investigate the sorption of BF(4)(-) anions on a highly porous, high surface area carbon, and different binding sites have been identified. By implementing in situ NMR approaches, the migration of ions between the electrodes of the supercapacitors and changes in the nature of ion binding to the surface have been observed in real time.

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

    ERIC Educational Resources Information Center

    Thompson, Laura E.; Rovnyak, David

    2007-01-01

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

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

    ERIC Educational Resources Information Center

    Thompson, Laura E.; Rovnyak, David

    2007-01-01

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

  4. Localization and interaction of hydroxyflavones with lipid bilayer model membranes: a study using DSC and multinuclear NMR.

    PubMed

    Sinha, Ragini; Joshi, Akshada; Joshi, Urmila J; Srivastava, Sudha; Govil, Girjesh

    2014-06-10

    The localization and interaction of six naturally occurring flavones (FLV, 5HF, 6HF, 7HF, CHY and BLN) in DPPC bilayers were studied using DSC and multi-nuclear NMR. DSC results indicate that FLV and 6HF interact with alkyl chains. The (1)H NMR shows interaction of flavones with the sn-glycero region. Ring current induced chemical shifts indicate that 6HF and BLN acquire parallel orientation in bilayers. 2D NOESY spectra indicate partitioning of the B-ring into the alkyl chain region. The DSC, NMR and binding studies indicate that 5HF and 7HF are located near head group region, while 6HF, CHY and BLN are located in the vicinity of sn-glycero region, and FLV is inserted deepest in the membrane.

  5. NMR analyses of the cold cataract. III. /sup 13/C acrylamide studies

    SciTech Connect

    Lerman, S.; Megaw, J.M.; Moran, M.N.

    1985-10-01

    /sup 13/C-enriched acrylamide was employed to further delineate the action of this compound in preventing the cold cataract phenomenon when it is incorporated (in vitro) into young human and rabbit lenses. The extent of acrylamide incorporation, in the dark and with concurrent UV exposure, was monitored by /sup 13/C NMR spectroscopy. These studies provide further evidence that UV exposure causes permanent acrylamide photobinding within the lens. In such lenses, the gamma crystallin fraction of the soluble lens proteins is affected to the greatest extent. It appears to become aggregated and/or combined with the alpha and beta fractions resulting in an apparent loss of most of the gamma monomers. There is also an age-related effect with respect to the amount of acrylamide that can be incorporated into the lens. The decrease in acrylamide incorporation with age directly parallels the age-related decline in gamma crystallin levels.

  6. Moisture transport in heated concrete, as studied by NMR, and its consequences for fire spalling

    SciTech Connect

    Heijden, G.H.A. van der; Bijnen, R.M.W. van; Pel, L. . E-mail: l.pel@tue.nl; Huinink, H.P.

    2007-06-15

    During the past 30 years concrete has developed enormously in both strength and durability. A drawback of these improvements is the increased risk of explosive spalling in case of fire. The moisture inside the concrete plays an important role in the spalling mechanism. In order to study the moisture migration inside concrete during intense heating, a dedicated nuclear magnetic resonance (NMR) setup was built. This setup can be placed inside a 1.5-T MRI scanner. With this setup one-dimensional moisture profiles can be measured while the concrete sample is heated up to 250 deg. C. Besides concrete, measurements were performed on fired-clay brick and calcium-silicate brick. The results show that water inside the concrete sample is superheated to a temperature of 170 deg. C, which results in an increased pressure inside the concrete. A model was developed to predict the movement of the observed drying front.

  7. Various forms of coexistence of superconductivity and magnetism in iron-pnictide superconductors: a NMR study

    NASA Astrophysics Data System (ADS)

    Bobroff, Julien

    2013-03-01

    Our NMR studies of iron pnictides allowed us to discover various forms of coexistence between superconductivity and magnetism. In Co-doped BaFe2As2, superconductivity and incommensurate antiferromagnetism coexist at the atomic level in an homogeneous state. In contrast, Ru isovalent doping leads to a disorderd situation where superconducting clusters appear in an antiferromagnetic background. Finally, in the 245 iron-selenide RbFeSe, antiferromagnetism and superconductivity separate in alternate layers of nanometer thickness. But in all these componds, the superconducting state remains similar in terms of local susceptibility and carrier doping. It looks as if, for superconductivity to appear, frozen Fe magnetic moments need to be small enough or far enough in distance, whatever the cause. Y. Texier et al., PRL 108, 237002 (2012); Y. Laplace et al., PRB Rapid Com 86, 020510(R) (2012); Y. Laplace, PRB Rapid Com 80, 140501 (2009) This work benefited from the support of the ANR PNICTIDES.

  8. 1H NMR study of the complexation of aromatic drugs with dimethylxanthine derivatives

    NASA Astrophysics Data System (ADS)

    Hernandez Santiago, A. A.; Gonzalez Flores, M.; Rosas Castilla, S. A.; Cervantes Tavera, A. M.; Gutierrez Perez, R.; Khomich, V. V.; Ovchinnikov, D. V.; Parkes, H. G.; Evstigneev, M. P.

    2012-02-01

    With an aim of searching efficient interceptors of aromatic drugs, the self- and hetero-association of dimethylxanthine derivatives with different structures, selected according to Strategy 1 (variation of the position of methyl groups) and Strategy 2 (variation of the length of sbnd (CH2)nsbnd COOH group), with aromatic drug molecules: Ethidium Bromide, Proflavine and Daunomycin, were studied using 1H NMR spectroscopy. It was found that the association proceeds in a form of stacking-type complexation and its energetics is relatively independent on the structure of the dimethylxanthines. However, on average, the dimethylxanthines possess higher hetero-association constant and, hence, higher interceptor ability as compared to the trimethylxanthine, Caffeine, used during the past two decades as a typical interceptor molecule.

  9. From a Simple Liquid to a Polymer Melt: NMR Relaxometry Study of Polybutadiene

    NASA Astrophysics Data System (ADS)

    Kariyo, S.; Gainaru, C.; Schick, H.; Brodin, A.; Novikov, V. N.; Rössler, E. A.

    2006-11-01

    We utilize NMR field cycling relaxometry to study the crossover from glassy dynamics (t≳τα) through Rouse to reptation behavior in a series of monodisperse polybutadienes with molecular weights M=355 to 817000g/mol. We separate characteristic polymer dynamics from the total spectrum dominated by glassy dynamics. The polymer dynamics show typical Rouse relaxation features that grow with M and saturate at high M. Comparing to Rouse theory, we determine the Rouse unit size MR≃500 and entanglement weight Me≃2000; the Rouse spectrum saturates at Mmax⁡≃4000. The local order parameter S≈0.11 is relatively large, indicating noticeable local packing already in the Rouse regime. The M dependence of the glass transition temperature Tg, obtained from dielectric relaxation spectra, shows distinctive kinks at MR and Me.

  10. Conformational studies by liquid crystal NMR and ab initio calculations: methyl nicotinate and methyl isonicotinate

    NASA Astrophysics Data System (ADS)

    Kon, Masao; Kurokawa, Hideki; Takeuchi, Hiroshi; Konaka, Shigehiro

    1992-04-01

    Conformational properties of methyl nicotinate and methyl isonicotinate have been studied by liquid crystal 1H-NMR spectroscopy combined with ab initio calculations. The solvent used is a mixture of 80 mol.% of EBBA and 20 mol.% of MBBA.Ab initio calculations have been performed with 4-21G and MINI-4 basis sets to estimate molecular structures and the potential functions for internal rotation. Some structural parameters and the energy difference between rotational isomers have been refined by using observed dipolar coupling constants. The correlation between internal rotation and reorientational molecular motion has been taken into account according to the theory of Emsley, Luckhurst and Stockley. The parameters of the mean external potential are found to take similar values for methyl nicotinate and methyl isonicotinate. The energy difference of the two stable conformers of methyl nicotinate is in agreement with the analysis neglecting the correlation between the two motions.

  11. NMR studies of a new family of DNA binding proteins: the THAP proteins.

    PubMed

    Gervais, Virginie; Campagne, Sébastien; Durand, Jade; Muller, Isabelle; Milon, Alain

    2013-05-01

    The THAP (THanatos-Associated Protein) domain is an evolutionary conserved C2CH zinc-coordinating domain shared with a large family of cellular factors (THAP proteins). Many members of the THAP family act as transcription factors that control cell proliferation, cell cycle progression, angiogenesis, apoptosis and epigenetic gene silencing. They recognize specific DNA sequences in the promoters of target genes and subsequently recruit effector proteins. Recent structural and functional studies have allowed getting better insight into the nuclear and cellular functions of some THAP members and the molecular mechanisms by which they recognize DNA. The present article reviews recent advances in the knowledge of the THAP domains structures and their interaction with DNA, with a particular focus on NMR. It provides the solution structure of the THAP domain of THAP11, a recently characterized human THAP protein with important functions in transcription and cell growth in colon cancer. PMID:23306615

  12. NMR study of electric quadrupole interactions in GdCo 2

    NASA Astrophysics Data System (ADS)

    Barata, A. C.; Guimarães, A. P.

    1985-05-01

    Quadrupole oscillations have been observed with 59Co pulsed NMR in the intermetallic compound GdCo 2. From these oscillations the nuclear electric quadrupole interaction (EQI) has been studied as a function of temperature in the range 4-312 K. The value measured at 4 K, ν Q=672±3 kHz, is the largest so far reported for the cobalt EQI in the RCo 2 intermetallics. The EQI decreases with increasing temperature, reaching 432±10 kHz at 312 K. The amplitude of the oscillations tends to decrease with temperature, being also dependent on the easy direction of magnetization of the compound. Thus, above 200 K, as the direction of magnetization changes, large oscillations are again visible in the satellite line; the main line shows no oscillations in this range. The observed temperature dependence of the EQI is roughly linear, as found in othr transition metal systems.

  13. Computational and experimental studies into NMR characterization of [2+2] cycloaddition products of norbornene

    NASA Astrophysics Data System (ADS)

    Mierzwicki, Krzysztof; Rzepecka, Ewa; Czeluśniak, Izabela; Szymańska-Buzar, Teresa

    2011-06-01

    The geometry of six stereoisomers of pentacyclo[8.2.1.14,7.02,9.03,8]tetradecane formed in [2+2] cycloaddition reaction of bicyclo[2.2.1]hept-2-ene (norbornene) were optimized by a theoretical method at the DFT level with the B3LYP functional. The calculated GIAO 1H and 13C shieldings were transformed to chemical shifts (δ) on the TMS scale and next compared with those obtained experimentally for two stereoisomers. The 1H and 13C NMR chemical shifts calculated using the DFT method were found to be in very good agreement with the available experimental data. This is the first example of studying the [2+2] cycloaddition products of norbornene by theoretical method.

  14. Diffusion NMR studies of macromolecular complex formation, crowding and confinement in soft materials.

    PubMed

    Barhoum, Suliman; Palit, Swomitra; Yethiraj, Anand

    2016-05-01

    Label-free methods to obtain hydrodynamic size from diffusion measurements are desirable in environments that contain multiple macromolecular species at a high total concentration: one example is the crowded cellular environment. In complex, multi-species macromolecular environments - in this article, we feature aqueous systems involving polymers, surfactants and proteins - the link between dynamics and size is harder to unpack due to macromolecular crowding and confinement. In this review, we demonstrate that the pulsed-field gradient NMR technique, with its spectral separation of different chemical components, is ideal for studying the dynamics of the entire system simultaneously and without labelling, in a wide range of systems. The simultaneous measurement of the dynamics of multiple components allows for internal consistency checks and enables quantitative statements about the link between macromolecular dynamics, size, complex formation and crowding in soft materials.

  15. 1H NMR Cryoporometry Study of the Melting Behavior of Water in White Cement

    NASA Astrophysics Data System (ADS)

    Boguszyńska, Joanna; Tritt-Goc, Jadwiga

    2004-09-01

    The pore size of white cement samples is studied by the melting behaviour of water confined in it, using 1H NMR cryopormetry. The influence of the preparing method and antifreeze admixture on the pore size and distribution in cement samples is investigated at 283 K. The addition of an antifreeze admixture [containing 1% Sika Rapid 2 by weight of the dry cement] influences the porosity. In wet prepared samples we observed a significant increase in the quantity of mesopores between 0.8 and 5 nm and a smaller increase of mesopores between 5 and 10 nm, when compared to cement without admixture. The compressive strength is related to the porosity of the cement. Therefore the cement with Sika Rapid 2, wet prepared at 278 K shows a higher strength than all other measured samples.

  16. The polymorphic phases of the hexaalkanoyloxytriphenylene liquid crystals, as studied by deuterium NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Goldfarb, D.; Lifshitz, E.; Zimmermann, H.; Luz, Z.

    1985-06-01

    Deuterium NMR spectra are reported for several specifically deuterated hexaalkanoyloxytriphenylenes in their corresponding liquid crystalline phases. The higher homologs of this series are polymorphic and exhibit a variety of discotic mesophases, including both biaxial (D0 and D1) and uniaxial (D2) columnar phases. The ordering characteristics of these phases are studied using the quadrupolar splittings of the aromatic and aliphatic deuterons. The results show that during the transition from the biaxial D1 to the axial D2 phase the major susceptibility tensor switch orientation, apparently due to strong tilting of the molecules with respect to the columnar axis in the biaxial phase. Characteristic features which appear in the spectra of these phases are interpreted in terms of intercolumnar jumps of mesogen molecules.

  17. NMR and X-ray studies of isomeric 22,23-dihydroxy stigmastanes

    NASA Astrophysics Data System (ADS)

    Khripach, Vladimir A.; Zhabinskii, Vladimir N.; Ivanova, Galina V.; Fando, Galina P.; Tsavlovskii, Dmitrii V.; Khripach, Natalya B.; Lyakhov, Alexander S.; Misharin, Alexander Yu.

    2010-06-01

    A comparative conformational study of steroidal side chain of (22 R,23 R)- and (22 S,23 S)-dihydroxy stigmastane derivatives was performed using single crystal X-ray diffraction and NMR spectroscopy. The preferred conformation in solution was shown to be close to that in the crystal. (22 R,23 R)-Isomers typical for natural plant steroid hormones brassinosteroids adopt a conformation in which both hydroxyl groups are pointed toward unhindered α-side of the steroidal plane and can thus participate in biochemical processes. Unnatural (22 S,23 S)-counterparts exhibit a conformation with the two hydroxyl groups oriented in the opposite direction and sterically hindered by 21-methyl group and terminal side chain fragment.

  18. Spatially selective heteronuclear multiple-quantum coherence (HMQC) spectroscopy for bio-molecular NMR studies

    PubMed Central

    Sathyamoorthy, Bharathwaj; Parish, David M.; Montelione, Gaetano T.; Xiao, Rong; Szyperski, Thomas

    2014-01-01

    Spatially selective heteronuclear multiple-quantum coherence (SS HMQC) NMR spectroscopy was devised for solution studies of proteins. Due to ‘time-staggered’ acquisition of free induction decays (FIDs) in different slices, SS HMQC allows one to employ long delays for longitudinal nuclear spin relaxation at high repetition rates for the acquisition of the FIDs. To also achieve high intrinsic sensitivity, SS HMQC was implemented by combing a single spatially selective 1H excitation pulse with non-selective 1H 180° pulses. High-quality spectra could be obtained within 66 seconds for a 7.6 kDa uniformly 13C,15N-labeled protein, and within 45 and 90 seconds for, respectively, two uniformly 2H,13C,15N-labeled but isoleucine, leucine and valine methyl group protonated proteins with molecular weights of 7.5 and 43 kDa. PMID:24789578

  19. A Kinetic Study of DDGS Hemicellulose Acid Hydrolysis and NMR Characterization of DDGS Hydrolysate.

    PubMed

    Chen, Hanchi; Liu, Shijie

    2015-09-01

    Liquid hot water (LHW) extraction was used as a pretreatment method to separate the hemicellulose fraction from dried distiller's grain with solubles (DDGS) into liquid phase. Acid hydrolysis using 3.264 % w/w sulfuric acid at 130 °C was performed to convert polysaccharides in LHW extract to monosaccharides. The structure characterization of DDGS in anomeric carbon region based on proton NMR and heteronuclear single quantum coherence (HSQC) during acid hydrolysis was studied in this work. It reveals that the sugar units in DDGS hemicelluloses are constructed with (1-4)-β-D-xylopyranose and α-L-arabinofuranosyl residues. A kinetic model is included to explain the changing concentration of monomer, oligomer, and sugar units. The model was further tested based on the changing concentration of five carbon sugar units during hydrolysis. PMID:26198022

  20. 1H NMR studies distinguish the water soluble metabolomic profiles of untransformed and RAS-transformed cells

    PubMed Central

    Marks, Vered; Munoz, Anisleidys; Rai, Priyamvada

    2016-01-01

    Metabolomic profiling is an increasingly important method for identifying potential biomarkers in cancer cells with a view towards improved diagnosis and treatment. Nuclear magnetic resonance (NMR) provides a potentially noninvasive means to accurately characterize differences in the metabolomic profiles of cells. In this work, we use 1H NMR to measure the metabolomic profiles of water soluble metabolites extracted from isogenic control and oncogenic HRAS-, KRAS-, and NRAS-transduced BEAS2B lung epithelial cells to determine the robustness of NMR metabolomic profiling in detecting differences between the transformed cells and their untransformed counterparts as well as differences among the RAS-transformed cells. Unique metabolomic signatures between control and RAS-transformed cell lines as well as among the three RAS isoform-transformed lines were found by applying principal component analysis to the NMR data. This study provides a proof of principle demonstration that NMR-based metabolomic profiling can robustly distinguish untransformed and RAS-transformed cells as well as cells transformed with different RAS oncogenic isoforms. Thus, our data may potentially provide new diagnostic signatures for RAS-transformed cells. PMID:27330862

  1. (1)H NMR studies distinguish the water soluble metabolomic profiles of untransformed and RAS-transformed cells.

    PubMed

    Marks, Vered; Munoz, Anisleidys; Rai, Priyamvada; Walls, Jamie D

    2016-01-01

    Metabolomic profiling is an increasingly important method for identifying potential biomarkers in cancer cells with a view towards improved diagnosis and treatment. Nuclear magnetic resonance (NMR) provides a potentially noninvasive means to accurately characterize differences in the metabolomic profiles of cells. In this work, we use (1)H NMR to measure the metabolomic profiles of water soluble metabolites extracted from isogenic control and oncogenic HRAS-, KRAS-, and NRAS-transduced BEAS2B lung epithelial cells to determine the robustness of NMR metabolomic profiling in detecting differences between the transformed cells and their untransformed counterparts as well as differences among the RAS-transformed cells. Unique metabolomic signatures between control and RAS-transformed cell lines as well as among the three RAS isoform-transformed lines were found by applying principal component analysis to the NMR data. This study provides a proof of principle demonstration that NMR-based metabolomic profiling can robustly distinguish untransformed and RAS-transformed cells as well as cells transformed with different RAS oncogenic isoforms. Thus, our data may potentially provide new diagnostic signatures for RAS-transformed cells. PMID:27330862

  2. Calcination products of gibbsite studied by X-ray diffraction, XPS and solid-state NMR

    SciTech Connect

    Malki, A.; Mekhalif, Z.; Detriche, S.; Fonder, G.; Boumaza, A.; Djelloul, A.

    2014-07-01

    The changes caused by heat treatment of gibbsite powder at 300–1473 K were studied using the X-ray diffraction (XRD), X-ray photoemission (XPS) spectra and {sup 27}Al magic angle spinning nuclear magnetic resonance spectroscopy ({sup 27}Al MAS NMR). XRD analysis indicates that the transformation sequence involves the formation of κ-Al{sub 2}O{sub 3} as an intermediate phase between χ- and α-Al{sub 2}O{sub 3}. The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. XPS analysis indicates that the ratio of aluminium atoms to oxygen atoms in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3} increases, whereas the expected ratio is observed in α-Al{sub 2}O{sub 3}. The percentage of AlO{sub 4} units in the transition aluminas follows the same behaviour as the ratio of Al/O. - Graphical abstract: The percentage of AlO{sub 4} units in transition aluminas follows the same behaviour as the ratio of Al/O. - Highlights: • Calcination products of gibbsite studied by XRD, XPS and solid-state NMR. • The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. • The Al/O atomic ratio determined by XPS is larger than 2/3 in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3}. • The percentage of AlO{sub 4} in the aluminas follows the same behaviour as the Al/O atomic ratio.

  3. Spectroscopic (FT-IR, FT-Raman and NMR) and computational studies on 3-methoxyaniline

    NASA Astrophysics Data System (ADS)

    Sivaranjini, T.; Periandy, S.; Govindarajan, M.; Karabacak, M.; Asiri, A. M.

    2014-01-01

    In this work, the molecular structure, vibrational, UV and NMR spectra of 3-methoxyaniline (abbreviated as 3MOA, C7H9NO) were studied. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies were calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d, p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Comparison of the observed fundamental vibrational frequencies of 3MOA with calculated results by HF and DFT methods indicates that B3LYP is superior to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, Frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) and thermodynamic properties were performed and compared with methoxybenzene and aniline. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the 3MOA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. The 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results.

  4. Membrane interactions in small fast-tumbling bicelles as studied by 31P NMR.

    PubMed

    Bodor, Andrea; Kövér, Katalin E; Mäler, Lena

    2015-03-01

    Small fast-tumbling bicelles are ideal for studies of membrane interactions at molecular level; they allow analysis of lipid properties using solution-state NMR. In the present study we used 31P NMR relaxation to obtain detailed information on lipid head-group dynamics. We explored the effect of two topologically different membrane-interacting peptides on bicelles containing either dimyristoylphosphocholine (DMPC), or a mixture of DMPC and dimyristoylphosphoglycerol (DMPG), and dihexanoylphosphocholine (DHPC). KALP21 is a model transmembrane peptide, designed to span a DMPC bilayer and dynorphin B is a membrane surface active neuropeptide. KALP21 causes significant increase in bicelle size, as evidenced by both dynamic light scattering and 31P T2 relaxation measurements. The effect of dynorphin B on bicelle size is more modest, although significant effects on T2 relaxation are observed at higher temperatures. A comparison of 31P T1 values for the lipids with and without the peptides showed that dynorphin B has a greater effect on lipid head-group dynamics than KALP21, especially at elevated temperatures. From the field-dependence of T1 relaxation data, a correlation time describing the overall lipid motion was derived. Results indicate that the positively charged dynorphin B decreases the mobility of the lipid molecules--in particular for the negatively charged DMPG--while KALP21 has a more modest influence. Our results demonstrate that while a transmembrane peptide has severe effects on overall bilayer properties, the surface bound peptide has a more dramatic effect in reducing lipid head-group mobility. These observations may be of general importance for understanding peptide-membrane interactions. PMID:25497765

  5. An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters

    NASA Astrophysics Data System (ADS)

    Babic, Steven; Schreiner, L. John

    2006-09-01

    In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

  6. An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters.

    PubMed

    Babic, Steven; Schreiner, L John

    2006-09-01

    In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters. PMID:16912375

  7. DNP enhanced NMR using a high-power 94 GHz microwave source: a study of the TEMPOL radical in toluene.

    PubMed

    Kryukov, Eugeny V; Newton, Mark E; Pike, Kevin J; Bolton, David R; Kowalczyk, Radoslaw M; Howes, Andrew P; Smith, Mark E; Dupree, Ray

    2010-06-14

    DNP enhanced (1)H NMR at 143 MHz in toluene is investigated using an NMR spectrometer coupled with a modified EPR spectrometer operating at 94 GHz and TEMPOL as the polarisation agent. A 100 W microwave amplifier was incorporated into the output stage of the EPR instrument so that high microwave powers could be delivered to the probe in either CW or pulsed mode. The maximum enhancement for the ring protons increases from approximately -16 for a 5 mM TEMPOL solution to approximately -50 for a 20 mM solution at a microwave power of approximately 480 mW. The temperature dependence of the enhancement, the NMR relaxation rates and the ESR spectrum of TEMPOL were also studied in an effort to obtain information on the dynamics of the system.

  8. (19)F-modified proteins and (19)F-containing ligands as tools in solution NMR studies of protein interactions.

    PubMed

    Sharaf, Naima G; Gronenborn, Angela M

    2015-01-01

    (19)F solution NMR is a powerful and versatile tool to study protein structure and protein-ligand interactions due to the favorable NMR characteristics of the (19)F atom, its absence in naturally occurring biomolecules, and small size. Protocols to introduce (19)F atoms into both proteins and their ligands are readily available and offer the ability to conduct protein-observe (using (19)F-labeled proteins) or ligand-observe (using (19)F-containing ligands) NMR experiments. This chapter provides two protocols for the (19)F-labeling of proteins, using an Escherichia coli expression system: (i) amino acid type-specific incorporation of (19)F-modified amino acids and (ii) site-specific incorporation of (19)F-modified amino acids using recombinantly expressed orthogonal amber tRNA/tRNA synthetase pairs. In addition, we discuss several applications, involving (19)F-modified proteins and (19)F-containing ligands.

  9. Interaction between beta-Purothionin and dimyristoylphosphatidylglycerol: a (31)P-NMR and infrared spectroscopic study.

    PubMed Central

    Richard, Julie-Andrée; Kelly, Isabelle; Marion, Didier; Pézolet, Michel; Auger, Michèle

    2002-01-01

    The interaction of beta-purothionin, a small basic and antimicrobial protein from the endosperm of wheat seeds, with multilamellar vesicles of dimyristoylphosphatidylglycerol (DMPG) was investigated by (31)P solid-state NMR and infrared spectroscopy. NMR was used to study the organization and dynamics of DMPG in the absence and presence of beta-purothionin. The results indicate that beta-purothionin does not induce the formation of nonlamellar phases in DMPG. Two-dimensional exchange spectroscopy shows that beta-purothionin decreases the lateral diffusion of DMPG in the fluid phase. Infrared spectroscopy was used to investigate the perturbations, induced by beta-purothionin, of the polar and nonpolar regions of the phospholipid bilayers. At low concentration of beta-purothionin, the temperature of the gel-to-fluid phase transition of DMPG increases from 24 degrees C to ~33 degrees C, in agreement with the formation of electrostatic interactions between the cationic protein and the anionic phospholipid. At higher protein concentration, the lipid transition is slightly shifted toward lower temperature and a second transition is observed below 20 degrees C, suggesting an insertion of the protein in the hydrophobic core of the lipid bilayer. The results also suggest that the presence of beta-purothionin significantly modifies the lipid packing at the surface of the bilayer to increase the accessibility of water molecules in the interfacial region. Finally, orientation measurements indicate that the alpha-helices and the beta-sheet of beta-purothionin have tilt angles of ~60 degrees and 30 degrees, respectively, relative to the normal of the ATR crystal. PMID:12324425

  10. 15N NMR study of nitrate ion structure and dynamics in hydrotalcite-like compounds

    USGS Publications Warehouse

    Hou, X.; James, Kirkpatrick R.; Yu, P.; Moore, D.; Kim, Y.

    2000-01-01

    We report here the first nuclear magnetic resonance (NMR) spectroscopic study of the dynamical and structural behavior of nitrate on the surface and in the interlayer of hydrotalcite-like compounds (15NO3--HT). Spectroscopically resolvable surface-absorbed and interlayer NO3- have dramatically different dynamical characteristics. The interlayer nitrate shows a well defined, temperature independent uniaxial chemical shift anisotropy (CS A) powder pattern. It is rigidly held or perhaps undergoes rotation about its threefold axis at all temperatures between -100 ??C and +80 ??C and relative humidities (R.H.) from 0 to 100% at room temperature. For surface nitrate, however, the dynamical behavior depends substantially on temperature and relative humidity. Analysis of the temperature and R.H. dependences of the peak width yields reorieritational frequencies which increase from essentially 0 at -100 ??C to 2.6 ?? 105 Hz at 60 ??C and an activation energy of 12.6 kJ/mol. For example, for samples at R.H. = 33%, the surface nitrate is isotropically mobile at frequencies greater than 105 Hz at room temperature, but it becomes rigid or only rotates on its threefold axis at -100 ??C. For dry samples and samples heated at 200 ??C (R.H. near 0%), the surface nitrate is not isotropically averaged at room temperature. In contrast to our previous results for 35Cl--containing hydrotalcite (35Cl--HT), no NMR detectable structural phase transition is observed for 15NO3--HT. The mobility of interlayer nitrate in HT is intermediate between that of carbonate and chloride.

  11. Methyl quantum tunneling and nitrogen-14 NQR NMR studies using a SQUID magnetic resonance spectrometer

    SciTech Connect

    Black, B.E. |

    1993-07-01

    Nuclear Magnetic Resonance (NMR) and Nuclear Quadrupole Resonance (NQR) techniques have been very successful in obtaining molecular conformation and dynamics information. Unfortunately, standard NMR and NQR spectrometers are unable to adequately detect resonances below a few megahertz due to the frequency dependent sensitivity of their Faraday coil detectors. For this reason a new spectrometer with a dc SQUID (Superconducting Quantum Interference Device) detector, which has no such frequency dependence, has been developed. Previously, this spectrometer was used to observe {sup 11}B and {sup 27}Al NQR resonances. The scope of this study was increased to include {sup 23}Na, {sup 51}V, and {sup 55}Mn NQR transitions. Also, a technique was presented to observe {sup 14}N NQR resonances through cross relaxation of the nitrogen polarization to adjacent proton spins. When the proton Zeeman splitting matches one nitrogen quadrupoler transition the remaining two {sup 14}N transitions can be detected by sweeping a saturating rf field through resonance. Additionally, simultaneous excitation of two nitrogen resonances provides signal enhancement which helps to connect transitions from the same site. In this way, nitrogen-14 resonances were observed in several amino acids and polypeptides. This spectrometer has also been useful in the direct detection of methyl quantum tunneling splittings at 4.2 K. Tunneling, frequencies of a homologous series of carboxylic acids were measured and for solids with equivalent crystal structures, an exponential correlation between the tunneling frequency and the enthalpy of fusion is observed. This correlation provides information about the contribution of intermolecular interactions to the energy barrier for methyl rotation.

  12. 1D and 2D NMR studies of isobornyl acrylate - Methyl methacrylate copolymers

    NASA Astrophysics Data System (ADS)

    Khandelwal, Deepika; Hooda, Sunita; Brar, A. S.; Shankar, Ravi

    2011-10-01

    Isobornyl acrylate - methyl methacrylate (B/M) copolymers of different compositions were synthesized by atom transfer radical polymerization (ATRP) using methyl-2-bromopropionate as an initiator and PMDETA copper complex as catalyst under nitrogen atmosphere at 70 °C. 1H NMR spectrum was used to determine the compositions of copolymer. The copolymer compositions were then used to determine the reactivity ratios of monomers. Reactivity ratios of co-monomers in B/M copolymer, determined from linear Kelen-Tudos method (KT) and non linear Error-in-Variable Method (EVM), are rB = 0.41 ± 0.11, rM = 1.11 ± 0.33 and rB = 0.52, rM = 1.31 respectively. The complete resonance assignments of 1H and 13C{ 1H} NMR spectra were carried out with the help of Distortion less Enhancement by Polarization Transfer (DEPT), two-dimensional Heteronuclear Single Quantum Coherence (HSQC). 2D HSQC assignments were further confirmed by 2D Total Correlation Spectroscopy (TOCSY). The carbonyl carbon of B and M units and methyl carbon of M unit were assigned up to triad compositional and configurational sequences whereas β-methylene carbons were assigned up to tetrad compositional and configurational sequences. Similarly the methine carbon of B unit was assigned up to pentad level. 1,3 and 1,4 bond order couplings of carbonyl carbon and quaternary carbon resonances with methine, methylene and methyl protons were studied in detail using 2D Hetero Nuclear Multiple Bond Correlation (HMBC) spectra.

  13. Structural studies of the activation of the two component receiver domain NTRC by multidimensional heteronuclear NMR

    SciTech Connect

    Nohaile, M J

    1996-05-01

    Multidimensional heteronuclear NMR spectroscopy was used to investigate the N-terminal domain of the transcriptional enhancer NTRC (NiTrogen Regulatory protein C). This domain belongs to the family of receiver domains of two-component regulatory systems involved in signal transduction. Phosphorylation of NTRC at D54 leads to an activated form of the molecule which stimulates transcription of genes involved in nitrogen regulation. Three and four dimensional NMR techniques were used to determine an intermediate resolution structure of the unphosphorylated, inactive form of the N-terminal domain of NTRC. The structure is comprised of five {alpha}-helices and a five-stranded {beta}-sheet in a ({beta}/{alpha}){sub 5} topology. Analysis of the backbone dynamics of NTRC indicate that helix 4 and strand 5 are significantly more flexible than the rest of the secondary structure of the protein and that the loops making up the active site are flexible. The short lifetime of phospho-NTRC hampers the study of this form. However, conditions for determining the resonance assignments and, possibly, the three dimensional structure of phosphorylated NTRC have been obtained. Tentative assignments of the phosphorylated form indicate that the majority of the changes that NTRC experiences upon phosphorylation occur in helix 3, strand 4, helix 4, strand 5, and the loop between strand 5 and helix 5 (the 3445 face of NTRC) as well as near the site of phosphorylation. In order to examine a stable, activated form of the protein, constitutively active mutants of NTRC were investigated.

  14. Sparse (13)C labelling for solid-state NMR studies of P. pastoris expressed eukaryotic seven-transmembrane proteins.

    PubMed

    Liu, Jing; Liu, Chang; Fan, Ying; Munro, Rachel A; Ladizhansky, Vladimir; Brown, Leonid S; Wang, Shenlin

    2016-05-01

    We demonstrate a novel sparse (13)C labelling approach for methylotrophic yeast P. pastoris expression system, towards solid-state NMR studies of eukaryotic membrane proteins. The labelling scheme was achieved by co-utilizing natural abundance methanol and specifically (13)C labelled glycerol as carbon sources in the expression medium. This strategy improves the spectral resolution by 1.5 fold, displays site-specific labelling patterns, and has advantages for collecting long-range distance restraints for structure determination of large eukaryotic membrane proteins by solid-state NMR.

  15. Studies of Secondary Melanoma on C57BL/6J Mouse Liver Using 1H NMR Metabolomics

    SciTech Connect

    Feng, Ju; Isern, Nancy G.; Burton, Sarah D.; Hu, Jian Z.

    2013-10-31

    NMR metabolomics, consisting of solid state high resolution (hr) magic angle spinning (MAS) 1H NMR (1H hr-MAS), liquid state high resolution 1H-NMR, and principal components analysis (PCA) has been used to study secondary metastatic B16-F10 melanoma in C57BL/6J mouse liver . The melanoma group can be differentiated from its control group by PCA analysis of the absolute concentrations or by the absolute peak intensities of metabolites from either 1H hr-MAS NMR data on intact liver tissues or liquid state 1H-NMR spectra on liver tissue extracts. In particular, we found that the absolute concentrations of alanine, glutamate, creatine, creatinine, fumarate and cholesterol are elevated in the melanoma group as compared to controls, while the absolute concentrations of succinate, glycine, glucose, and the family of linear lipids including long chain fatty acids, total choline and acylglycerol are decreased. The ratio of glycerophosphocholine to phosphocholine is increased by about 1.5 fold in the melanoma group, while the absolute concentration of total choline is actually lower in melanoma mice. These results suggest the following picture in secondary melanoma metastasis: Linear lipid levels are decreased by beta oxidation in the melanoma group, which contributes to an increase in the synthesis of cholesterol, and also provides an energy source input for TCA cycle. These findings suggest a link between lipid oxidation, the TCA cycle and the hypoxia-inducible factors (HIF) signal pathway in tumor metastases. Thus this study indicates that the metabolic profile derived from NMR analysis can provide a valuable bio-signature of malignancy and cell hypoxia in metastatic melanoma.

  16. Use of NMR saturation transfer difference spectroscopy to study ligand binding to membrane proteins.

    PubMed

    Venkitakrishnan, Rani Parvathy; Benard, Outhiriaradjou; Max, Marianna; Markley, John L; Assadi-Porter, Fariba M

    2012-01-01

    Detection of weak ligand binding to membrane-spanning proteins, such as receptor proteins at low physiological concentrations, poses serious experimental challenges. Saturation transfer difference nuclear magnetic resonance (STD-NMR) spectroscopy offers an excellent way to surmount these problems. As the name suggests, magnetization transferred from the receptor to its bound ligand is measured by directly observing NMR signals from the ligand itself. Low-power irradiation is applied to a (1)H NMR spectral region containing protein signals but no ligand signals. This irradiation spreads quickly throughout the membrane protein by the process of spin diffusion and saturates all protein (1)H NMR signals. (1)H NMR signals from a ligand bound transiently to the membrane protein become saturated and, upon dissociation, serve to decrease the intensity of the (1)H NMR signals measured from the pool of free ligand. The experiment is repeated with the irradiation pulse placed outside the spectral region of protein and ligand, a condition that does not lead to saturation transfer to the ligand. The two resulting spectra are subtracted to yield the difference spectrum. As an illustration of the methodology, we review here STD-NMR experiments designed to investigate binding of ligands to the human sweet taste receptor, a member of the large family of G-protein-coupled receptors. Sweetener molecules bind to the sweet receptor with low affinity but high specificity and lead to a variety of physiological responses.

  17. NMR studies of a bacterial cell culture medium (LB broth): cyclic nucleotides in yeast extracts.

    PubMed

    Rayner, M H; Sadler, P J; Scawen, M D

    1990-03-01

    The composition of LB broth (tryptone, yeast extract and NaCl) was investigated by 1H,31P-NMR spectroscopy, FPLC and gel electrophoresis. An unexpected finding was the high level of 2'3'-cyclic nucleotides, detected by characteristic 31P-NMR resonances in the region 20-21 ppm, originating from the yeast component. 31P-NMR resonances for cyclic nucleotides were observed during the autolysis of Saccharomyces cerevisiae cells, and in model reactions of RNase with RNA.

  18. NMR studies of granular media and two-phase flow in porous media

    NASA Astrophysics Data System (ADS)

    Yang, Xiaoyu

    This dissertation describes two experimental studies of a vibrofluidized granular medium and a preliminary study of two-phase fluid flow in a porous medium using Nuclear Magnetic Resonance (NMR). The first study of granular medium is to test a scaling law of the rise in center of mass in a three-dimensional vibrofluidized granular system. Our granular system consisted of mustard seeds vibrated vertically at 40 Hz from 0g to 14g. We used Magnetic Resonance Imaging (MRI) to measure density profile in vibrated direction. We observed that the rise in center of mass scaled as nu 0alpha/Nlbeta with alpha = 1.0 +/- 0.2 and beta = 0.5 +/- 0.1, where nu 0 is the vibration velocity and Nl is the number of layers of grains in the container. A simple theory was proposed to explain the scaling exponents. In the second study we measured both density and velocity information in the same setup of the first study. Pulsed Field Gradient (PFG)-NMR combined with MRI was used to do this measurement. The granular system was fully fluidized at 14.85g 50 Hz with Nl ≤ 4. The velocity distributions at horizontal and vertical direction at different height were measured. The distributions were nearly-Gaussian far from sample bottom and non-Gaussian near sample bottom. Granular temperature profiles were calculated from the velocity distributions. The density and temperature profile were fit to a hydrodynamic theory. The theory agreed with experiments very well. A temperature inversion near top was also observed and explained by additional transport coefficient from granular hydrodynamics. The third study was the preliminary density measurement of invading phase profile in a two-phase flow in porous media. The purpose of this study was to test an invasion percolation with gradient (IPG) theory in two-phase flow of porous media. Two phases are dodecane and water doped with CuSO4. The porous medium was packed glass beads. The front tail width sigma and front width of invading phase were

  19. Compartmentation of Nucleotides in Corn Root Tips Studied by 31P-NMR and HPLC 1

    PubMed Central

    Hooks, Mark A.; Clark, Robert A.; Nieman, Richard H.; Roberts, Justin K. M.

    1989-01-01

    Corn (Zea mays L.) root tips were subjected to different conditions so that nucleotide levels varied over a wide range. Levels of nucleotides in corn root tips were measured using 31P nuclear magnetic resonance (NMR) spectroscopy and high performance liquid chromatography. Results indicate: (a) Similar amounts of NTP and sugar nucleotides were observed by in vivo NMR and in extracts. In contrast, a significant amount of NDP observed in root tip extracts was not detected by in vivo NMR. Thus, for a given sample, [NTP]/[NDP] ratios determined in vivo by 31P-NMR are always higher than ratios observed in extracts, deviating by ∼4-fold at the highest ratios. The NMR-invisible pool of NDP appeared quite metabolically inert, barely changing in size as total cell NDP changed. We conclude that NDP in corn root tips is compartmented with respect to NMR visibility, and that it is the NMR-visible pool which responds dynamically to metabolic state. The NMR-invisible NDP could either be immobilized (and so have broad, undetectable NMR signals), or be complexed with species that cause the chemical shift of NDP to change (so it does not contribute to the NMR signal of free NDP), or both. (b) 31P-NMR cannot distinguish between bases (A, U, C, and G) of nucleotides. HPLC analysis of root tip extracts showed that the relative amount of each base in the NTP and NDP pools was quite constant in the different samples. (c) In extracts, for each of the nonadenylate nucleotides, [NTP]/[NDP] was linearly proportional to [ATP]/[ADP], indicating near equilibrium in the nucleoside diphosphokinase (NDPK) reaction. However, the apparent equilibrium constants for the phosphorylation of GDP and UDP by ATP were significantly lower than 1, the true equilibrium constant for the NDPK reaction. Thus, for a given sample, [ATP]/[ADP] ∼ [CTP]/[CDP] > [UTP]/[UDP] > [GTP]/[GDP]. This result suggests that the different NDPs in corn root tips do not have equal access to NDPK. PMID:16666649

  20. NMR Study of Ion Dynamics and Charge Storage in Ionic Liquid Supercapacitors

    PubMed Central

    2015-01-01

    Ionic liquids are emerging as promising new electrolytes for supercapacitors. While their higher operating voltages allow the storage of more energy than organic electrolytes, they cannot currently compete in terms of power performance. More fundamental studies of the mechanism and dynamics of charge storage are required to facilitate the development and application of these materials. Here we demonstrate the application of nuclear magnetic resonance spectroscopy to study the structure and dynamics of ionic liquids confined in porous carbon electrodes. The measurements reveal that ionic liquids spontaneously wet the carbon micropores in the absence of any applied potential and that on application of a potential supercapacitor charging takes place by adsorption of counterions and desorption of co-ions from the pores. We find that adsorption and desorption of anions surprisingly plays a more dominant role than that of the cations. Having elucidated the charging mechanism, we go on to study the factors that affect the rate of ionic diffusion in the carbon micropores in an effort to understand supercapacitor charging dynamics. We show that the line shape of the resonance arising from adsorbed ions is a sensitive probe of their effective diffusion rate, which is found to depend on the ionic liquid studied, as well as the presence of any solvent additives. Taken as whole, our NMR measurements allow us to rationalize the power performances of different electrolytes in supercapacitors. PMID:25973552

  1. Intracellular pH and inorganic phosphate content of heart in vivo: A sup 31 P-NMR study

    SciTech Connect

    Katz, L.A.; Swain, J.A.; Portman, M.A.; Balaban, R.S. )

    1988-07-01

    Studies were performed to determine the contribution of red blood cells to the {sup 31}P-nuclear magnetic resonance (NMR) spectrum of the canine heart in vivo and the feasibility of measuring myocardial intracellular phosphate and pH. This was accomplished by replacing whole blood with a perfluorochemical perfusion emulsion blood substitute, Oxypherol, and noting the difference in the {sup 31}P-NMR spectrum of the heart. NMR data were collected with a NMR transmitter-receiver coil on the surface of the distal portion of the left ventricle. These studies demonstrated that a small contribution from 2,3-diphosphoglycerate (2,3-DPG) and phosphodiesters in the blood could be detected. The magnitude and shift of these blood-borne signals permitted the relative quantification of intracellular inorganic phosphate (P{sub i}) content as well as intracellular pH. Under resting conditions, the intracellular ATP/P{sub i} was 7.0 {plus minus} 0.08. This corresponds to a free intracellular P{sub 1} content of {approx} 0.8 {mu}mol./g wet wt. The intracellular pH was 7.10 {plus minus} 0.01. Acute respiratory alkalosis and acidosis, with the arterial pH ranging from {approximately}7.0 to 7.7, resulted in only small changes in the intracellular pH. These latter results demonstrate an effective myocardial intracellular proton-buffering mechanism in vivo.

  2. Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy, a new approach to study humic material?

    NASA Astrophysics Data System (ADS)

    Knicker, Heike; Lange, Sascha; van Rossum, Barth; Oschkinat, Hartmut

    2016-04-01

    Compared to solution NMR spectroscopy, solid-state NMR spectra suffer from broad resonance lines and low resolution. This could be overcome by the use of 2-dimenstional solid-state NMR pulse sequences. Until recently, this approach has been unfeasible as a routine tool in soil chemistry, mainly because of the low NMR sensitivity of the respective samples. A possibility to circumvent those sensitivity problems represents high-field Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy (Barnes et al., 2008), allowing considerable signal enhancements (Akbey et al., 2010). This is achieved by a microwave-driven transfer of polarization from a paramagnetic center to nuclear spins. Application of DNP to MAS spectra of biological systems (frozen solutions) showed enhancements of the factor 40 to 50 (Hall et al., 1997). Enhancements of this magnitude, thus may enable the use of at least some of the 2D solid-state NMR techniques that are presently already applied for pure proteins but are difficult to apply to soil peptides in their complex matrix. After adjusting the required acquisition parameters to the system "soil organic matter", lower but still promising enhancement factors were achieved. Additional optimization was performed and allowed the acquisition of 2D 13C and 15N solid-state NMR spectra of humified 13C and 15N enriched plant residues. Within the present contribution, the first solid-state DNP NMR spectra of humic material are presented. Those data demonstrate the great potential of this approach which certainly opens new doors for a better understanding of biochemical processes in soils, sediments and water. Akbey, Ü., Franks, W.T., Linden, A., Lange, S., Griffin, R.G., van Rossum, B.-J., Oschkinat, H., 2010. Dynamic nuclear polarization of deuterated proteins. Angewandte Chemie International Edition 49, 7803-7806. Barnes, A.B., De Paëpe, G., van der Wel, P.C.A., Hu, K.N., Joo, C.G., Bajaj, V.S., Mak-Jurkauskas, M.L., Sirigiri, J.R., Herzfeld, J

  3. /sup 31/P NMR studies of ATP synthesis and hydrolysis kinetics in the intact myocardium

    SciTech Connect

    Kingsley-Hickman, P.B.; Sako, E.Y.; Mohanakrishnan, P.; Robitaille, P.M.L.; From, A.H.L.; Foker, J.E.; Ugurbil, K.

    1987-11-17

    The origin of the nuclear magnetic resonance (NMR)-measurable ATP in equilibrium P/sub i/ exchange and whether it can be used to determine net oxidative ATP synthesis rates in the intact myocardium were examined by detailed measurements of ATP in equilibrium P/sub i/ exchange rates in both directions as a function of the myocardial oxygen consumption rate (MVO/sub 2/) in (1) glucose-perfused, isovolumic rat hearts with normal glycolytic activity and (2) pyruvate-perfused hearts where glycolytic activity was reduced or eliminated either by depletion of their endogenous glycogen or by use of the inhibitor iodoacetate. In glucose-perfused hearts, the P/sub i/ ..-->.. ATP rate measured by the conventional two-site saturation transfer (CST) technique remained constant while MVO2 was increased approximately 2-fold. When the glycolytic activity was reduced, the P/sub i/ ..-->.. ATP rate decreased significantly, demonstrating the existence of a significant glycolytic contribution. The ATP ..-->.. P/sub i/ rates and rate:MVO ratios measured by the multiple-site saturation transfer method at two MVO/sub 2/ levels were equal to the corresponding P/sub i/..-->.. ATP rates and rate:MVO ratios obtained in the absence of a glycolytic contribution. The following conclusions are drawn from these studies: (1) unless the glycolytic contribution to the ATP in equilibrium P/sub i/ exchange is inhibited or is specifically shown not to exist, the myocardial P/sub i/ in equilibrium ATP exchange due to oxidative phosphorylation cannot be studied by NMR; (2) at moderate MVO/sub 2/ levels, the reaction catalyzed by the two glycolytic enzymes glyceraldehyde-3-phosphate dehydrogenase and 3-phosphoglycerate kinase is near equilibrium; (3) the ATP synthesis by the mitochondrial H/sup +/-ATPase occurs unidirectionally (i.e., the reaction is far out of equilibrium); (4) the operative P:O ratio in the intact myocardium under our conditions is significantly less than the canonically accepted value

  4. Compositional differences among Chinese soy sauce types studied by (13)C NMR spectroscopy coupled with multivariate statistical analysis.

    PubMed

    Kamal, Ghulam Mustafa; Wang, Xiaohua; Bin Yuan; Wang, Jie; Sun, Peng; Zhang, Xu; Liu, Maili

    2016-09-01

    Soy sauce a well known seasoning all over the world, especially in Asia, is available in global market in a wide range of types based on its purpose and the processing methods. Its composition varies with respect to the fermentation processes and addition of additives, preservatives and flavor enhancers. A comprehensive (1)H NMR based study regarding the metabonomic variations of soy sauce to differentiate among different types of soy sauce available on the global market has been limited due to the complexity of the mixture. In present study, (13)C NMR spectroscopy coupled with multivariate statistical data analysis like principle component analysis (PCA), and orthogonal partial least square-discriminant analysis (OPLS-DA) was applied to investigate metabonomic variations among different types of soy sauce, namely super light, super dark, red cooking and mushroom soy sauce. The main additives in soy sauce like glutamate, sucrose and glucose were easily distinguished and quantified using (13)C NMR spectroscopy which were otherwise difficult to be assigned and quantified due to serious signal overlaps in (1)H NMR spectra. The significantly higher concentration of sucrose in dark, red cooking and mushroom flavored soy sauce can directly be linked to the addition of caramel in soy sauce. Similarly, significantly higher level of glutamate in super light as compared to super dark and mushroom flavored soy sauce may come from the addition of monosodium glutamate. The study highlights the potentiality of (13)C NMR based metabonomics coupled with multivariate statistical data analysis in differentiating between the types of soy sauce on the basis of level of additives, raw materials and fermentation procedures. PMID:27343582

  5. NMR studies of DNA oligomers and their interactions with minor groove binding ligands

    SciTech Connect

    Fagan, P A

    1996-05-01

    The cationic peptide ligands distamycin and netropsin bind noncovalently to the minor groove of DNA. The binding site, orientation, stoichiometry, and qualitative affinity of distamycin binding to several short DNA oligomers were investigated by NMR spectroscopy. The oligomers studied contain A,T-rich or I,C-rich binding sites, where I = 2-desaminodeoxyguanosine. I{center_dot}C base pairs are functional analogs of A{center_dot}T base pairs in the minor groove. The different behaviors exhibited by distamycin and netropsin binding to various DNA sequences suggested that these ligands are sensitive probes of DNA structure. For sites of five or more base pairs, distamycin can form 1:1 or 2:1 ligand:DNA complexes. Cooperativity in distamycin binding is low in sites such as AAAAA which has narrow minor grooves, and is higher in sites with wider minor grooves such as ATATAT. The distamycin binding and base pair opening lifetimes of I,C-containing DNA oligomers suggest that the I,C minor groove is structurally different from the A,T minor groove. Molecules which direct chemistry to a specific DNA sequence could be used as antiviral compounds, diagnostic probes, or molecular biology tools. The author studied two ligands in which reactive groups were tethered to a distamycin to increase the sequence specificity of the reactive agent.

  6. Docking, synthesis, and NMR studies of mannosyl trisaccharide ligands for DC-SIGN lectin.

    PubMed

    Reina, José J; Díaz, Irene; Nieto, Pedro M; Campillo, Nuria E; Páez, Juan A; Tabarani, Georges; Fieschi, Franck; Rojo, Javier

    2008-08-01

    DC-SIGN, a lectin, which presents at the surface of immature dendritic cells, constitutes nowadays a promising target for the design of new antiviral drugs. This lectin recognizes highly glycosylated proteins present at the surface of several pathogens such as HIV, Ebola virus, Candida albicans, Mycobacterium tuberculosis, etc. Understanding the binding mode of this lectin is a topic of tremendous interest and will permit a rational design of new and more selective ligands. Here, we present computational and experimental tools to study the interaction of di- and trisaccharides with DC-SIGN. Docking analysis of complexes involving mannosyl di- and trisaccharides and the carbohydrate recognition domain (CRD) of DC-SIGN have been performed. Trisaccharides Manalpha1,2[Manalpha1,6]Man 1 and Manalpha1,3[Manalpha1,6]Man 2 were synthesized from an orthogonally protected mannose as a common intermediate. Using these ligands and the soluble extracellular domain (ECD) of DC-SIGN, NMR experiments based on STD and transfer-NOE were performed providing additional information. Conformational analysis of the mannosyl ligands in the free and bound states was done. These studies have demonstrated that terminal mannoses at positions 2 or 3 in the trisaccharides are the most important moiety and present the strongest contact with the binding site of the lectin. Multiple binding modes could be proposed and therefore should be considered in the design of new ligands. PMID:18633532

  7. Activation of dehydrogenase activity and cardiac respiration: A sup 31 P-NMR study

    SciTech Connect

    Katz, L.A.; Koretsky, A.P.; Balaban, R.S. )

    1988-07-01

    {sup 31}P-NMR studies were performed to determine the tissue phosphate and oxygen consumption effects of known maneuvers on the activation of pyruvate dehydrogenase during work jumps in the perfused rat heart. In control studies of the glucose-perfused heart, work jumps, with pacing, resulted in a 32% increase in oxygen consumption ({dot char}Qo{sub 2}) from 1.72 {plus minus} 0.09 to 2.29 {plus minus} 0.12 mmol O{sub 2}{center dot}h{sup {minus}1}{center dot}g dry wt{sup {minus}1}. During this transition no significant change in the high energy phosphates were detected. In contrast, work jumps did cause changes in the phosphates when the activation of pyruvate dehydrogenase was blocked with 2.5 {mu}g of ruthenium red per milliliter or maximally stimulated with 11 mM pyruvate before the increase in work. The observed increase in {dot char}Qo{sub 2} and inorganic phosphate and calculated increase in ADP are consistent with these phosphates controlling mitochondrial respiration under these conditions. These results suggest that the activation of pyruvate dehydrogenase and/or other dehydrogenases may be an important step in the orchestration of work and {dot char}Qo{sub 2}.

  8. Isoflurane and desflurane at clinically relevant concentrations induce amyloid {beta}-peptide oligomerization: An NMR study

    SciTech Connect

    Mandal, Pravat K Fodale, Vincenzo

    2009-02-13

    Current understanding on Alzheimer's disease (AD) reveals that soluble amyloid {beta}-peptide (A{beta}) oligomeric formation plays an important role in AD pathophysiology. A potential role for several inhaled anesthetics in promoting A{beta} oligomer formation has been suggested. Using a nuclear magnetic resonance (NMR) study, we previously demonstrated that at a high concentration (higher than clinically relevant concentrations), the inhaled anesthetics halothane and isoflurane, interact with specific amino acid residues (G29, A30, and I31) and induce A{beta} oligomerization. The present study confirms this is true at a clinically relevant concentration. Isoflurane and desflurane induce A{beta} oligomerization by inducing chemical shift changes of the critical amino acid residues (G29, A30, and I31), reinforcing the evidence that perturbation of these three crucial residues indeed plays an important role in oligomerization. These findings support the emerging hypothesis that several commonly used inhaled anesthetics could be involved in neurodegeneration, as well as risk factor for accelerating the onset of AD.

  9. A REDOR NMR Study of a Phosphorylated Statherin Fragment Bound to Hydroxyapatite Crystals

    SciTech Connect

    Gibson, James M.; Raghunathan, Vinodhkumar; Popham, Jennifer M.; Stayton, Patrick; Drobny, Gary P.

    2005-06-09

    Acidic proteins found in mineralized tissues act as nature's crystal engineers, where they play a key role in promoting or inhibiting the growth of minerals such as hydroxyapatite (HAP), Ca10(PO4)6- (OH)2, the main mineral component of bone and teeth. There is remarkably little known about the protein structure-function relationships and the recognition processes governing hard tissue engineering. It is well-known that several salivary proteins (statherin) and peptides (SN-15, N-terminal 15 amino fragment of statherin) bind strongly to HAP to regulate crystal growth.1 In this work, we describe how solid-state NMR can be used to identify which amino acid side chains of SN-15 (DpSpSEE15NKFLRRIGRFG) interact with the HAP surface, even in the presence of phosphorylated side chains. Prior structural studies have indicated that the second through twelfth amino acids are R-helical in full length statherin on HAP, while the SN-15 fragment is in an extended structure toward the N-terminus, only gaining R-helical structure at the seventh amino acid. Additionally, prior dynamics studies have indicated that the region from the seventh amino acid to the C-terminus interacts less strongly with the HAP surface than the first six amino acids.

  10. NMR relaxation study of water dynamics in superparamagnetic iron-oxide-loaded vesicles

    NASA Astrophysics Data System (ADS)

    Chen, Yu-Wen; Hsieh, Chu-Jung; Lin, Chao-Min; Hwang, Dennis W.

    2013-02-01

    Superparamagnetic iron oxide (SPIO) nanoparticles have been introduced as contrast agents for clinical applications in magnetic resonance imaging. Recently, SPIO has been also used for tracking cells. However, NMR relaxation of water molecules behaves differently in a SPIO solution and SPIO-loaded cells. In this study, we used water-in-oil-in-water double emulsions to mimic cellular environments. The MR relaxation induced by the SPIO-loaded vesicles and SPIO solution indicates that T2* is sensitive to the iron concentration alone, and the behavior was very similar in both SPIO-loaded vesicles and SPIO solution. However, T2 relaxation of water in SPIO-loaded vesicles was faster than that in a SPIO solution. In addition, the contribution of water inside and outside the vesicles was clarified by replacing H2O with D2O, and water inside the vesicles was found to cause a nonlinear iron concentration dependency. The studied dilution revealed that vesicle aggregation undergoes a structural transition upon dilution by a certain amount of water. R2* relaxation is sensitive to this structural change and shows an obvious nonlinear iron concentration dependency when the SPIO loading is sufficiently high. Random walk simulations demonstrated that in the assumed model, the vesicles aggregate structures causing the differences between R2* and R2 relaxation of water in vesicles in the presence of SPIO particles.

  11. NMR studies of the equilibria and reaction rates in aqueous solutions of formaldehyde.

    PubMed

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2015-03-26

    Formaldehyde has an important role in the chemical industry and in biological sciences. In dilute aqueous solutions of formaldehyde only traces of the molecular formaldehyde are present and the predominant species are methylene glycol and in lower concentrations, dimethylene glycol. The chemical equilibria and reaction rates of the hydration of formaldehyde in H2O and D2O solutions at low concentrations were studied by (1)H and (13)C NMR at various conditions of pH (1.8-7.8) and temperature (278-333 K). These measurements became possible by direct detection of formaldehyde (13)C and (1)H peaks. The equilibrium and rate constants of the dimerization reaction of methylene glycol were also measured. The rate constants for both the hydration and the dimerization reactions were measured by a new version of the conventional selective inversion transfer method. This study, together with previous published work, completes the description of dynamics and equilibria of all the processes occurring in dilute aqueous formaldehyde solutions.

  12. NMR and molecular dynamics studies of the interaction of melatonin with calmodulin

    PubMed Central

    Turjanski, Adrián G.; Estrin, Darío A.; Rosenstein, Ruth E.; McCormick, John E.; Martin, Stephen R.; Pastore, Annalisa; Biekofsky, Rodolfo R.; Martorana, Vincenzo

    2004-01-01

    Pineal hormone melatonin (N-acetyl-5-methoxytryptamine) is thought to modulate the calcium/calmodulin signaling pathway either by changing intracellular Ca2+ concentration via activation of its G-protein–coupled membrane receptors, or through a direct interaction with calmodulin (CaM). The present work studies the direct interaction of melatonin with intact calcium-saturated CaM both experimentally, by fluorescence and nuclear magnetic resonance spectroscopies, and theoretically, by molecular dynamics simulations. The analysis of the experimental data shows that the interaction is calcium-dependent. The affinity, as obtained from monitoring 15N and 1H chemical shift changes for a melatonin titration, is weak (in the millimolar range) and comparable for the N- and C-terminal domains. Partial replacement of diamagnetic Ca2+ by paramagnetic Tb3+ allowed the measurement of interdomain NMR pseudocontact shifts and residual dipolar couplings, indicating that each domain movement in the complex is not correlated with the other one. Molecular dynamics simulations allow us to follow the dynamics of melatonin in the binding pocket of CaM. Overall, this study provides an example of how a combination of experimental and theoretical approaches can shed light on a weakly interacting system of biological and pharmacological significance. PMID:15498938

  13. Methodology for solid state NMR off-resonance study of molecular dynamics in heteronuclear systems.

    PubMed

    Jurga, Kazimierz; Woźniak-Braszak, Aneta; Baranowski, Mikołaj

    2015-10-01

    Methodology for the study of dynamics in heteronuclear systems in the laboratory frame was described in the previous paper [1]. Now the methodology for the study of molecular dynamics in the solid state heteronuclear systems in the rotating frame is presented. The solid state NMR off-resonance experiments were carried out on a homemade pulse spectrometer operating at the frequency of 30.2 MHz for protons. This spectrometer includes a specially designed probe which contains two independently tuned and electrically isolated coils installed in the coaxial position on the dewar. A unique probe design allows working at three slightly differing frequencies off and on resonance for protons and at the frequency of 28.411 MHz for fluorine nuclei with complete absence of their electrical interference. The probe allows simultaneously creating rf magnetic fields at off-resonance frequencies within the range of 30.2-30.6 MHz and at the frequency of 28.411 MHz. Presented heteronuclear cross-relaxation off-resonance experiments in the rotating frame provide information about molecular dynamics.

  14. Docking, synthesis, and NMR studies of mannosyl trisaccharide ligands for DC-SIGN lectin.

    PubMed

    Reina, José J; Díaz, Irene; Nieto, Pedro M; Campillo, Nuria E; Páez, Juan A; Tabarani, Georges; Fieschi, Franck; Rojo, Javier

    2008-08-01

    DC-SIGN, a lectin, which presents at the surface of immature dendritic cells, constitutes nowadays a promising target for the design of new antiviral drugs. This lectin recognizes highly glycosylated proteins present at the surface of several pathogens such as HIV, Ebola virus, Candida albicans, Mycobacterium tuberculosis, etc. Understanding the binding mode of this lectin is a topic of tremendous interest and will permit a rational design of new and more selective ligands. Here, we present computational and experimental tools to study the interaction of di- and trisaccharides with DC-SIGN. Docking analysis of complexes involving mannosyl di- and trisaccharides and the carbohydrate recognition domain (CRD) of DC-SIGN have been performed. Trisaccharides Manalpha1,2[Manalpha1,6]Man 1 and Manalpha1,3[Manalpha1,6]Man 2 were synthesized from an orthogonally protected mannose as a common intermediate. Using these ligands and the soluble extracellular domain (ECD) of DC-SIGN, NMR experiments based on STD and transfer-NOE were performed providing additional information. Conformational analysis of the mannosyl ligands in the free and bound states was done. These studies have demonstrated that terminal mannoses at positions 2 or 3 in the trisaccharides are the most important moiety and present the strongest contact with the binding site of the lectin. Multiple binding modes could be proposed and therefore should be considered in the design of new ligands.

  15. Probing the surface of a sweet protein: NMR study of MNEI with a paramagnetic probe

    PubMed Central

    Niccolai, Neri; Spadaccini, Roberta; Scarselli, Maria; Bernini, Andrea; Crescenzi, Orlando; Spiga, Ottavia; Ciutti, Arianna; Di Maro, Daniela; Bracci, Luisa; Dalvit, Claudio; Temussi, Piero A.

    2001-01-01

    The design of safe sweeteners is very important for people who are affected by diabetes, hyperlipemia, and caries and other diseases that are linked to the consumption of sugars. Sweet proteins, which are found in several tropical plants, are many times sweeter than sucrose on a molar basis. A good understanding of their structure–function relationship can complement traditional SAR studies on small molecular weight sweeteners and thus help in the design of safe sweeteners. However, there is virtually no sequence homology and very little structural similarity among known sweet proteins. Studies on mutants of monellin, the best characterized of sweet proteins, proved not decisive in the localization of the main interaction points of monellin with its receptor. Accordingly, we resorted to an unbiased approach to restrict the search of likely areas of interaction on the surface of a typical sweet protein. It has been recently shown that an accurate survey of the surface of proteins by appropriate paramagnetic probes may locate interaction points on protein surface. Here we report the survey of the surface of MNEI, a single chain monellin, by means of a paramagnetic probe, and a direct assessment of bound water based on an application of ePHOGSY, an NMR experiment that is ideally suited to detect interactions of small ligands to a protein. Detailed surface mapping reveals the presence, on the surface of MNEI, of interaction points that include residues previously predicted by ELISA tests and by mutagenesis. PMID:11468346

  16. Application of solid state NMR for the study of surface bound species and fossil fuels

    NASA Astrophysics Data System (ADS)

    Althaus, Stacey

    Recent advances in solid state NMR have been utilized to study a variety of systems. These advancements have allowed for the acquisition of sequences previously only available for solution state detection. The protocol for the measurement of coals and other carbonaceous materials was updated to incorporate the recent advancements in fast magic angle spinning (MAS) and high magnetic fields. Argonne Premium Coals were used to test the sensitivity and resolution of the experiments preformed at high field and fast MAS. The higher field spectra were shown to be slightly less sensitive than the traditional lower field spectra, however, the new high field fast MAS spectra had better resolution. This increased resolution allowed for the separation of a variety of different functional groups, thereby allowing the composition of the coal to be determined. The use of 1 H detection allowed for 2D spectra of coals for the first time. These spectra could be filtered to examine either through-space or through-bond correlations. Indirect detection via 1 H was also pivotal in the detection of natural abundance 15 N spectra. Through-space and through-bond 2D spectra of natural abundance bulk species are shown with a sensitivity increase of 15 fold over traditional detection. This sensitivity enhancement allowed for the detection of natural abundance 15 N surface bound species in 2D, something that could not be acquired via traditional methods. The increased efficiency of the through-space magnetization transfer, Cross polarization, at fast MAS compared to the slower MAS rates is shown. The through-bond magnetization transfer via INEPT was examined and the effect of J-coupling is confirmed. Solid State NMR can be utilized to help improve catalytic interactions. Solid state NMR was used to examine the aldol condensation between p-nitrobenzaldehyde and acetone. The formation of a stable intermediate with p-nitrobenzaldehyde was found on the primary functionalized amine mesoporous

  17. Transport Properties of Ibuprofen Encapsulated in Cyclodextrin Nanosponge Hydrogels: A Proton HR-MAS NMR Spectroscopy Study.

    PubMed

    Ferro, Monica; Castiglione, Franca; Punta, Carlo; Melone, Lucio; Panzeri, Walter; Rossi, Barbara; Trotta, Francesco; Mele, Andrea

    2016-01-01

    The chemical cross-linking of β-cyclodextrin (β-CD) with ethylenediaminetetraacetic dianhydride (EDTA) led to branched polymers referred to as cyclodextrin nanosponges (CDNSEDTA). Two different preparations are described with 1:4 and 1:8 CD-EDTA molar ratios. The corresponding cross-linked polymers were contacted with 0.27 M aqueous solution of ibuprofen sodium salt (IP) leading to homogeneous, colorless, drug loaded hydrogels. The systems were characterized by high resolution magic angle spinning (HR-MAS) NMR spectroscopy. Pulsed field gradient spin echo (PGSE) NMR spectroscopy was used to determine the mean square displacement (MSD) of IP inside the polymeric gel at different observation times td. The data were further processed in order to study the time dependence of MSD: MSD = f(td). The proposed methodology is useful to characterize the different diffusion regimes that, in principle, the solute may experience inside the hydrogel, namely normal or anomalous diffusion. The full protocols including the polymer preparation and purification, the obtainment of drug-loaded hydrogels, the NMR sample preparation, the measurement of MSD by HR-MAS NMR spectroscopy and the final data processing to achieve the time dependence of MSD are here reported and discussed. The presented experiments represent a paradigmatic case and the data are discussed in terms of innovative approach to the characterization of the transport properties of an encapsulated guest within a polymeric host of potential application for drug delivery. PMID:27585291

  18. Metabolic profiling for studying chemotype variations in Withania somnifera (L.) Dunal fruits using GC-MS and NMR spectroscopy.

    PubMed

    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.

  19. One new and six known triterpene xylosides from Cimicifuga racemosa: FT-IR, Raman and NMR studies and DFT calculations

    NASA Astrophysics Data System (ADS)

    Jamróz, Marta K.; Jamróz, Michał H.; Cz. Dobrowolski, Jan; Gliński, Jan A.; Gleńsk, Michał

    One new and six known triterpene xylosides were isolated from Cimicifuga racemosa (black cohosh, Actaea racemosa). The structure of a new compound, designated as isocimipodocarpaside (1), was established to be (24S)-3β-hydroxy-24,25-oxiirane-16,23-dione-9,10-seco-9,19-cyclolanost-1(10),7(8),9(11)-trien 3-O-β-D-xylopyranoside, by means of 1H and 13C NMR, IR and Raman spectroscopies and Mass Spectrometry. The six known compounds are: 23-epi-26-deoxycimicifugoside (2), 23-epi-26-deoxyactein (3), 25-anhydrocimigenol xyloside (4), 23-O-acetylshengmanol xyloside (5), 25-O-acetylcimigenol xyloside (6) and 3'-O-acetylcimicifugoside H-1 (7). On the basis of NMR data supported by DFT calculations of NMR shielding constants of (2), its structure, previously described as 26-deoxycimicifugoside was corrected and determined as 23-epi-26-deoxycimicifugoside. The 13C CPMAS NMR spectra of the studied compounds (1)-(7) provided data on their solid-state interactions. The IR and Raman spectra in the Cdbnd O, Cdbnd C, and Csbnd H stretching vibration regions clearly discriminate different triterpenes found in C. racemosa.

  20. Metabolic Characterization of Advanced Liver Fibrosis in HCV Patients as Studied by Serum 1H-NMR Spectroscopy

    PubMed Central

    Embade, Nieves; Mariño, Zoe; Diercks, Tammo; Cano, Ainara; Lens, Sabela; Cabrera, Diana; Navasa, Miquel; Falcón-Pérez, Juan M.; Caballería, Joan; Castro, Azucena; Bosch, Jaume; Mato, José M.; Millet, Oscar

    2016-01-01

    Several etiologies result in chronic liver diseases including chronic hepatitis C virus infection (HCV). Despite its high incidence and the severe economic and medical consequences, liver disease is still commonly overlooked due to the lack of efficient non-invasive diagnostic methods. While several techniques have been tested for the detection of fibrosis, the available biomarkers still present severe limitations that preclude their use in clinical diagnostics. Liver diseases have also been the subject of metabolomic analysis. Here, we demonstrate the suitability of 1H NMR spectroscopy for characterizing the metabolism of liver fibrosis induced by HCV. Serum samples from HCV patients without fibrosis or with liver cirrhosis were analyzed by NMR spectroscopy and the results were submitted to multivariate and univariate statistical analysis. PLS-DA test was able to discriminate between advanced fibrotic and non-fibrotic patients and several metabolites were found to be up or downregulated in patients with cirrhosis. The suitability of the most significantly regulated metabolites was validated by ROC analysis. Our study reveals that choline, acetoacetate and low-density lipoproteins are the most informative biomarkers for predicting cirrhosis in HCV patients. Our results demonstrate that statistical analysis of 1H-NMR spectra is able to distinguish between fibrotic and non-fibrotic patients suffering from HCV, representing a novel diagnostic application for NMR spectroscopy. PMID:27158896

  1. LED based NMR illumination device for mechanistic studies on photochemical reactions - Versatile and simple, yet surprisingly powerful

    NASA Astrophysics Data System (ADS)

    Feldmeier, C.; Bartling, H.; Riedle, E.; Gschwind, R. M.

    2013-07-01

    An LED based illumination device for mechanistic studies on photochemical reactions by means of NMR spectroscopy is presented. The LEDs are directly switched by the NMR spectrometer with the help of a one-stage electronic circuit. This allows for continuous or alternatively pulsed operation of the LEDs. Continuous operation provides direct comparability with conditions in synthetic chemistry, in pulsed operation the short time light power can be enhanced ninefold. The LEDs are efficiently coupled to a 1000 μm core optical fiber guiding the light into the spectrometer by simply bringing it in close contact to the fiber. The tip of the fiber is roughened by sandblasting and thus emits light in a uniform and efficient way over the full length of the receiver coil. The combination of these techniques tremendously increases the amount of light brought into the NMR sample and makes LEDs an easy, versatile and handy light source for the in situ illumination of NMR samples allowing even for single millisecond time resolved Photo-CIDNP spectroscopy.

  2. Homonuclear and Heteronuclear NMR Studies of a Statherin Fragment Bound to Hydroxyapatite Crystals

    SciTech Connect

    Raghunathan, Vinodhkumar; Gibson, James M.; Goobes, Gil; Popham, Jennifer M.; Louie, Elizabeth; Stayton, Patrick; Drobny, Gary P.

    2006-05-11

    Acidic proteins found in mineralized tissues act as nature's crystal engineers, where they play a key role in promoting or inhibiting the growth of minerals such as hydroxyapatite (HAP), Ca10(PO4)6(OH)2, the main mineral component of bone and teeth. Key to understanding the structural basis of protein-crystal recognition and protein control of hard tissue growth is the nature of interactions between the protein side chains and the crystal surface. In an earlier work we have measured the proximity of the lysine (K6) side chain in an SN-15 peptide fragment of the salivary protein statherin adsorbed to the Phosphorus-rich surface of HAP using solid-state NMR recoupling experiments. 15N(31P) rotational echo double resonance (REDOR) NMR data on the side-chain nitrogen in K6 gave rise to three different models of protein-surface interaction to explain the experimental data acquired. In this work we extend the analysis of the REDOR data by examining the contribution of interactions between surface phosphorus atoms to the observed 15N REDOR decay. We performed 31P-31P recoupling experiments in HAP and (NH4)2HPO4 (DHP) to explore the nature of dipolar coupled 31P spin networks. These studies indicate that extensive networks of dipolar coupled 31P spins can be represented as stronger effective dipolar couplings, the existence of which must be included in the analysis of REDOR data. We carried out 15N(31P) REDOR in the case of DHP to determine how the size of the dephasing spin network influences the interpretation of the REDOR data. Although use of an extended 31P coupled spin network simulates the REDOR data well, a simplified 31P dephasing system composed of two spins with a larger dipolar coupling also simulates the REDOR data and only perturbs the heteronuclear couplings very slightly. The 31P-31P dipolar couplings between phosphorus nuclei in HAP can be replaced by an effective dipolar interaction of 600 Hz between two 31P spins. We incorporated this coupling and

  3. (31)P NMR study of post mortem changes in pig muscle.

    PubMed

    Miri, A; Talmant, A; Renou, J P; Monin, G

    1992-01-01

    The rate and the extent of post mortem pH changes in pig muscle largely determine pork quality. Fast pH fall combined with low ultimate pH leads to pale soft exudative (PSE) meat; high ultimate pH leads to dark firm dry (DFD) meat. Post mortem metabolism was studied in pig muscle using(31)P NMR. Fifteen pigs, i.e. 7 Large White pigs and 8 Pietrain pigs, were used. Five pigs of each breed were slaughtered, taking care to minimize preslaughter stress. The other pigs (3 Large Whites and 2 Pietrains) were injected with 0·1 mg adrenaline per kg liveweight before slaughter, in order to increase meat ultimate pH. All the animals were killed by electronarcosis and exsanguination. Three of the adrenaline-treated pigs (1 Large White and 2 Pietrains) gave meat with ultimate pH above 6 (DFD meat). The pigs with normal muscle ultimate pH, i.e. 6 Large Whites and 6 Pietrains, had very variable rates of post mortem muscle metabolism (pH at 30 min after slaughter: 6·17-6·85 in Large Whites; 6·04-6·23 in Pietrains). The relationships between pH and ATP changes were similar in all pigs showing normal muscle ultimate pH, whereas ATP disappeared at a high pH value (on average pH 6·4) in pigs with high ultimate pH. The course of post mortem biochemical changes in a given animal could be predicted rather well by examination of a single(31)P NMR spectrum obtained around 30 min after death. At this time, muscle with a low rate of metabolism simultaneously showed medium to high pH, high ATP content (4-6·8 μmol/g) and rather low Pi content (6-14 μmol/g); muscle with a fast rate of metabolism (PSE-prone muscle) had low pH, low to medium ATP content (1·1-4 μmol/g) and generally high phosphomonoester (PME) content (9-23 μmol/g); muscle with high ultimate pH (DFD-prone muscle) had high pH, low PME content (4-8 μmol/g) and high Pi content (22-27 μmol/g).

  4. An advanced phantom study assessing the feasibility of neuronal current imaging by ultra-low-field NMR

    NASA Astrophysics Data System (ADS)

    Körber, Rainer; Nieminen, Jaakko O.; Höfner, Nora; Jazbinšek, Vojko; Scheer, Hans-Jürgen; Kim, Kiwoong; Burghoff, Martin

    2013-12-01

    In ultra-low-field (ULF) NMR/MRI, a common scheme is to magnetize the sample by a polarizing field of up to hundreds of mT, after which the NMR signal, precessing in a field on the order of several μT, is detected with superconducting quantum interference devices (SQUIDs). In our ULF-NMR system, we polarize with up to 50 mT and deploy a single-stage DC-SQUID current sensor with an integrated input coil which is connected to a wire-wound Nb gradiometer. We developed this system (white noise 0.50 fT/√{Hz}) for assessing the feasibility of imaging neuronal currents by detecting their effect on the ULF-NMR signal. Magnetoencephalography investigations of evoked brain activity showed neuronal dipole moments below 50 nAm. With our instrumentation, we have studied two different approaches for neuronal current imaging. In the so-called DC effect, long-lived neuronal activity shifts the Larmor frequency of the surrounding protons. An alternative strategy is to exploit fast neuronal activity as a tipping pulse. This so-called AC effect requires the proton Larmor frequency to match the frequency of the neuronal activity, which ranges from near-DC to ∼kHz. We emulated neuronal activity by means of a single dipolar source in a physical phantom, consisting of a hollow sphere filled with an aqueous solution of CuSO4 and NaCl. In these phantom studies, with physiologically relevant dipole depths, we determined resolution limits for our set-up for the AC and the DC effect of ∼10 μAm and ∼50 nAm, respectively. Hence, the DC effect appears to be detectable in vivo by current ULF-NMR technology.

  5. An advanced phantom study assessing the feasibility of neuronal current imaging by ultra-low-field NMR.

    PubMed

    Körber, Rainer; Nieminen, Jaakko O; Höfner, Nora; Jazbinšek, Vojko; Scheer, Hans-Jürgen; Kim, Kiwoong; Burghoff, Martin

    2013-12-01

    In ultra-low-field (ULF) NMR/MRI, a common scheme is to magnetize the sample by a polarizing field of up to hundreds of mT, after which the NMR signal, precessing in a field on the order of several μT, is detected with superconducting quantum interference devices (SQUIDs). In our ULF-NMR system, we polarize with up to 50mT and deploy a single-stage DC-SQUID current sensor with an integrated input coil which is connected to a wire-wound Nb gradiometer. We developed this system (white noise 0.50fT/√Hz) for assessing the feasibility of imaging neuronal currents by detecting their effect on the ULF-NMR signal. Magnetoencephalography investigations of evoked brain activity showed neuronal dipole moments below 50nAm. With our instrumentation, we have studied two different approaches for neuronal current imaging. In the so-called DC effect, long-lived neuronal activity shifts the Larmor frequency of the surrounding protons. An alternative strategy is to exploit fast neuronal activity as a tipping pulse. This so-called AC effect requires the proton Larmor frequency to match the frequency of the neuronal activity, which ranges from near-DC to ∼kHz. We emulated neuronal activity by means of a single dipolar source in a physical phantom, consisting of a hollow sphere filled with an aqueous solution of CuSO4 and NaCl. In these phantom studies, with physiologically relevant dipole depths, we determined resolution limits for our set-up for the AC and the DC effect of ∼10μAm and ∼50nAm, respectively. Hence, the DC effect appears to be detectable in vivo by current ULF-NMR technology.

  6. STRUCTURAL STUDIES OF BIOMATERIALS USING DOUBLE-QUANTUM SOLID-STATE NMR SPECTROSCOPY

    SciTech Connect

    Drobny, Gary P.; Long, J. R.; Karlsson, T.; Shaw, Wendy J.; Popham, Jennifer M.; Oyler, N.; Bower, Paula M.; Stringer, J.; Gregory, D.; Mehta, M.; Stayton, Patrick S.

    2004-10-31

    Proteins directly control the nucleation and growth of biominerals, but the details of molecular recognition at the protein-biomineral interface remain poorly understood. The elucidation of recognition mechanisms at this interface may provide design principles for advanced materials development in medical and ceramic composites technologies. Here, we describe both the theory and practice of double-quantum solid-stateNMR(ssNMR) structure-determination techniques, as they are used to determine the secondary structures of surface-adsorbed peptides and proteins. In particular, we have used ssNMR dipolar techniques to provide the first high-resolution structural and dynamic characterization of a hydrated biomineralization protein, salivary statherin, adsorbed to its biologically relevant hydroxyapatite (HAP) surface. Here, we also review NMR data on peptides designed to adsorb from aqueous solutions onto highly porous hydrophobic surfaces with specific helical secondary structures. The adsorption or covalent attachment of biological macromolecules onto polymer materials to improve their biocompatibility has been pursued using a variety of approaches, but key to understanding their efficacy is the verification of the structure and dynamics of the immobilized biomolecules using double-quantum ssNMR spectroscopy.

  7. 31P NMR Kinetics Study of Cardiac Metabolism under Mild Hypoxia

    NASA Astrophysics Data System (ADS)

    Goudemant, J. F.; Elst, L. V.; Vanhaverbeke, Y.; Muller, R. N.

    The effects of mild hypoxia on the metabolic and mechanical functions of isovolumic perfused rat hearts have been studied. 31P NMR has been used to follow the metabolite concentrations as well as the intracellular pH. Additionally, the energy transfer through the creatine kinase reaction was estimated by the magnetization-transfer technique. The needs of myofibrillar energy and of mitochondrial ATP production have been assessed through mechanical activity and oxygen-consumption rate. It has been observed that mild hypoxia simultaneously impairs contractile and metabolic functions. The aerobic ATP production is maintained under these conditions while anaerobic energy metabolism seems accelerated. The accumulation of some metabolites (ADP and P i) and the decrease of creatine kinase forward flux ( Vfor) tend, however, to prove that ATP availability for myofibrils is lowered. The large aerobic energy production observed must therefore be explained by an energy wastage in the mitochondria. In spite of normal ATP concentration, a contractile dysfunction is observed and can be explained by the P i accumulation, which is known to impair the use of the myofibrillar ATP. Another hypothesis supported by the magnetization transfer experiments is the poor ATP availability resulting from the ATP wastage in the mitochondria and from the inefficient energy transport by the PCr-Cr shuttle.

  8. Potentiometric and NMR complexation studies of phenylboronic acid PBA and its aminophosphonate analog with selected catecholamines

    NASA Astrophysics Data System (ADS)

    Ptak, Tomasz; Młynarz, Piotr; Dobosz, Agnieszka; Rydzewska, Agata; Prokopowicz, Monika

    2013-05-01

    Boronic acids are a class of intensively explored compounds, which according to their specific properties have been intensively explored in last decades. Among them phenylboronic acids and their derivatives are most frequently examined as receptors for diverse carbohydrates. In turn, there is a large gap in basic research concerning complexation of catecholamines by these compounds. Therefore, we decided to undertake studies on interaction of chosen catecholamines, namely: noradrenaline (norephinephrine), dopamine, L-DOPA, DOPA-P (phosphonic analog of L-DOPA) and catechol, with simple phenyl boronic acid PBA by means of potentiometry and NMR spectroscopy. For comparison, the binding properties of recently synthesized phenylboronic receptor 1 bearing aminophosphonate function in meta-position were investigated and showed promising ability to bind catecholamines. The protonation and stability constants of PBA and receptor 1 complexes were examined by potentiometry. The obtained results demonstrated that PBA binds the catecholamines with the following affinity order: noradrenaline ⩾ dopamine ≈ L-DOPA > catechol > DOPA-P, while its modified analog 1 reveals slightly different preferences: dopamine > noradrenaline > catechol > L-DOPA > DOPA-P.

  9. Thermodynamic Study on the Protonation Reactions of Glyphosate in Aqueous Solution: Potentiometry, Calorimetry and NMR spectroscopy.

    PubMed

    Liu, Bijun; Dong, Lan; Yu, Qianhong; Li, Xingliang; Wu, Fengchang; Tan, Zhaoyi; Luo, Shunzhong

    2016-03-10

    Glyphosate [N-(phosphonomethyl)glycine] has been described as the ideal herbicide because of its unique properties. There is some conflicting information concerning the structures and conformations involved in the protonation process of glyphosate. Protonation may influence the chemical and physical properties of glyphosate, modifying its structure and the chemical processes in which it is involved. To better understand the species in solution associated with changes in pH, thermodynamic study (potentiometry, calorimetry and NMR spectroscopy) about the protonation pathway of glyphosate is performed. Experimental results confirmed that the order of successive protonation sites of totally deprotonated glyphosate is phosphonate oxygen, amino nitrogen, and finally carboxylate oxygen. This trend is in agreement with the most recent theoretical work in the literature on the subject (J. Phys. Chem. A 2015, 119, 5241-5249). The result is important because it confirms that the protonated site of glyphosate in pH range 7-8, is not on the amino but on the phosphonate group instead. This corrected information can improve the understanding of the glyphosate chemical and biochemical action.

  10. Pyrolysis GC-MS and NMR studies of humics in contaminated sediments

    SciTech Connect

    Higashi, R.M.; Fan, T.W.M.; Lane, A.N.

    1994-12-31

    Sediment ``humics`` play a major role in sorption and chemical reactions of organic and metal pollutants, as well as of nutrients, detritus, and other naturally-occurring chemicals. Not surprisingly, the chemical structure of humics is very important in this regard. The problem is, humics are among the most complex and least-understood substances in the world. This is because the primary structure is heterologous, unlike most other macromolecules which are polymeric; thus, researchers could not obtain coherent structures to identify with properties. However, recent advances in NMR spectroscopy and pyrolysis GC-MS have enabled researchers to begin relating primary and higher order structural motifs germane to the chemistry of the refractory humics. The authors have explored various means of sediment extraction for humics analysis by these techniques, including direct analysis of unextracted sediments. Marine sediments from near produced water discharges, salt marshes, and dredge material were surveyed. The study has revealed interpretive pitfalls, depending on the method of humic extraction. These difficulties are expected since the approach is at its infancy, but the overall approach is clearly useful in probing the humic structure profile of marine sediments.

  11. High-resolution proton NMR studies of intracellular metabolites in yeast using 13C decoupling

    NASA Astrophysics Data System (ADS)

    Sillerud, Laurel O.; Alger, Jeffry R.; Shulman, Robert G.

    The resolution and specificity of 1H NMR in studies of yeast cellular metabolism were increased by feeding a 13C-labeled substrate and observing 1H difference spectra in the presence and absence of 13C decoupling fields. [2- 13C]Acetate was utilized as a respiratory substrate in an aerobic suspension of Saccharomyces cerevisiae. The broad cellular background proton resonances are removed by the technique, leaving only signals from the protons of the substrate, or its metabolites, that are coupled to 13C. Spectra of the yeast suspension after acetate feeding show the disappearance of label from the acetate pool and the subsequent appearance of 13C in glutamate C 3 and C 4 and in aspartate C 3. These results are in accord with the known fluxes of metabolites. Selective single-frequency 13C decoupling was used to provide assignments for the difference signals. The limitations on single-frequency decoupling coming from finite decoupling fields are investigated. The technique shows a potential for application in a wide variety of systems where the resolution of the 13C spectrum may be combined with the sensitivity for proton detection to observe metabolites that have been previously unobservable.

  12. 1H NMR study of the effect of heme insertion on the folding of apomyoglobin

    NASA Astrophysics Data System (ADS)

    Yamamoto, Yasuhiko; Takemoto, Kenji; Matsuo, Hitomi

    2002-01-01

    NMR signals arising from His EF5 and His GH1 N ɛH protons of sperm whale myoglobin and apomyoglobin have been assigned, and the protein folding has been studied through the analysis of these signals. His EF5 and His GH1 N ɛH protons participate in the internal hydrogen bonds at the B-GH and EF-H interfaces, respectively, and their signals are remarkably sensitive to local structural alterations at these sites. The shifts of these signals in alkaline pH condition were only slightly affected by the removal of heme, indicating that the overall protein folding is essentially retained in apoprotein. The line width of His EF5 proton signal, however, increased largely in the spectra of apomyoglobin and this result suggests a conformational lability of the EF-H interface in the absence of heme. Furthermore, the His EF5 proton signal was found to be influenced by not only the orientation of heme relative to the protein, but also by the type of hemin used to reconstitute apomyoglobin. These results clearly demonstrate the presence of a long-range structural correlation between the heme active site and the EF-H interface.

  13. 31P-NMR studies of isolated adult heart cells: effect of myoglobin inactivation.

    PubMed

    Gupta, R K; Wittenberg, B A

    1991-10-01

    31P nuclear magnetic resonance (NMR) studies of isolated adult rat heart cells revealed that the cells maintained high-energy phosphates for up to 6 h in polyamide hollow fibers perfused with well-oxygenated nutrient medium. Glucose plus pyruvate superfused heart cells maintained [phosphocreatine]/[ATP] at 1.4 +/- 0.1, internal pH at 7.09 +/- 0.04 (external pH = 7.25), and intracellular free Mg2+ at 0.51 +/- 0.04 mM. In glucose-containing media, hypoxia was accompanied by a reversible decrease in intracellular ATP and phosphocreatine of approximately 50% and 80%, respectively, while the intracellular free Mg2+ was reversibly increased by 40%. However, inhibition of glycolysis by iodoacetate in aerobic pyruvate-containing medium did not significantly alter high-energy phosphate content. Inactivation of intracellular myoglobin with 1-2 mM sodium nitrite, which reduces the steady-state respiratory oxygen consumption rate by 30%, caused a significant (30%) decrease in intracellular phosphocreatine peak, which was reversed upon removal of sodium nitrite. The nitrite-induced decrease in phosphocreatine was also observed in iodoacetate-treated myocytes but not in oligomycin-treated cells. These results indicate that functional myoglobin enhances high-energy phosphate synthesis in well-oxygenated myocytes. PMID:1928397

  14. 1H and 2H NMR studies of water in work-free wheat flour doughs.

    PubMed

    d'Avignon, D A; Hung, C C; Pagel, M T; Hart, B; Bretthorst, G L; Ackerman, J J

    1991-01-01

    Proton and deuterium NMR relaxation methods were used to characterize water compartmentalization and hydration in work-free wheat flour doughs. Transverse (spin-spin) relaxation measurements define three motionally unique water compartments in the work-free dough preparations. The apparent occupancy fraction and relative mobility of each water domain are found to be functions of moisture content, temperature, and flour type. Additionally, the number of relaxation-resolved water compartments and their characteristic relaxation rate constants are found to depend critically on both moisture content and the interpulse-delay employed for the multi-pulse relaxation experiments. Under controlled experimental conditions, dynamics between the three water compartments can be observed to be consistent with the onset of flour hydration. The most notable observation during the initial period of hydration is a loss of "free" or "loosely bound" water to environments characterized by less mobility. Freezing studies show that hard wheat doughs have slightly less amorphous, non-freezable water than do soft wheat flour doughs prepared under similar conditions. PMID:1746346

  15. Covalent binding of aniline to humic substances. 2. 15N NMR studies of nucleophilic addition reactions

    USGS Publications Warehouse

    Thorn, K.A.; Pettigrew, P.J.; Goldenberg, W.S.; Weber, E.J.

    1996-01-01

    Aromatic amines are known to undergo covalent binding with humic substances in the environment. Although previous studies have examined reaction conditions and proposed mechanisms, there has been no direct spectroscopic evidence for the covalent binding of the amines to the functional groups in humic substances. In order to further elucidate the reaction mechanisms, the Suwannee River and IHSS soil fulvic and humic acids were reacted with 15N-labeled aniline at pH 6 and analyzed using 15N NMR spectrometry. Aniline underwent nucleophilic addition reactions with the quinone and other carbonyl groups in the samples and became incorporated in the form of anilinohydroquinone, anilinoquinone, anilide, imine, and heterocyclic nitrogen, the latter comprising 50% or more of the bound amine. The anilide and anilinohydroquinone nitrogens were determined to be susceptible to chemical exchange by ammonia. In the case of Suwannee River fulvic acid, reaction under anoxic conditions and pretreatment with sodium borohydride or hydroxylamine prior to reaction under oxic conditions resulted in a decrease in the proportion of anilinohydroquinone nitrogen incorporated. The relative decrease in the incorporation of anilinohydroquinone nitrogen with respect to anilinoquinone nitrogen under anoxic conditions suggested that inter- or intramolecular redox reactions accompanied the nucleophilic addition reactions.

  16. A neutron-X-ray, NMR and calorimetric study of glassy Probucol synthesized using containerless techniques

    NASA Astrophysics Data System (ADS)

    Weber, J. K. R.; Benmore, C. J.; Tailor, A. N.; Tumber, S. K.; Neuefeind, J.; Cherry, B.; Yarger, J. L.; Mou, Q.; Weber, W.; Byrn, S. R.

    2013-10-01

    Acoustic levitation was used to trap 1-3 mm diameter drops of Probucol and other pharmaceutical materials in containerless conditions. Samples were studied in situ using X-ray diffraction and ex situ using neutron diffraction, NMR and DSC techniques. The materials were brought into non-equilibrium states by supersaturating solutions or by supercooling melts. The glass transition and crystallization temperatures of glassy Probucol were 29 ± 1 and 71 ± 1 °C respectively. The glassy form was stable with a shelf life of at least 8 months. A neutron/X-ray difference function of the glass showed that while molecular sub-groups remain rigid, many of the hydrogen correlations observed in the crystal become smeared out in the disordered material. The glass is principally comprised of slightly distorted Form I Probucol molecules with disordered packing rather than large changes in the individual molecular structure. Avoiding surface contact-induced nucleation provided access to highly non-equilibrium phases and enabled synthesis of phase-pure glasses.

  17. Solid state 1H NMR studies of cell wall materials of potatoes

    NASA Astrophysics Data System (ADS)

    Tang, Huiru; Belton, Peter S.; Ng, Annie; Waldron, Keith W.; Ryden, Peter

    1999-04-01

    Cell wall materials from potatoes ( Solanum tuberosum) prepared by two different methods have been studied using NMR proton relaxation times. Spin lattice relaxation in both the rotating and laboratory frames as well as transverse relaxation have been measured over a range of temperatures and hydration levels. It was observed that the sample prepared using a DMSO extraction showed anomalous behaviour of spin lattice relaxation in the laboratory frame probably due to residual solvent in the sample. Spin lattice relaxation in the laboratory frame is the result of hydroxymethyl rotation and another unidentified high frequency motion. In the rotating frame relaxation is adequately explained by hydroxymethyl rotation alone. In neither experiment is methyl group rotation observed, calculation suggests that this is due to the low density of methyl groups in the sample. Non-freezing water in potato cell walls, α-cellulose and pectin was found about 0.2, 0.04 and 0.18 g per gram dry matter, indicating preferable hydration of pectin compared to cellulose. The effects of hydration are most noticeable in the measurements that reflect low frequency motions, particularly transverse relaxation, where both second moments and the relative intensity of signals arising from immobile material are reduced by hydration.

  18. Structure and dynamics of aqueous 2-propanol: a THz-TDS, NMR and neutron diffraction study.

    PubMed

    McGregor, James; Li, Ruoyu; Zeitler, J Axel; D'Agostino, Carmine; Collins, James H P; Mantle, Mick D; Manyar, Haresh; Holbrey, John D; Falkowska, Marta; Youngs, Tristan G A; Hardacre, Christopher; Stitt, E Hugh; Gladden, Lynn F

    2015-11-11

    Aqueous liquid mixtures, in particular, those involving amphiphilic species, play an important role in many physical, chemical and biological processes. Of particular interest are alcohol/water mixtures; however, the structural dynamics of such systems are still not fully understood. Herein, a combination of terahertz time-domain spectroscopy (THz-TDS) and NMR relaxation time analysis has been applied to investigate 2-propanol/water mixtures across the entire composition range; while neutron diffraction studies have been carried out at two specific concentrations. Excellent agreement is seen between the techniques with a maximum in both the relative absorption coefficient and the activation energy to molecular motion occurring at ∼90 mol% H2O. Furthermore, this is the same value at which well-established excess thermodynamic functions exhibit a maximum/minimum. Additionally, both neutron diffraction and THz-TDS have been used to provide estimates of the size of the hydration shell around 2-propanol in solution. Both methods determine that between 4 and 5 H2O molecules per 2-propanol are found in the 2-propanol/water clusters at 90 mol% H2O. Based on the acquired data, a description of the structure of 2-propanol/water across the composition range is presented.

  19. Reverse micelle encapsulation of membrane anchored proteins for solution NMR studies

    PubMed Central

    Valentine, Kathleen G.; Peterson, Ronald; Saad, Jamil S.; Summers, Michael F.; Xu, Xianzhong; Ames, James B.; Wand, A. Joshua

    2010-01-01

    SUMMARY Perhaps 5 to 10% of proteins bind to the membranes via a covalently attached lipid. Post-translational attachment of fatty acids such as myristate occurs on a variety of viral and cellular proteins. High-resolution information about the nature of lipidated proteins is remarkably sparse, often because of solubility problems caused by the exposed fatty acids. Reverse micelle encapsulation is used here to study two myristoylated proteins in their lipid-extruded states: myristoylated recoverin, which is a switch in the Ca+2 signaling pathway in vision and the myristoylated HIV-1 matrix protein, which is postulated to be targeted to the plasma membrane through its binding to phosphatidylinositol(4,5)bisphosphate. Both proteins have been successfully encapsulated in the lipid extruded state and high-resolution NMR spectra obtained. Both proteins bind their activating ligands in the reverse micelle. This approach seems broadly applicable to membrane proteins with exposed fatty acid chains that have eluded structural characterization by conventional approaches. PMID:20152148

  20. Solution NMR Spectroscopy Provides an Avenue for the Study of Functionally Dynamic Molecular Machines: The Example of Protein Disaggregation.

    PubMed

    Rosenzweig, Rina; Kay, Lewis E

    2016-02-10

    Solution-based NMR spectroscopy has been an important tool for studying the structure and dynamics of relatively small proteins and protein complexes with aggregate molecular masses under approximately 50 kDa. The development of new experiments and labeling schemes, coupled with continued improvements in hardware, has significantly reduced this size limitation, enabling atomic-resolution studies of molecular machines in the 1 MDa range. In this Perspective, some of the important advances are highlighted in the context of studies of molecular chaperones involved in protein disaggregation. New insights into the structural biology of disaggregation obtained from NMR studies are described, focusing on the unique capabilities of the methodology for obtaining atomic-resolution descriptions of dynamic systems.

  1. A multinuclear solid state NMR spectroscopic study of the structural evolution of disordered calcium silicate sol-gel biomaterials.

    PubMed

    Lin, Zhongjie; Jones, Julian R; Hanna, John V; Smith, Mark E

    2015-01-28

    Disordered sol-gel prepared calcium silicate biomaterials show significant, composition dependent ability to bond with bone. Bone bonding is attributed to rapid hydroxycarbonate apatite (HCA) formation on the glass surface after immersion in body fluid (or implantation). Atomic scale details of the development of the structure of (CaO)x(SiO2)1-x (x = 0.2, 0.3 and 0.5) under heat treatment and subsequent dissolution in simulated body fluid (SBF) are revealed through a multinuclear solid state NMR approach using one-dimensional (17)O, (29)Si, (31)P and (1)H. Central to this study is the combination of conventional static and magic angle spinning (MAS) and two-dimensional (2D) triple quantum (3Q) (17)O NMR experiments that can readily distinguish and quantify the bridging (BOs) and non-bridging (NBOs) oxygens in the silicate network. Although soluble calcium is present in the sol, the (17)O NMR results reveal that the sol-gel produced network structure is initially dominated by BOs after gelation, aging and drying (e.g. at 120 °C), indicating a nanoscale mixture of the calcium salt and a predominantly silicate network. Only once the calcium salt is decomposed at elevated temperatures do the Ca(2+) ions become available to break BO. Apatite forming ability in SBF depends strongly on the surface OH and calcium content. The presence of calcium aids HCA formation via promotion of surface hydration and the ready availability of Ca(2+) ions. (17)O NMR shows the rapid loss of NBOs charge balanced by calcium as it is leached into the SBF. The formation of nanocrystalline, partially ordered HCA can be detected via(31)P NMR. This data indicates the importance of achieving the right balance of BO/NBO for optimal biochemical response and network properties.

  2. A multinuclear solid state NMR spectroscopic study of the structural evolution of disordered calcium silicate sol-gel biomaterials.

    PubMed

    Lin, Zhongjie; Jones, Julian R; Hanna, John V; Smith, Mark E

    2015-01-28

    Disordered sol-gel prepared calcium silicate biomaterials show significant, composition dependent ability to bond with bone. Bone bonding is attributed to rapid hydroxycarbonate apatite (HCA) formation on the glass surface after immersion in body fluid (or implantation). Atomic scale details of the development of the structure of (CaO)x(SiO2)1-x (x = 0.2, 0.3 and 0.5) under heat treatment and subsequent dissolution in simulated body fluid (SBF) are revealed through a multinuclear solid state NMR approach using one-dimensional (17)O, (29)Si, (31)P and (1)H. Central to this study is the combination of conventional static and magic angle spinning (MAS) and two-dimensional (2D) triple quantum (3Q) (17)O NMR experiments that can readily distinguish and quantify the bridging (BOs) and non-bridging (NBOs) oxygens in the silicate network. Although soluble calcium is present in the sol, the (17)O NMR results reveal that the sol-gel produced network structure is initially dominated by BOs after gelation, aging and drying (e.g. at 120 °C), indicating a nanoscale mixture of the calcium salt and a predominantly silicate network. Only once the calcium salt is decomposed at elevated temperatures do the Ca(2+) ions become available to break BO. Apatite forming ability in SBF depends strongly on the surface OH and calcium content. The presence of calcium aids HCA formation via promotion of surface hydration and the ready availability of Ca(2+) ions. (17)O NMR shows the rapid loss of NBOs charge balanced by calcium as it is leached into the SBF. The formation of nanocrystalline, partially ordered HCA can be detected via(31)P NMR. This data indicates the importance of achieving the right balance of BO/NBO for optimal biochemical response and network properties. PMID:25494341

  3. Studies of 3He polarization losses during NMR and EPR measurment and Polarized 3He target cell lifetime

    NASA Astrophysics Data System (ADS)

    An, Peibo

    2014-09-01

    The 3He target cell polarized by spin-exchange optical pumping(SEOP) is used as a neutron substitute to study the inner structure of the neutron. In our lab, nuclear-magnetic-resonance(NMR) is used to measure the relative polarization and electron-paramagnetic-resonance(EPR) is used to measure the spin exchange EPR frequency shift parameter of potassium and rubidium in our target cell presented in magnetic fields. The alkali in the cell is used to facilitate the polarization of 3He. The first part of my work presents the study of the polarization losses of the cell during both NMR and EPR. With the help of improved RF coils, we keep the background noise received by pickup coils reasonably low, but three other kinds of losses are inevitable: losses during Adiabatic Fast Passage (AFP) sweep, losses due to flux change caused by different cell orientation with respect to RF fields and physical losses. Fortunately there is only flux change in NMR measurements. The second part of my work presents the study of cell lifetime improvement. The polarization decreases in a process called relaxation exponentially. The lifetime of a cell is how long it can keep its polarization. The typical lifetime of cells produced in our lab is about 22 hours. With a newly designed vacuum system. The 3He target cell polarized by spin-exchange optical pumping(SEOP) is used as a neutron substitute to study the inner structure of the neutron. In our lab, nuclear-magnetic-resonance(NMR) is used to measure the relative polarization and electron-paramagnetic-resonance(EPR) is used to measure the spin exchange EPR frequency shift parameter of potassium and rubidium in our target cell presented in magnetic fields. The alkali in the cell is used to facilitate the polarization of 3He. The first part of my work presents the study of the polarization losses of the cell during both NMR and EPR. With the help of improved RF coils, we keep the background noise received by pickup coils reasonably low, but

  4. NMR structural study of the prototropic equilibrium in solution of Schiff bases as model compounds.

    PubMed

    Ortegón-Reyna, David; Garcías-Morales, Cesar; Padilla-Martínez, Itzia; García-Báez, Efren; Aríza-Castolo, Armando; Peraza-Campos, Ana; Martínez-Martínez, Francisco

    2013-12-31

    An NMR titration method has been used to simultaneously measure the acid dissociation constant (pKa) and the intramolecular NHO prototropic constant ΔKNHO on a set of Schiff bases. The model compounds were synthesized from benzylamine and substituted ortho-hydroxyaldehydes, appropriately substituted with electron-donating and electron-withdrawing groups to modulate the acidity of the intramolecular NHO hydrogen bond. The structure in solution was established by 1H-, 13C- and 15N-NMR spectroscopy. The physicochemical parameters of the intramolecular NHO hydrogen bond (pKa, ΔKNHO and ΔΔG°) were obtained from 1H-NMR titration data and pH measurements. The Henderson-Hasselbalch data analysis indicated that the systems are weakly acidic, and the predominant NHO equilibrium was established using Polster-Lachmann δ-diagram analysis and Perrin model data linearization.

  5. Study on 1H-NMR fingerprinting of Rhodiolae Crenulatae Radix et Rhizoma.

    PubMed

    Wen, Shi-yuan; Zhou, Jiang-tao; Chen, Yan-yan; Ding, Li-qin; Jiang, Miao-miao

    2015-07-01

    Nuclear magnetic resonance (1H-NMR) fingerprint of Rhodiola rosea medicinal materials was established, and used to distinguish the quality of raw materials from different sources. Pulse sequence for water peak inhibition was employed to acquire 1H-NMR spectra with the temperature at 298 K and spectrometer frequency of 400.13 MHz. Through subsection integral method, the obtained NMR data was subjected to similarity analysis and principal component analysis (PCA). 10 batches raw materials of Rhodiola rosea from different origins were successfully distinguished by PCA. The statistical results indicated that rhodiola glucoside, butyl alcohol, maleic acid and alanine were the main differential ingredients. This method provides an auxiliary method of Chinese quality approach to evaluate the quality of Rhodiola crenulata without using natural reference substances. PMID:26697690

  6. In situ solid-state NMR study of methanol-to-gasoline chemistry in zeolite HZSM-5

    SciTech Connect

    Munson, E.J.; Kheir, A.A.; Lazo, N.D.; Haw, J.F.

    1992-09-17

    This paper uses {sup 13}C solid-state NMR to study the chemistry of a variety of absorbates related to the methanol-to-gasoline process. This study has resulted in a better understanding of the chemical reaction occurring inside the zeolite HZSM-5 used in this process. It is shown that ethylene is the first olefin formed and ethyl methyl ether is also formed during this hydrocarbon synthesis on zeolite HZSM-5.

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

    PubMed

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

    2007-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-04-01

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

  9. Synthesis, characterization and dynamic NMR studies of a novel chalcone based N-substituted morpholine derivative

    NASA Astrophysics Data System (ADS)

    Baskar, R.; Baby, C.; Moni, M. S.; Subramanian, K.

    2013-05-01

    The synthesis of a novel chalcone based N-substituted morpholine derivative namely, (E)-1-(biphenyl-4-yl)-3-(4-(5-morpholinopentyloxy) phenyl) prop-2-en-1-one (BMPP), using a two step protocol is reported. The compound is characterized by FTIR, GC-MS and FTNMR spectroscopy techniques. Advanced 2D NMR techniques such as gradient enhanced COSY, HSQC, HMBC and NOESY were employed to establish through-bond and through-space correlations. Dynamic NMR measurements were carried out to obtain the energy barrier to ring inversion of the morpholine moiety.

  10. NMR studies on the chemical alteration of soil organic matter precursors during controlled charring

    NASA Astrophysics Data System (ADS)

    Knicker, Heike

    2010-05-01

    Beside the production of volatiles, vegetation fire transforms various amounts of labile organic components into recalcitrant dark colored and highly aromatic structures. They are incorporated into soils and are assumed to represent an important sink within the global carbon cycle. In order to elucidate the real importance of PyOM as a C-sink, a good understanding of its chemistry is crucial. Although several 'Black Carbon' (BC) models are reported, a commonly accepted view of the chemistry involved in its formation is still missing. Its biogeochemical recalcitrance is commonly associated with a highly condensed aromatic structure. However, recent studies indicated that this view may be oversimplified for PyOM derived from vegetation fire. In order to bring some more light on the structural properties of PyOM produced during vegetation fire, charred plant residues and model chars derived from typical plant macromolecules (casein, cellulose, lignin and condensed tannins) were subjected to controlled charring under oxic conditions (350°C and 450°C) and then characterized by nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Subsequently, the chemical features of the PyOM were related to its chemical recalcitrance as determined by chemical oxidation with acid potassium dichromate. Charring cellulose (350°C, 8 min) yielded in a low C-recovery (11%). Treating casein in the same way resulted in a survival of 62% of its C and 46% of its N. Comparable high C-recoveries are reported for lignin. After charring Lolium perenne, 34% of its N and C were recovered. NMR-spectroscopic studies revealed that for this sample most of the charred N and C occurred in pyrrole-type structures. Our studies further indicate that the aromatic skeleton of char accumulating after a vegetation fire must contain remains of the lignin backbone and considerable contributions of furans and anhydrosugars from thermally altered cellulose. Enhancing the temperature during the

  11. Neuroprotective effects of caffeine in MPTP model of Parkinson's disease: A (13)C NMR study.

    PubMed

    Bagga, Puneet; Chugani, Anup N; Patel, Anant B

    2016-01-01

    Parkinson's disease (PD) is a neurodegenerative disorder characterized by degeneration of nigrostriatal dopaminergic neurons with an accompanying neuroinflammation leading to loss of dopamine in the basal ganglia. Caffeine, a well-known A2A receptor antagonist is reported to slow down the neuroinflammation caused by activated microglia and reduce the extracellular glutamate in the brain. In this study, we have evaluated the neuroprotective effect of caffeine in the MPTP model of PD by monitoring the region specific cerebral energy metabolism. Adult C57BL6 mice were treated with caffeine (30 mg/kg, i.p.) 30 min prior to MPTP (25 mg/kg, i.p.) administration for 8 days. The paw grip strength of mice was assessed in order to evaluate the motor function after various treatments. For metabolic studies, mice were infused with [1,6-(13)C2]glucose, and (13)C labeling of amino acids was monitored using ex vivo(1)H-[(13)C]-NMR spectroscopy. The paw grip strength was found to be reduced following the MPTP treatment. The caffeine pretreatment showed significant protection against the reduction of paw grip strength in MPTP treated mice. The levels of GABA and myo-inositol were found to be elevated in the striatum of MPTP treated mice. The (13)C labeling of GluC4, GABAC2 and GlnC4 from [1,6-(13)C2]glucose was decreased in the cerebral cortex, striatum, olfactory bulb, thalamus and cerebellum suggesting impaired glutamatergic and GABAergic neuronal activity and neurotransmission of the MPTP treated mice. Most interestingly, the pretreatment of caffeine maintained the (13)C labeling of amino acids to the control values in cortical, olfactory bulb and cerebellum regions while it partially retained in striatal and thalamic regions in MPTP treated mice. The pretreatment of caffeine provides a partial neuro-protection against severe striatal degeneration in the MPTP model of PD.

  12. NMR Study of the Superconducting Gap Variation near the Mott Transition in Cs3C60

    NASA Astrophysics Data System (ADS)

    Wzietek, P.; Mito, T.; Alloul, H.; Pontiroli, D.; Aramini, M.; Riccò, M.

    2014-02-01

    Former extensive studies of superconductivity in the A3C60 compounds, where A is an alkali metal, have led one to consider that Bardeen-Cooper-Schrieffer electron-phonon pairing prevails in those compounds, though the incidence of electronic Coulomb repulsion has been highly debated. The discovery of two isomeric fulleride compounds Cs3C60 which exhibit a transition with pressure from a Mott insulator (MI) to a superconducting (SC) state clearly reopens that question. Using pressure (p) as a single control parameter of the C60 balls lattice spacing, one can now study the progressive evolution of the SC properties when the electronic correlations are increased towards the critical pressure pc of the Mott transition. We have used C13 and Cs133 NMR measurements on the cubic phase A15-Cs3C60 just above pc=5.0(3) kbar, where the SC transition temperature Tc displays a dome shape with decreasing cell volume. From the T dependence below Tc of the nuclear spin lattice relaxation rate (T1)-1 we determine the electronic excitations in the SC state, that is 2Δ, the gap value. The latter is found to be largely enhanced with respect to the Bardeen-Cooper-Schrieffer value established in the case of dense A3C60 compounds. It even increases slightly with decreasing p towards pc, where Tc decreases on the SC dome, so that 2Δ /kBTc increases regularly upon approaching the Mott transition. These results bring clear evidence that the increasing correlations near the Mott transition are not significantly detrimental to superconductivity. They rather suggest that repulsive electron interactions might even reinforce elecron-phonon superconductivity, being then partly responsible for the large Tc values, as proposed by theoretical models taking the electronic correlations as a key ingredient.

  13. Specific interactions of sticholysin I with model membranes: an NMR study.

    PubMed

    Castrillo, Inés; Araujo, Nelson A; Alegre-Cebollada, Jorge; Gavilanes, José G; Martínez-del-Pozo, Alvaro; Bruix, Marta

    2010-06-01

    Sticholysin I (StnI) is an actinoporin produced by the sea anemone Stichodactyla helianthus that binds biological and model membranes forming oligomeric pores. Both a surface cluster of aromatic rings and the N-terminal region are involved in pore formation. To characterize the membrane binding by StnI, we have studied by (1)H-NMR the environment of these regions in water and in the presence of membrane-mimicking micelles. Unlike other peptides from homologous actinoporins, the synthetic peptide corresponding to residues 1-30 tends to form helix in water and is more helical in either trifluoroethanol or dodecylphosphocholine (DPC) micelles. In these environments, it forms a helix-turn-helix motif with the last alpha-helical segment matching the native helix-alpha(1) (residues 14-24) present in the complete protein. The first helix (residues 4-9) is less populated and is not present in the water-soluble protein structure. The characterization of wild-type StnI structure in micelles shows that the helix-alpha(1) is maintained in its native structure and that this micellar environment does not provoke its detachment from the protein core. Finally, the study of the aromatic resonances has shown that the motional flexibility of specific rings is perturbed in the presence of micelles. On these bases, the implication of the aromatic rings of Trp-111, Tyr-112, Trp-115, Tyr-132, Tyr-136, and Tyr-137, in the interaction between StnI and the micelle is discussed. Based on all the findings, a revised model for StnI interaction with membranes is proposed, which accounts for differences in its behavior as compared with other highly homologous sticholysins.

  14. Specific interactions of sticholysin I with model membranes: an NMR study.

    PubMed

    Castrillo, Inés; Araujo, Nelson A; Alegre-Cebollada, Jorge; Gavilanes, José G; Martínez-del-Pozo, Alvaro; Bruix, Marta

    2010-06-01

    Sticholysin I (StnI) is an actinoporin produced by the sea anemone Stichodactyla helianthus that binds biological and model membranes forming oligomeric pores. Both a surface cluster of aromatic rings and the N-terminal region are involved in pore formation. To characterize the membrane binding by StnI, we have studied by (1)H-NMR the environment of these regions in water and in the presence of membrane-mimicking micelles. Unlike other peptides from homologous actinoporins, the synthetic peptide corresponding to residues 1-30 tends to form helix in water and is more helical in either trifluoroethanol or dodecylphosphocholine (DPC) micelles. In these environments, it forms a helix-turn-helix motif with the last alpha-helical segment matching the native helix-alpha(1) (residues 14-24) present in the complete protein. The first helix (residues 4-9) is less populated and is not present in the water-soluble protein structure. The characterization of wild-type StnI structure in micelles shows that the helix-alpha(1) is maintained in its native structure and that this micellar environment does not provoke its detachment from the protein core. Finally, the study of the aromatic resonances has shown that the motional flexibility of specific rings is perturbed in the presence of micelles. On these bases, the implication of the aromatic rings of Trp-111, Tyr-112, Trp-115, Tyr-132, Tyr-136, and Tyr-137, in the interaction between StnI and the micelle is discussed. Based on all the findings, a revised model for StnI interaction with membranes is proposed, which accounts for differences in its behavior as compared with other highly homologous sticholysins. PMID:20408172

  15. Application of NMR and UV spectroscopy in the study of interactions between anticancer drugs and their phospholipid carriers

    NASA Astrophysics Data System (ADS)

    Pentak, Danuta; Sułkowska, Anna; Sułkowski, Wiesław W.

    2008-09-01

    The aim of this work was to encapsulate two drugs: 1-β- D-arabinofuranosylcytosine (Ara-C) with the amphiphilic properties and 5-fluorouracil (5-FU) with the hydrophobic properties into liposomes prepared by the modified reverse-phase evaporation method (mREV) from L-α-phosphatidylcholine dipalmitoyl (DPPC). Both drugs are used together in the anticancer multidrug therapy. We studied the competition for their encapsulation in liposomes by the use of two spectroscopies: 1H NMR and UV on the basis of the analysis of the signals of each drug in the liposome-drug system. We concluded that the mREV method allows us to obtain liposomes which may transport more than one drug simultaneously. The NMR and UV studies of the drug competitive encapsulation and transport in liposomes formed from DPPC by the mREV method should be the basis for the analysis of the changes which may occur in vivo.

  16. A study by (1)H NMR on the influence of some factors affecting lipid in vitro digestion.

    PubMed

    Nieva-Echevarría, Bárbara; Goicoechea, Encarnación; Manzanos, María J; Guillén, María D

    2016-11-15

    This article focuses on the impact of several experimental factors, including gastric acidification, intestinal transit time, presence of gastric lipase, sample/digestive fluids ratio, concentration and nature of the enzymes in intestinal juice, and bile concentration, on the extent of in vitro lipolysis when using a static model that simulates human digestion processes in mouth, stomach and small intestine. The study was carried out by Proton Nuclear Magnetic Resonance ((1)H NMR). This technique provides a complete molecular picture of lipolysis, evidencing for the first time, whether preferential hydrolysis of certain glycerides over others occurs. A lipolysis degree similar to that reported in vivo was reached by varying certain variables within a physiological range; among them, bile concentration was found to be crucial. The holistic view of this (1)H NMR study provides information of paramount importance to design sound in vitro digestion models to determine the bioaccessibility and bioavailability of lipophilic compounds. PMID:27283602

  17. Effect of genetic and phenotypic factors on the composition of commercial marmande type tomatoes studied through HRMAS NMR spectroscopy.

    PubMed

    Iglesias, María José; García López, Jesús; Collados Luján, Juan Fernando; López Ortiz, Fernando; Bojórquez Pereznieto, Humberto; Toresano, Fernando; Camacho, Francisco

    2014-01-01

    The effects of genetic, technological and environmental factors on the chemical composition of four marmande type tomato varieties have been investigated. The study is based on the analysis of (1)H HRMAS NMR spectra of tomato purée using a combination of partial least squares (PLS) and assigned signal analysis (ASA). In agreement with genetic, morphological and taste characteristics of the tomatoes studied, the analysis of the NMR data allows two groups of samples to be differentiated. The type of culture and climatic conditions can reduce the compositional differences. The extension of the compositional changes produced by climatic conditions is variety-depend. Neither grafting nor perlite affect significantly the relative content of primary metabolites. This was not the case for tomatoes grown using the pure hydroponic production system based on the recirculation of nutrient solution, New Growing System NGS®, which seems to be an effective agricultural approach to improve tomato quality. PMID:24001806

  18. The interaction of small molecules with phospholipid membranes studied by 1H NOESY NMR under magic-angle spinning.

    PubMed

    Scheidt, Holger A; Huster, Daniel

    2008-01-01

    The interaction of small molecules with lipid membranes and the exact knowledge of their binding site and bilayer distribution is of great pharmacological importance and represents an active field of current biophysical research. Over the last decade, a highly resolved 1H solid-state NMR method has been developed that allows measuring localization and distribution of small molecules in membranes. The classical solution 1H NMR NOESY technique is applied to lipid membrane samples under magic-angle spinning (MAS) and NOESY cross-relaxation rates are determined quantitatively. These rates are proportional to the contact probability between molecular segments and therefore an ideal tool to study intermolecular interactions in membranes. Here, we review recent 1H MAS NOESY applications that were carried out to study lateral lipid organization in mixed membranes and the interaction of membranes with water, ethanol, small aromatic compounds, peptides, fluorescence labels, and lipophilic nucleosides.

  19. Effect of genetic and phenotypic factors on the composition of commercial marmande type tomatoes studied through HRMAS NMR spectroscopy.

    PubMed

    Iglesias, María José; García López, Jesús; Collados Luján, Juan Fernando; López Ortiz, Fernando; Bojórquez Pereznieto, Humberto; Toresano, Fernando; Camacho, Francisco

    2014-01-01

    The effects of genetic, technological and environmental factors on the chemical composition of four marmande type tomato varieties have been investigated. The study is based on the analysis of (1)H HRMAS NMR spectra of tomato purée using a combination of partial least squares (PLS) and assigned signal analysis (ASA). In agreement with genetic, morphological and taste characteristics of the tomatoes studied, the analysis of the NMR data allows two groups of samples to be differentiated. The type of culture and climatic conditions can reduce the compositional differences. The extension of the compositional changes produced by climatic conditions is variety-depend. Neither grafting nor perlite affect significantly the relative content of primary metabolites. This was not the case for tomatoes grown using the pure hydroponic production system based on the recirculation of nutrient solution, New Growing System NGS®, which seems to be an effective agricultural approach to improve tomato quality.

  20. Weak alignment offers new NMR opportunities to study protein structure and dynamics

    PubMed Central

    Bax, Ad

    2003-01-01

    Protein solution nuclear magnetic resonance (NMR) can be conducted in a slightly anisotropic environment, where the orientational distribution of the proteins is no longer random. In such an environment, the large one-bond internuclear dipolar interactions no longer average to zero and report on the average orientation of the corresponding vectors relative to the magnetic field. The desired very weak ordering, on the order of 10−3, can be induced conveniently by the use of aqueous nematic liquid crystalline suspensions or by anisotropically compressed hydrogels. The resulting residual dipolar interactions are scaled down by three orders of magnitude relative to their static values, but nevertheless can be measured at high accuracy. They are very precise reporters on the average orientation of bonds relative to the molecular alignment frame, and they can be used in a variety of ways to enrich our understanding of protein structure and function. Applications to date have focused primarily on validation of structures, determined by NMR, X-ray crystallography, or homology modeling, and on refinement of structures determined by conventional NMR approaches. Although de novo structure determination on the basis of dipolar couplings suffers from a severe multiple minimum problem, related to the degeneracy of dipolar coupling relative to inversion of the internuclear vector, a number of approaches can address this problem and potentially can accelerate the NMR structure determination process considerably. In favorable cases, where large numbers of dipolar couplings can be measured, inconsistency between measured values can report on internal motions. PMID:12493823

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

    ERIC Educational Resources Information Center

    Atkinson, D.; Chechik, V.

    2004-01-01

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

  2. Phosphorus solubility of agricultural soils: a surface charge and phosphorus-31 NMR speciation study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We investigated ten soils from six states in United States to determine the relationship between potentiometric titration derived soil surface charge and Phosphorus-31 (P) nuclear magnetic resonance (NMR) speciation with the concentration of water-extractable P (WEP). The surface charge value at the...

  3. 23Na NMR study of ionic mesophases in molten sodium carboxylates

    NASA Astrophysics Data System (ADS)

    Bonekamp, J.; Eguchi, T.; Jonas, J.

    1980-10-01

    The 23Na NMR lineshapes are reported for the ionic mesophase and isotropic phase of the melts of sodium n-butyrate and sodium isovalerate. The powder pattern for the central transition typical for the second-order quadrupole effect observed in the mesophase melts is of particular interest. Some analogies to 23Na behavior in sodium β-alumina are pointed out.

  4. An NMR study of diffusion in surfactant-free emulsions and molten triglyceride mixtures

    NASA Astrophysics Data System (ADS)

    MacLean, Duncan A.

    Nuclear magnetic resonance (NMR) diffusion measurements have become extensively used analytical techniques, with applications in many fields. In this thesis these measurements have been employed to elucidate a mechanism of emulsion stabilization and to examine mobility of a mixture of substances at the molecular level. Emulsions (liquid-in-liquid mixtures) have widespread applications (pharmaceutical, food science, petrochemical, agrochemical), therefore it is important to understand what governs emulsion stability. It has been previously demonstrated that a degassing process stabilizes oil-in-water emulsions, however the mechanism behind this is debated. In this thesis the Cotts 13-interval NMR sequence was used to examine the effects of degassing, establishing which of two suggested mechanisms is responsible for producing stable emulsions. Triglyceride mixtures are commonly separated before characterisation, however, NMR measurements of diffusion in molten trilaurin-trimyristin mixes have been made. This sheds light on the behaviour of these mixtures and assisted in developing new methods for their characterisation. These applications illustrate the versatility of NMR diffusion measurements.

  5. 7Li NMR study of intercalated lithium in curved carbon lattices

    NASA Astrophysics Data System (ADS)

    Gerald, R. E.; Johnson, C. S.; Rathke, J. W.; Klingler, R. J.; Sandí, G.; Scanlon, L. G.

    A device was invented that permits nuclear magnetic resonance (NMR) analysis of the internal elements of a coin cell battery. The Coin Cell Battery Imager was used to record wideline 7Li NMR spectra of the lithium ions that were electrochemically intercalated into three different types of carbon-based materials. The samples included graphite, corannulene, and carbon derived from sepiolite clay. All samples were excised from 2032-size coin cells that were cycled multiple times and left in a discharged state (i.e., fully lithiated). A comparison of the 7Li NMR spectra recorded for the three carbons revealed that the curved carbon lattice derived from sepiolite affected the lithium resonances in a manner similar to that observed for the curved molecule corannulene, while both differed from the flat lattice of graphite. In addition, it was possible to observe lithium dendrites on the surface of a hard carbon electrode even in the presence of a large lithium counter electrode using NMR imaging techniques.

  6. Advanced solids NMR studies of coal structure and chemistry. Progress report, September 1, 1995--February 28, 1996

    SciTech Connect

    Zilm, K.W.

    1996-09-01

    This report covers the progress made on the title project for the project period. The study of coal chemical structure is a vital component of research efforts to develop better chemical utilization of coals, and for furthering our basic understanding of coal geochemistry. In this grant we are addressing several structural questions pertaining to coals with advances in state of the art solids NMR methods. Our goals are twofold. First, we are interested in developing new methods that will enable us to measure important structural parameters in whole coals not directly accessible by other techniques. In parallel with these efforts we will apply these NMR methods in a study of the chemical differences between gas-sourcing and oil-sourcing coals. The NMR methods work will specifically focus on determination of the number and types of methylene groups, determination of the number and types of methine groups, identification of carbons adjacent to nitrogen and sites with exchangeable protons, and methods to more finely characterize the distribution of hydrogen in coals. We will also develop NMR methods for probing coal macropore structure using hyperpolarized {sup 129}Xe as a probe, and study the molecular dynamics of what appear to be mobile, CH{sub 2} rich, long chain hydrocarbons. The motivation for investigating these specific structural features of coals arises from their relevance to the chemical reactivity of some types of coals. The coals to be studied and contrasted include oil-prone coals from Australia and Indonesia, those comprising the Argonne Premium Coal Sample bank, and other relevant samples.

  7. NMR Studies of the Dynamics of Nitrophorin 2 Bound to Nitric Oxide†

    PubMed Central

    Muthu, Dhanasekaran; Berry, Robert E.; Zhang, Hongjun; Walker, F. Ann

    2013-01-01

    The Rhodnius nitrophorins are β-barrel proteins of the lipocalin fold with a heme protruding from the open end of the barrel. They are found in the saliva of the blood-sucking insect Rhodnius prolixus, which synthesizes and stores nitric oxide (NO) in the salivary glands, where NO is bound to iron. NO is released by dilution and pH rise when the insect spits its saliva into the tissues of a victim, to aid in obtaining a blood meal. In the adult insect there are four nitrophorins, NP1, NP2, NP3 and NP4. At pH 7.3, NP4 releases NO 17 times faster than does NP2, as measured by stopped-flow kinetics. A number of crystal structures of the least abundant protein, NP4, are available. These structures have been used to propose that two loops between adjacent β-strands at the front opening of the protein, the A-B and G-H loops, determine the rate of NO release. In order to learn how the protein loops contribute to release of NO for each of the nitrophorins, the dynamics of these proteins are being studied in our laboratory. In this work, the NP2-NO complex has been investigated by NMR relaxation measurements to probe the pico- to nanosecond and micro- to millisecond time scale motions at three pH values, 5.0, 6.5, and 7.3. It is found that at pH 5.0 and 6.5, NP2-NO is rigid and only a few residues in the loop regions show dynamics, while at pH 7.3 somewhat more dynamics, particularly of the A-B loop, are observed. Comparison to other lipocalins shows that all are relatively rigid, and that the dynamics of lipocalins in general are much more subtle than those of mainly α-helical proteins. PMID:24116947

  8. NMR study of the cold, heat, and pressure unfolding of ribonuclease A.

    PubMed

    Zhang, J; Peng, X; Jonas, A; Jonas, J

    1995-07-11

    The reversible cold, heat, and pressure unfolding of RNase A and RNase A--inhibitor complex were studied by 1D and 2D 1H NMR spectroscopy. The reversible pressure denaturation experiments in the pressure range from 1 bar to 5 kbar were carried out at pH 2.0 and 10 degrees C. The cold denaturation was carried out at 3 kbar, where the protein solution can be cooled down to -25 degrees C without freezing. Including heat denaturation experiments, the experimental data obtained allowed us to construct the pressure--temperature phase diagram of RNase A. The experimental results suggest the possibility that all three denaturation processes (cold, heat, and pressure) lead to non-cooperative unfolding. The appearance of a new histidine resonance in the cold-denatured and pressure-denatured RNase A spectra, compared to the absence of this resonance in the heat-denatured state, indicates that the pressure-denatured and cold-denatured states may contain partially folded structures that are similar to that of the early folding intermediate found in the temperature-jump experiment reported by Blum et al. [Blum, A. D., et al. (1978) J. Mol. Biol. 118, 305]. A hydrogen-exchange experiment was performed to confirm the presence of partially folded structures in the pressure-denatured state. Stable hydrogen-bonded structures protecting the backbone amide hydrogens from solvent exchange were observed in the pressure-denatured state. These experimental results suggest that the pressure-denatured RNase A displays the characteristics of a the inhibitor 3'-UMP show that the RNase A-inhibitor complex is more stable than RNase without the inhibitor. PMID:7612603

  9. 1H NMR studies of reactions of copper complexes with human blood plasma and urine.

    PubMed

    Bligh, S W; Boyle, H A; McEwen, A B; Sadler, P J; Woodham, R H

    1992-01-22

    Reactions of the copper complexes Cu(II)Cl2, [Cu(II)(EDTA)]2-, [Cu(II)2(DIPS)4] and [Cu(I)(DMP)2]+ (where DIPS is 3,5-diisopropylsalicylate and DMP is 2,9-dimethylphenanthroline) with human blood plasma and urine have been studied by 500 MHz 1H NMR spectroscopy, and CD spectroscopy has been used to monitor the transfer of Cu(II) onto albumin in plasma. The rate of transfer of Cu(II) from [Cu(II)(EDTA)]2- onto albumin as measured by CD (T1/2 26 min, 0.5 mM Cu, 21 degrees), was similar to the rate of Cu(II) binding to amino acids and citrate, and to the rate of formation of [Ca(II)(EDTA)]2- in plasma. Reactions of Cu(II)Cl2 and [Cu(II)2(DIPS)4] in plasma followed a similar course, but were more rapid. The latter complex also appeared to give rise to the displacement of lactate from protein binding. Reactions of copper complexes in plasma therefore involve a range of low Mr ligands as well as albumin, and the ligands play a major role in determining the kinetics of the reactions. These factors, as well as the partitioning of both complexes and displaced ligands into lipoproteins, are likely to play important roles in the molecular pharmacology of copper-containing drugs. In urine, His and formate were involved in EDTA and DIPS displacement from their respective copper complexes, and peaks for free DIPS and [Ca(II)(EDTA)]2- were observed. The complex (Cu(I)(DMP)2]+ appeared to be relatively stable in both plasma and urine. PMID:1739401

  10. Thermodynamic Profiles and NMR Studies of Oligonucleotide Duplexes Containing Single Diastereomeric Spiroiminodihydantoin Lesions

    PubMed Central

    Khutsishvili, Irine; Zhang, Na; Marky, Luis A.; Crean, Conor; Patel, Dinshaw J.; Geacintov, Nicholas E.; Shafirovich, Vladimir

    2013-01-01

    The spiroiminodihydantoins (Sp) are highly mutagenic oxidation products of guanine and 8-oxo-7,8-dihydroguanine in DNA. The Sp lesions have been recently detected in the liver and colon of mice infected with H. hepaticus that induces inflammation and development of liver and colon cancers in murine model systems [Mangerich, A., et al. (2012) Proc. Natl. Acad. Sci. U.S.A. 109, E1820–E1829]. The impact of Sp lesions on the thermodynamic characteristics and the effects of the diastereomeric Sp-R and Sp-S lesions on the conformational features of double-stranded 11-mer oligonucleotide duplexes have been studied by a combination of microcalorimetric, analysis of DNA melting curves, and two-dimensional NMR methods. The non-planar, propeller-like shapes of the Sp residues strongly diminish the local base stacking interactions that destabilize the DNA duplexes characterized by unfavorable enthalpy contributions. Relative to an unmodified duplex, the thermally induced unfolding of the duplexes with centrally positioned Sp-R and Sp-S lesions into single strands is accompanied by a smaller release of cationic counterions (ΔnNa+ = 0.6 mol Na+ per mol duplex) and water molecules (Δnw = 17 mol H2O per mol duplex). The unfolding parameters are similar for the Sp-R and Sp-S lesions although their orientations in the duplexes are different. The structural disturbances radiate one base pair beyond the flanking C:G pair, although Watson-Crick hydrogen bonding is maintained at all flanking base pairs. The observed relatively strong destabilization of B-form DNA by the physically small Sp lesions are expected to have a significant impact on the processing of these lesions in biological environments. PMID:23360616

  11. A general and efficient approach for NMR studies of peptide dynamics in class I MHC peptide binding grooves.

    PubMed

    Insaidoo, Francis K; Zajicek, Jaroslav; Baker, Brian M

    2009-10-20

    T-Cell receptor recognition of peptides bound by major histocompatibility complex (MHC) proteins initiates a cellular immune response. Dynamics of peptides within MHC binding grooves can influence TCR recognition, yet NMR studies which could address this rigorously have been hindered by the expense of isotopically labeled peptides and the large size of peptide-MHC complexes. Here we describe a methodology for characterizing peptide dynamics within MHC binding grooves via NMR, using a biosynthetic approach for producing labeled peptide. With the Tax(11-19) peptide bound to the human class I MHC HLA-A*0201, we demonstrate that peptide generated in this manner can be well characterized in MHC binding grooves by NMR, providing opportunities to more precisely study the role of peptide dynamics in TCR recognition. Demonstrating the utility of such studies, the data with the Tax(11-19) peptide indicate the presence of slow conformational exchange in the peptide, supporting an "induced-fit" style TCR binding mechanism.

  12. Environmental Weathering of Aluminosilicate Clay Minerals: Solid-State NMR Studies of Transformations Leading to Radionuclide Sequestration

    SciTech Connect

    Mueller, Karl T.; Crosson, Garry; Chorover, Jon; Choi, Sunkyung

    2004-03-28

    Mobilities of radionuclides (such as 137Cs and 90Sr) are governed by their interactions with natural soil particles in the saturated and unsaturated zones at Department of Energy sites. High surface area aluminosilicate clay minerals are a component of the natural soils beneath the leaking waste tanks at these sites and serve as possible radionuclide sorbents. However, due to the characteristics of the contaminant medium (high pH, high Al and high ionic strength), clay minerals are susceptible to transformations during exposure to tank waste leachates. We are currently studying the transformation of clays under specific chemical conditions that mimic the composition of known contaminant solutions. In these studies, specimen clay samples are reacted for varying time periods (up to one year) with simulated tank waste leachate solutions. Mineral dissolution and transformation are followed with solution analysis, x-ray diffraction and a number of other analytical methods. We report here results from 27Al MAS NMR at variable magnetic field strengths (up to 18.8 T), 29Si MAS NMR and 1H/29Si CPMAS NMR and evaluate these results along with those of other parallel analytic studies.

  13. A general and efficient approach for NMR studies of peptide dynamics in class I MHC peptide binding grooves.

    PubMed

    Insaidoo, Francis K; Zajicek, Jaroslav; Baker, Brian M

    2009-10-20

    T-Cell receptor recognition of peptides bound by major histocompatibility complex (MHC) proteins initiates a cellular immune response. Dynamics of peptides within MHC binding grooves can influence TCR recognition, yet NMR studies which could address this rigorously have been hindered by the expense of isotopically labeled peptides and the large size of peptide-MHC complexes. Here we describe a methodology for characterizing peptide dynamics within MHC binding grooves via NMR, using a biosynthetic approach for producing labeled peptide. With the Tax(11-19) peptide bound to the human class I MHC HLA-A*0201, we demonstrate that peptide generated in this manner can be well characterized in MHC binding grooves by NMR, providing opportunities to more precisely study the role of peptide dynamics in TCR recognition. Demonstrating the utility of such studies, the data with the Tax(11-19) peptide indicate the presence of slow conformational exchange in the peptide, supporting an "induced-fit" style TCR binding mechanism. PMID:19772349

  14. Using Oxygen 17 to assess the importance of Atmospherically Deposited N in the riverine flux of nitrogen in the Neuse River Basin, NC

    NASA Astrophysics Data System (ADS)

    Showers, B.

    2002-12-01

    The environmental impacts of atmospherically deposited nitrogen (ADN) is now recognized to be an important component of the eutrophication of streams, lakes, estuaries and coastal waters. Nitrogen limited coastal waters make up 15 % of the global ocean, but account for half of the new global oceanic primary productivity. It has been estimated that ADN accounts for 10-50 % of the total external nitrogen load for these coastal ecosystems, and that river systems deliver a significant proportion of this ADN load from watersheds. In the Neuse River Basin, NC the ADN flux has been previously calculated to be 1236 mg per square meter per year. Using conservative watershed retention rate estimates suggest that 10-45 % of the total N reaching the river and transported to the estuary in this basin is from ADN. We have developed a CF IRMS analytical technique that combines the thermal decomposition procedure of Michalski et al (in press) with FMAT Gasbench automation to efficiently measure the Oxygen 17 of riverine nitrate. This will determine the importance of ADN in the riverine flux of nitrate. In the Neuse River basin the Nitrogen 15 and Oxygen 18 of nitrate are not positively correlated in the river main stem, indicating that denitrification is not a significant process for in stream consumption of nitrogen. High Oxygen 18 values of nitrate are observed in the small order creeks and streams, which could possibly indicate de-nitrification or the importance of atmospheric deposition. High Oxygen 17 values of riverine nitrate during moderate to low flow conditions after rainfall events in small urban streams suggest that atmospheric deposition and not denitrification is responsible for the elevated Oxygen 18 nitrate values in these areas. Oxygen 17 values of riverine nitrate in agricultural and wooded areas in the lower portion of the basin suggest that these landscapes retain ADN. This means that current landscape retention models overestimate the importance of the

  15. The pH behavior of a 2-aminoethyl dihydrogen phosphate zwitterion studied with NMR-titrations

    NASA Astrophysics Data System (ADS)

    Myller, A. T.; Karhe, J. J.; Haukka, M.; Pakkanen, T. T.

    2013-02-01

    In this study a bifunctional 2-aminoethyl dihydrogen phosphate (AEPH2) was 1H and 31P NMR characterized in a pH range of 1-12 in order to determine the zwitterion properties in different pH regions in H2O and D2O solutions. NMR was also used to determine the pH range where AEPH2 exists as a zwitterion. The phosphate group has two deprotonation points, around pH 1 and 6, while the amino group deprotonates at pH 11. The zwitterion form of AEPH2 (NH3+sbnd CHsbnd CHsbnd OPOH) exists as the main ion between pH 1 and 6 in water solutions and also in the solid state.

  16. Proton NMR study of the organic metal {kappa}-(BETS){sub 2}Mn[N(CN){sub 2}]{sub 3}

    SciTech Connect

    Vyaselev, O. M.; Kushch, N. D.; Yagubskii, E. B.

    2011-11-15

    Magnetic properties of the organic conductor {kappa}-(BETS){sub 2}Mn[N(CN){sub 2}]{sub 3} above and below the temperature of the metal-insulator transition that occurs at T{sub MI} Almost-Equal-To 25 K are studied by {sup 1}H NMR. The proton spectrum is shown to be determined by the static dipolar fields from Mn{sup 2+} localized moments, while the {sup 1}H spin-lattice relaxation is dominated by fluctuating fields from Mn{sup 2+} electrons. The NMR data, both static (the spectra) and dynamic (the spin-lattice relaxation), indicate the freezing of Mn{sup 2+} moments into a short-range or an incommensurate long-range antiferromagnetic order below T{sub MI}.

  17. Proton NMR study of the organic metal κ-(BETS)2Mn[N(CN)2]3

    NASA Astrophysics Data System (ADS)

    Vyaselev, O. M.; Kushch, N. D.; Yagubskii, E. B.

    2011-11-01

    Magnetic properties of the organic conductor κ-(BETS)2Mn[N(CN)2]3 above and below the temperature of the metal-insulator transition that occurs at T MI ≈ 25 K are studied by 1H NMR. The proton spectrum is shown to be determined by the static dipolar fields from Mn2+ localized moments, while the 1H spin-lattice relaxation is dominated by fluctuating fields from Mn2+ electrons. The NMR data, both static (the spectra) and dynamic (the spin-lattice relaxation), indicate the freezing of Mn2+ moments into a short-range or an incommensurate long-range antiferromagnetic order below T MI.

  18. Study of the Cardiotoxicity of Venenum Bufonis in Rats using an 1H NMR-Based Metabolomics Approach

    PubMed Central

    Wang, Junsong; Guo, Pingping; Li, Minghui; Yang, Minghua; Kong, Lingyi

    2015-01-01

    Venenum Bufonis, a well-known traditional Chinese medicine, has been widely used in Asia and has gained popularity in Western countries over the last decade. Venenum Bufonis has obvious side effects that have been observed in clinical settings, but few studies have reported on its cardiotoxicity. In this work, the cardiotoxicity of Venenum Bufonis was investigated using a 11H NMR-based metabolomics approach. The 1H NMR profiles of the serum, myocardial extracts and liver extracts of specific-pathogen-free rats showed that Venenum Bufonis produced significant metabolic perturbations dose-dependently with a distinct time effect, peaking at 2 hr after dosing and attenuating gradually. Clinical chemistry, electrocardiographic recordings, and histopathological evaluation provided additional evidence of Venenum Bufonis-induced cardiac damage that complemented and supported the metabolomics findings. The combined results demonstrated that oxidative stress, mitochondrial dysfunction, and energy metabolism perturbations were associated with the cardiac damage that results from Venenum Bufonis. PMID:25781638

  19. Solution NMR studies of supramolecular complexes of [60]- and [70]fullerenes with mono O-substituted calix[6]arene

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Sumanta; Chattopadhyay, Subrata; Nayak, Sandip K.; Banerjee, Manas

    2005-11-01

    Supramolecular complexation of [60]- and [70]fullerenes with 37-allyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4- tert butyl)calix[6]arene ( I) has been studied in CCl 4 medium by NMR spectrometric method. All of the complexes are found to be stable with 1:1 stoichiometry. Formation constants ( K) of the above supramolecular complexes have been determined from systematic variation of NMR chemical shifts of specific protons of I in the presence of [60]- and [70]fullerenes. Trends in the K value suggest that [70]fullerene binds more strongly with I relative to [60]fullerene. Both PM3 and ab initio calculations reveal that the intermolecular interaction in the [70]fullerene/ I complex proceeds through quite deep energy minima.

  20. Integrated NMR and computational study of push-pull NLO probes: interplay of solvent and structural effects.

    PubMed

    Marini, Alberto; Macchi, Sara; Jurinovich, Sandro; Catalano, Donata; Mennucci, Benedetta

    2011-09-01

    In this study we combined QM calculations and NMR measurements to understand at a detailed level the complex interplay of structural/electronic properties with the effects of the solvent in the NLO activity of push-pull systems, quantified in terms of variations of the static hyperpolarizability. Different parameters (bond lengths and bond length alternation, vibrational frequencies, electronic charge distribution) are introduced and tested to rationalize both the solvent sensitivity of three molecular systems (namely, p-nitroaniline, ethyl 4-ammino benzoate, and 5-nitro-1H-indole) and the differences among them. This analysis has finally allowed us to establish a clear correlation between the charge transfer behavior of the systems, their NLO properties, and NMR parameters also validating simplified but effective chemical analyses based on resonance limit forms.

  1. Carbon-13 NMR study of switch variant anti-dansyl antibodies: Antigen binding and domain-domain interactions

    SciTech Connect

    Kato, Koichi; Matsunaga, Chigusa; Odaka, Asano; Yamato, Sumie; Takaha, Wakana; Shimada, Ichio; Arata, Yoji )

    1991-07-02

    A {sup 13}C NMR study is reported of switch variant anti-dansyl antibodies, which possess the identical V{sub H}, V{sub L}, and C{sub L} domains in conjunction with highly homologous but not identical heavy-chain constant regions. Each of the antibodies has been selectively labeled with {sup 13}C at the carbonyl carbon of Trp, Tyr, His, or Cys residue by growing hybridoma cells in serum-free medium. Spectral assignments have been made by folowing the procedure described previously for the switch variant antibodies labeled with (1-{sup 13}C)Met. On the basis of the spectral data collected for the antibodies and their proteolytic fragments, the authors discuss how {sup 13}C NMR spectroscopy can be used for the structural analyses of antigen binding and also of domain-domain interactions in the antibody molecule.

  2. Deuterium Magic Angle Spinning NMR Used to Study the Dynamics of Peptides Adsorbed onto Polystyrene and Functionalized Polystyrene Surfaces

    PubMed Central

    Breen, Nicholas F.; Li, Kun; Olsen, Gregory L.; Drobny, Gary P.

    2011-01-01

    LKα14 is a 14 amino acid peptide with a periodic sequence of leucine and lysine residues consistent with an amphipathic α-helix. This “hydrophobic periodicity” has been found to result in an α-helical secondary structure at air-water interfaces and on both polar and non-polar solid polymer surfaces. In this paper the dynamics of LKα14 peptides, selectively deuterated at a single leucine and adsorbed onto polystyrene and carboxylated polystyrene beads, are studied using 2H Magic Angle Spinning (MAS) solid state NMR over a 100 degree temperature range. We first demonstrate the sensitivity enhancement possible with 2H MAS techniques, which in turn enables us to obtain high quality 2H NMR spectra for selectively deuterated peptides adsorbed onto solid polymer surfaces. An extensive literature shows that the dynamics of leucine side chains are sensitive to the local structural environment of the protein. Therefore the degree to which the dynamics of leucine side chains and the backbone of the peptide LKα14 are influenced by surface proximity and surface chemistry is studied as a function of temperature with 2H MAS NMR. It is found that the dynamics of the leucine side chains in LKα14 depend strongly upon the orientation of the polymer on the surface, which in turn depends on whether the LKα14 peptide adsorbs onto a polar or non-polar surface. 2H MAS line shapes therefore permit probes of surface orientation over a wide temperature range. PMID:21650191

  3. Molecular Recognition of Ligands by Native Viruses and Virus-Like Particles as Studied by NMR Experiments

    NASA Astrophysics Data System (ADS)

    Rademacher, Christoph; Peters, Thomas

    Viral entry into host cells is a process that in the majority of cases is not understood in its molecular details. The first step of viral entry is the recognition of cellular receptors on host cells by viruses, and although X-ray crystallography had yielded some spectacular results in individual cases, in general there is little data available to unravel the principles of virus-ligand recognition at atomic resolution. Therefore, new techniques that uncover the molecular details of these recognition processes are needed. The investigation of virus-ligand interactions using ligand-based NMR techniques is an emerging field with the potential to substantially contribute to a deeper understanding of the molecular aspects of viral entry into host cells. Here, we give an overview that covers some of the systems studied so far. This comprises native viruses as well as virus-like particles (VLPs). We will not address studies that have been performed with individual proteins that are not in a native environment. It turns out that STD NMR in particular has a great potential to shine light on the viral entry process as this technique requires only very moderate amounts of viruses or VLPs and corresponding ligands. As a further advantage, this approach is also applicable to ligands that bind to viruses with medium to low affinity. Therefore, STD NMR is extremely well suited for development of antiviral entry inhibitors utilizing fragment-based approaches with low molecular weight compounds.

  4. NMR studies of recombinant Coprinus peroxidase and three site-directed mutants. Implications for peroxidase substrate binding.

    PubMed

    Veitch, N C; Tams, J W; Vind, J; Dalbøge, H; Welinder, K G

    1994-06-15

    Proton nuclear magnetic resonance spectroscopy has been used to characterise and compare wild-type fungal and recombinant Coprinus cinereus peroxidase (CIP) and three mutants in which Gly156 and/or Asn157 was replaced by Phe. Analysis of one- and two-dimensional NMR spectra of recombinant CIP was undertaken for comparison with the fungal enzyme and in order to establish a meaningful basis for solution studies of CIP mutants. Proton resonance assignments of haem and haem-linked residues obtained for the cyanide-ligated form of recombinant CIP revealed a high degree of spectral similarity with those of lignin and manganese-dependent peroxidases and extend previously reported NMR data for fungal CIP. The three mutants examined by NMR spectroscopy comprised site-specific substitutions made to a region of the structure believed to form part of the peroxidase haem group access channel for substrate and ligand molecules. Proton resonances of the aromatic side-chains of Phe156 and Phe157 were found to have similar spectral characteristics to those of two phenylalanine residues known to be involved in the binding of aromatic donor molecules to the plant peroxidase, horseradish peroxidase isoenzyme C. The results are discussed in the context of complementary reactivity studies on the mutants in order to develop a more detailed understanding of aromatic donor molecule binding to fungal and plant peroxidases.

  5. An NMR study and ab initio molecular orbital calculation of substituted benzofuroxans and the salt of 4,6-dinitrobenzofuroxan

    NASA Astrophysics Data System (ADS)

    Cmoch, P.; Wiench, J. W.; Stefaniak, L.; Webb, G. A.

    1999-09-01

    13C, 15N and 17O NMR data are reported for a series of substituted benzofuroxans in aprotic and acidic solutions and for a potassium salt of a substituted benzofuroxan. Some of the title compounds can exhibit fast furoxan valence equilibrium at room temperature regardless of a solvent used, whereas for the others no evidence of above-mentioned process exists. The NMR parameters most sensitive to salt formation are the chemical shifts of the C7, N1, N3 and all of the oxygen nuclei. Hence these are reported as the most satisfactory chemical shifts to be used in distinguishing between the salt and non-ionic forms of the substituted benzofuroxans studied. Calculated energies at the self-consistent field (SCF) level of theory for both tautomeric forms (N1- and N3-oxide) of some compounds studied are used for predicting the tautomeric equilibrium constants. Absolute 17O shieldings are employed in the reversal of the assignments of 17O NMR signals existing in the literature.

  6. Double threading through DNA: NMR structural study of a bis-naphthalene macrocycle bound to a thymine–thymine mismatch

    PubMed Central

    Jourdan, Muriel; Granzhan, Anton; Guillot, Regis; Dumy, Pascal; Teulade-Fichou, Marie-Paule

    2012-01-01

    The macrocyclic bis-naphthalene macrocycle (2,7-BisNP), belonging to the cyclobisintercalator family of DNA ligands, recognizes T–T mismatch sites in duplex DNA with high affinity and selectivity, as evidenced by thermal denaturation experiments and NMR titrations. The binding of this macrocycle to an 11-mer DNA oligonucleotide containing a T–T mismatch was studied using NMR spectroscopy and NMR-restrained molecular modeling. The ligand forms a single type of complex with the DNA, in which one of the naphthalene rings of the ligand occupies the place of one of the mismatched thymines, which is flipped out of the duplex. The second naphthalene unit of the ligand intercalates at the A-T base pair flanking the mismatch site, leading to encapsulation of its thymine residue via double stacking. The polyammonium linking chains of the macrocycle are located in the minor and the major grooves of the oligonucleotide and participate in the stabilization of the complex by formation of hydrogen bonds with the encapsulated thymine base and the mismatched thymine remaining inside the helix. The study highlights the uniqueness of this cyclobisintercalation binding mode and its importance for recognition of DNA lesion sites by small molecules. PMID:22362757

  7. NMR studies of conformational states of proteins involved in biosynthesis of iron-sulfur clusters

    NASA Astrophysics Data System (ADS)

    Dai, Ziqi

    Iron-sulfur (Fe-S) clusters are the most ancient and ubiquitous cofactors that exist throughout evolution. The most important biosynthetic system of the cluster in both prokaryotes and eukaryotes is the ISC system. Defects in this system can be lethal and have been associated with a number of human diseases. Previous works show that a number of proteins are involved in the [Fe-S] biosynthetic processes and the structural flexibility may play an important role. For example, it was shown that apo-IscU, the scaffold protein, from Escherichia coli populates two functionally important conformational states, one dynamically disordered (D-state) and the other more structured (S-state) (Kim et al., 2009; Kim et al., 2012c). To further investigate the characteristics and transition of the conformational states of proteins involved in this system, I performed extensive NMR studies. Here, I present the findings based on my studies of two important players of the ISC system, IscU and HscB. In this research, I find that a peptidyl-prolyl cis/trans isomerization might account for the slow step in the S-D interconversion of IscU. More specifically, P14 and P101 are trans in the S-state, but become cis in the D-state. In addition, I discover that IscU is very responsive to pH changes, and I postulate that this response is correlated to conserved histidine residues, H10 and H105. Moreover, my thermodynamic analyses reveal that the S-D equilibrium of IscU is also very sensitive to change in temperature, pressure, and amino acid sequence compared to other proteins. In the study, I also discovered a novel state of IscU, the unfolded U-state. I suspect that this state may serve as an intermediate of interconversion between IscU S-/D-states. Finally, I extended the effort to HscB, and find that it may possess more conformational flexibility than expected earlier. I postulate that this flexibility may be the cause of the line-broadening observed during interaction of HscB with Isc

  8. Changes in Porcine Muscle Water Characteristics during Growth—An in Vitro Low-Field NMR Relaxation Study

    NASA Astrophysics Data System (ADS)

    Bertram, Hanne Christine; Rasmussen, Marianne; Busk, Hans; Oksbjerg, Niels; Karlsson, Anders Hans; Andersen, Henrik Jørgen

    2002-08-01

    This study investigates the effects of developmental stage and muscle type on the mobility and distribution of water within skeletal muscles, using low-field 1H-NMR transverse relaxation measurements in vitro on four different porcine muscles ( M. longissimus dorsi, M. semitendinosus, M. biceps femoris, M. vastus intermedius) from a total of 48 pigs slaughtered at various weight classes between 25 kg and 150 kg. Principal component analysis (PCA) revealed effects of both slaughter weight and muscle type on the transverse relaxation decay. Independent of developmental stage and muscle type, distributed exponential analysis of the NMR T 2 relaxation data imparted the existence of three distinct water populations, T 2b, T 21, and T 22, with relaxation times of approximately 1-10, 45-120, and 200-500 ms, respectively. The most profound change during muscle growth was a shift toward faster relaxation in the intermediate time constant, T 21. It decreased by approx. 24% in all four muscle types during the period from 25 to 150 kg live weight. Determination of dry matter, fat, and protein content in the muscles showed that the changes in relaxation time of the intermediate time constant, T 21, during growth should be ascribed mainly to a change in protein content, as the protein content explained 77% of the variation in the T 21 time constant. Partial least squares (PLS) regression revealed validated correlations in the region of 0.58 to 0.77 between NMR transverse relaxation data and muscle development for all the four muscle types, which indicates that NMR relaxation measurements may be used in the prediction of muscle developmental stage.

  9. NMR cryoporometry characterisation studies of the relation between drug release profile and pore structural evolution of polymeric nanoparticles.

    PubMed

    Gopinathan, Navin; Yang, Bin; Lowe, John P; Edler, Karen J; Rigby, Sean P

    2014-07-20

    PLGA/PLA polymeric nanoparticles could potentially enhance the effectiveness of convective delivery of drugs, such as carboplatin, to the brain, by enabling a more sustained dosage over a longer time than otherwise possible. However, the link between the controlled release nanoparticle synthesis route, and the subsequent drug release profile obtained, is not well-understood, which hinders design of synthesis routes and availability of suitable nanoparticles. In particular, despite pore structure evolution often forming a key aspect of past theories of the physical mechanism by which a particular drug release profile is obtained, these theories have not been independently tested and validated against pore structural information. Such validation is required for intelligent synthesis design, and NMR cryoporometry can supply the requisite information. Unlike conventional pore characterisation techniques, NMR cryoporometry permits the investigation of porous particles in the wet state. NMR cryoporometry has thus enabled the detailed study of the evolving, nanoscale structure of nanoparticles during drug release, and thus related pore structure to drug release profile in a way not done previously for nanoparticles. Nanoparticles with different types of carboplatin drug release profiles were compared, including burst release, and various forms of delayed release. ESEM and TEM images of these nanoparticles also provided supporting data showing the rapid initial evolution of some nanoparticles. Different stages, within a complex, varying drug release profile, were found to be associated with particular types of changes in the nanostructure which could be distinguished by NMR. For a core-coat nanoparticle formulation, the development of smaller nanopores, following an extended induction period with no structural change, was associated with the onset of substantial drug release. This information could be used to independently validate the rationale for a particular synthesis

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

    PubMed

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

    2015-05-01

    (1)H and (13)C NMR spectra of allyl isothiocyanate (AITC) were measured, and the exchange dynamics were studied to explain the near-silence of the ITC carbon in (13)C NMR spectra. The dihedral angles α = ∠(C1-C2-C3-N4) and β = ∠(C2-C3-N4-C5) describe the conformational dynamics (conformation change), and the bond angles γ = ∠(C3-N4-C5) and ε = ∠(N4-C5-S6) dominate the molecular dynamics (conformer flexibility). The conformation space of AITC contains three minima, Cs-M1 and enantiomers M2 and M2'; the exchange between conformers is very fast, and conformational effects on (13)C chemical shifts are small (νM1 - νM2 < 3 ppm). Isotropic chemical shifts, ICS(γ), were determined for sp, sp(x), and sp(2) N-hybridization, and the γ dependencies of δ(N4) and δ(C5) are very large (10-33 ppm). Atom-centered density matrix propagation trajectories show that every conformer can access a large region of the potential energy surface AITC(γ,ε,...) with 120° < γ < 180° and 155° < ε < 180°. Because the extreme broadening of the (13)C NMR signal of the ITC carbon is caused by the structural flexibility of every conformer of AITC, the analysis provides a general explanation for the near-silence of the ITC carbon in (13)C NMR spectra of organic isothiocyanates.

  11. NMR cryoporometry characterisation studies of the relation between drug release profile and pore structural evolution of polymeric nanoparticles.

    PubMed

    Gopinathan, Navin; Yang, Bin; Lowe, John P; Edler, Karen J; Rigby, Sean P

    2014-07-20

    PLGA/PLA polymeric nanoparticles could potentially enhance the effectiveness of convective delivery of drugs, such as carboplatin, to the brain, by enabling a more sustained dosage over a longer time than otherwise possible. However, the link between the controlled release nanoparticle synthesis route, and the subsequent drug release profile obtained, is not well-understood, which hinders design of synthesis routes and availability of suitable nanoparticles. In particular, despite pore structure evolution often forming a key aspect of past theories of the physical mechanism by which a particular drug release profile is obtained, these theories have not been independently tested and validated against pore structural information. Such validation is required for intelligent synthesis design, and NMR cryoporometry can supply the requisite information. Unlike conventional pore characterisation techniques, NMR cryoporometry permits the investigation of porous particles in the wet state. NMR cryoporometry has thus enabled the detailed study of the evolving, nanoscale structure of nanoparticles during drug release, and thus related pore structure to drug release profile in a way not done previously for nanoparticles. Nanoparticles with different types of carboplatin drug release profiles were compared, including burst release, and various forms of delayed release. ESEM and TEM images of these nanoparticles also provided supporting data showing the rapid initial evolution of some nanoparticles. Different stages, within a complex, varying drug release profile, were found to be associated with particular types of changes in the nanostructure which could be distinguished by NMR. For a core-coat nanoparticle formulation, the development of smaller nanopores, following an extended induction period with no structural change, was associated with the onset of substantial drug release. This information could be used to independently validate the rationale for a particular synthesis

  12. NMR cryoporometry characterisation studies of the relation between drug release profile and pore structural evolution of polymeric nanoparticles

    PubMed Central

    Gopinathan, Navin; Yang, Bin; Lowe, John P.; Edler, Karen J.; Rigby, Sean P.

    2014-01-01

    PLGA/PLA polymeric nanoparticles could potentially enhance the effectiveness of convective delivery of drugs, such as carboplatin, to the brain, by enabling a more sustained dosage over a longer time than otherwise possible. However, the link between the controlled release nanoparticle synthesis route, and the subsequent drug release profile obtained, is not well-understood, which hinders design of synthesis routes and availability of suitable nanoparticles. In particular, despite pore structure evolution often forming a key aspect of past theories of the physical mechanism by which a particular drug release profile is obtained, these theories have not been independently tested and validated against pore structural information. Such validation is required for intelligent synthesis design, and NMR cryoporometry can supply the requisite information. Unlike conventional pore characterisation techniques, NMR cryoporometry permits the investigation of porous particles in the wet state. NMR cryoporometry has thus enabled the detailed study of the evolving, nanoscale structure of nanoparticles during drug release, and thus related pore structure to drug release profile in a way not done previously for nanoparticles. Nanoparticles with different types of carboplatin drug release profiles were compared, including burst release, and various forms of delayed release. ESEM and TEM images of these nanoparticles also provided supporting data showing the rapid initial evolution of some nanoparticles. Different stages, within a complex, varying drug release profile, were found to be associated with particular types of changes in the nanostructure which could be distinguished by NMR. For a core-coat nanoparticle formulation, the development of smaller nanopores, following an extended induction period with no structural change, was associated with the onset of substantial drug release. This information could be used to independently validate the rationale for a particular synthesis

  13. N-15 NMR study of the immobilization of 2,4- and 2,6-dinitrotoluene in aerobic compost

    USGS Publications Warehouse

    Thorn, K.A.; Pennington, J.C.; Kennedy, K.R.; Cox, L.G.; Hayes, C.A.; Porter, B.E.

    2008-01-01

    Large-scale aerobic windrow composting has been used to bioremediate washout lagoon soils contaminated with the explosives TNT (2,4,6- trinitrotoluene) and RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) at several sites within the United States. We previously used 15N NMR to investigate the reduction and binding of T15NT in aerobic bench -scale reactors simulating the conditions of windrow composting. These studies have been extended to 2,4-dinitrotoluene (2,4DNT) and 2,6-dinitrotoluene (2,6DNT), which, as impurities in TNT, are usually present wherever soils have been contaminated with TNT. Liquid-state 15N NMR analyses of laboratory reactions between 4-methyl-3-nitroaniline-15N, the major monoamine reduction product of 2,4DNT, and the Elliot soil humic acid, both in the presence and absence of horseradish peroxidase, indicated that the amine underwent covalent binding with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and non-heterocyclic condensation products. Liquid-state 15N NMR analyses of the methanol extracts of 20 day aerobic bench-scale composts of 2,4-di-15N-nitrotoluene and 2,6-di-15N-nitrotoluene revealed the presence of nitrite and monoamine, but not diamine, reduction products, indicating the occurrence of both dioxygenase enzyme and reductive degradation pathways. Solid-state CP/MAS 15N NMR analyses of the whole composts, however, suggested that reduction to monoamines followed by covalent binding of the amines to organic matter was the predominant pathway. ?? 2008 American Chemical Society.

  14. Experimental and theoretical studies on compositions, structures, and IR and NMR spectra of functionalized protic ionic liquids.

    PubMed

    Cui, Yingna; Yin, Jingmei; Li, Changping; Li, Shenmin; Wang, Ailing; Yang, Guang; Jia, Yingping

    2016-07-20

    The compositions and structures of amine-based functionalized protic ionic liquids (PILs), namely N,N-dimethyl(cyanoethyl)ammonium propionate (DMCEAP) and N,N-dimethyl(hydroxyethyl)ammonium propionate (DMEOAP) have been investigated systematically by IR and (1)H NMR spectroscopy and density functional theory (DFT) calculations. Analysis of the IR spectra suggests that both DMCEAP and DMEOAP are composed of neutral and ionized species in the liquid phase, the former one mainly existing in the state of precursor molecules, and the latter mainly as ion-pairs. The ratio of precursor molecules to ion-pairs in the liquid phase depends on the types of precursors, especially the functional groups of cations. (1)H NMR spectra indicate that there is a dynamic equilibrium between the neutral and ionized species, probably due to the formation of some intermediates in the PILs. The DFT calculations have been carried out to reveal the conformation, and obtain the corresponding IR and (1)H NMR spectra of the neutral and ionized species, so that the theoretical support to the experimental results can be provided. The present study will help understand the properties of PILs and provide guidance for further applications of PILs. PMID:27385035

  15. 1H NMR and Rheological Studies of the Calcium Induced Gelation Process in Aqueous Low Methoxyl Pectin Solutions

    NASA Astrophysics Data System (ADS)

    Dobies, M.; Kuśmia, S.; Jurga, S.

    2006-07-01

    The 1H NMR relaxometry in combination with water proton spin-spin relaxation time measurements and rheometry have been applied to study the ionic gelation of 1% w/w aqueous low methoxyl pectin solution induced by divalent Ca2+ cations from a calcium chloride solution. The model-free approach to the analysis of 1H NMR relaxometry data has been used to separate the information on the static (β) and dynamic (<τ_c>) behaviour of the systems tested. The 1H NMR results confirm that the average mobility of both water and the pectin molecules is largely dependent on the concentration of the cross-linking agent. The character of this dependency (β,<τc> and T2 vs. CaCl2 concentration) is consistent with the two-stage gelation process of low methoxyl pectin, in which the formation of strongly linked dimer associations (in the range of 0-2.5 mM CaCl2) is followed by the appearance of weak inter-dimer aggregations (for CaCl2≥ 3.5 mM). The presence of the weak gel structure for the sample with 3.5 mM CaCl2 has been confirmed by rheological measurements. Apart from that, the T1 and T2 relaxation times have been found to be highly sensitive to the syneresis phenomenon, which can be useful to monitor the low methoxyl pectin gel network stability.

  16. X-ray, NMR and DFT studies on benzo[h]thiazolo[2,3-b]quinazoline derivatives

    NASA Astrophysics Data System (ADS)

    Gupta, Richa; Chaudhary, R. P.

    2013-10-01

    4-Phenyl-3,4,5,6-tetrahydrobenzo[h]quinazoline-2(1H)-thione 3, obtained by the condensation of 2-Benzylidene-3,4-dihydronapthalen-1(2H)-one 2 with thiourea, on reaction with chloroacetic acid and 1,2-dibromoethane furnish compounds 4 and 5 and not their possible isomers 7 and 8 respectively. The regiochemistry of the cyclized products and their structure is established by elemental analysis, 1H NMR, 13C NMR, IR and mass spectral data. Density functional theory (DFT) calculations have been carried out for compounds 4, 5 and their isomers 7 and 8 with Jaguar version 6.5112 using B3LYP density functional method and 6-31G∗∗ basis set. X-ray diffraction technique indicates that compound 4 crystallizes in the triclinic space group P-1, with Z = 2 and cell parameters a = 6.3404 (11) Å, b = 9.997 (3) Å, c = 13.560 (2) Å, α = 107.532(19)°, β = 94.108(14)°, γ = 97.469(17)°. 1H and 13C NMR of compounds 4, 5, 7 and 8 have been calculated and correlated with experimental results. 2-Arylidene derivatives of 4 were obtained by two routes and their structure was established by spectral data. The lowest energy optimized geometry of the compound 4 in gas phase is consistent with that obtained by X-ray crystallographic studies.

  17. Unfolding the mechanism of the AAA+ unfoldase VAT by a combined cryo-EM, solution NMR study.

    PubMed

    Huang, Rui; Ripstein, Zev A; Augustyniak, Rafal; Lazniewski, Michal; Ginalski, Krzysztof; Kay, Lewis E; Rubinstein, John L

    2016-07-19

    The AAA+ (ATPases associated with a variety of cellular activities) enzymes play critical roles in a variety of homeostatic processes in all kingdoms of life. Valosin-containing protein-like ATPase of Thermoplasma acidophilum (VAT), the archaeal homolog of the ubiquitous AAA+ protein Cdc48/p97, functions in concert with the 20S proteasome by unfolding substrates and passing them on for degradation. Here, we present electron cryomicroscopy (cryo-EM) maps showing that VAT undergoes large conformational rearrangements during its ATP hydrolysis cycle that differ dramatically from the conformational states observed for Cdc48/p97. We validate key features of the model with biochemical and solution methyl-transverse relaxation optimized spectroscopY (TROSY) NMR experiments and suggest a mechanism for coupling the energy of nucleotide hydrolysis to substrate unfolding. These findings illustrate the unique complementarity between cryo-EM and solution NMR for studies of molecular machines, showing that the structural properties of VAT, as well as the population distributions of conformers, are similar in the frozen specimens used for cryo-EM and in the solution phase where NMR spectra are recorded.

  18. A solid state NMR study of layered double hydroxides intercalated with para-amino salicylate, a tuberculosis drug.

    PubMed

    Jensen, Nicholai Daugaard; Bjerring, Morten; Nielsen, Ulla Gro

    2016-09-01

    Para-amino salicylate (PAS), a tuberculosis drug, was intercalated in three different layered double hydroxides (MgAl, ZnAl, and CaAl-LDH) and the samples were studied by multi-nuclear ((1)H, (13)C, and (27)Al) solid state NMR (SSNMR) spectroscopy in combination with powder X-ray diffraction (PXRD), elemental analysis and IR-spectroscopy to gain insight into the bulk and atomic level structure of these LDHs especially with a view to the purity of the LDH-PAS materials and the concentration of impurities. The intercalations of PAS in MgAl-, ZnAl-, and CaAl-LDH's were confirmed by (13)C SSNMR and PXRD. Moreover, (13)C MAS NMR and infrared spectroscopy show that PAS did not decompose during synthesis. Large amounts (20-41%) of amorphous aluminum impurities were detected in the structure using (27)Al single pulse and 3QMAS NMR spectra, which in combination with (1)H single and double quantum experiments also showed that the M(II):Al ratio was higher than predicted from the bulk metal composition of MgAl-PAS and ZnAl-PAS. Moreover, the first high-resolution (1)H SSNMR spectra of a CaAl LDH is reported and assigned using (1)H single and double quantum experiments in combination with (27)Al{(1)H} HETCOR.

  19. NMR study comparing capillary trapping in Berea sandstone of air, carbon dioxide, and supercritical carbon dioxide after imbibition of water

    NASA Astrophysics Data System (ADS)

    Prather, Cody A.; Bray, Joshua M.; Seymour, Joseph D.; Codd, Sarah L.

    2016-02-01

    Nuclear magnetic resonance (NMR) techniques were used to study the capillary trapping mechanisms relevant to carbon sequestration. Capillary trapping is an important mechanism in the initial trapping of supercritical CO2 in the pore structures of deep underground rock formations during the sequestration process. Capillary trapping is considered the most promising trapping option for carbon sequestration. NMR techniques noninvasively monitor the drainage and imbibition of air, CO2, and supercritical CO2 with DI H2O at low capillary numbers in a Berea sandstone rock core under conditions representative of a deep underground saline aquifer. Supercritical CO2 was found to have a lower residual nonwetting (NW) phase saturation than that of air and CO2. Supercritical CO2 behaves differently than gas phase air or CO2 and leads to a reduction in capillary trapping. NMR relaxometry data suggest that the NW phase, i.e., air, CO2, or supercritical CO2, is preferentially trapped in larger pores. This is consistent with snap-off conditions being more favorable in macroscale pores, as NW fluids minimize their contact area with the solid and hence prefer larger pores.

  20. A 45Sc-NMR and DFT calculation study of crystalline scandium compounds

    NASA Astrophysics Data System (ADS)

    Bräuniger, Thomas; Hofmann, Andreas J.; Moudrakovski, Igor L.; Hoch, Constantin; Schnick, Wolfgang

    2016-01-01

    A series of scandium compounds, namely ScPO4, ScOF, Li3Sc(BO3)2, and CaSc2O4, were prepared according to procedures described in the literature, and then characterised by powder X-ray diffraction and solid-state 45Sc-NMR spectroscopy. By computer fitting, the quadrupolar interaction parameters χ and η, as well as the isotropic chemical shifts δiso were extracted from the NMR spectra. For comparison and site assignment of 45Sc, density functional theory (DFT) calculations of the EFG tensor were carried out with the CASTEP code. For the compounds with a well-defined formal coordination number (CN), a convincing linear correlation between CN and isotropic chemical shift could be established.

  1. Field-induced periodic distortions in a nematic liquid crystal: deuterium NMR study and theoretical analysis.

    PubMed

    Sugimura, A; Zakharov, A V

    2011-08-01

    The peculiarities in the dynamic of the director reorientation in a liquid crystal (LC) film under the influence of the electric E field directed at an angle α to the magnetic B field have been investigated both experimentally and theoretically. Time-resolved deuterium NMR spectroscopy is employed to investigate the field-induced director dynamics. Analysis of the experimental results, based on the predictions of hydrodynamic theory including both the director motion and fluid flow, provides an evidence for the appearance of the spatially periodic patterns in 4-n-pentyl-4'-cyanobiphenyl LC film, at the angles α>60∘, in response to the suddenly applied E. These periodic distortions produce a lower effective rotational viscosity. This gives a faster response of the director rotation than for a uniform mode, as observed in our NMR experiment. PMID:21929001

  2. New class of aggregates in aqueous solution: an NMR, thermodynamic, and dynamic light scattering study.

    PubMed

    Sanna, Cecilia; La Mesa, Camillo; Mannina, Luisa; Stano, Pasquale; Viel, Stéphane; Segre, Annalaura

    2006-07-01

    We investigated the aggregation properties of two classes of aromatic and hydrophobic compounds, namely chloroacetamides and ethyl 3-phenyl-2-nitropropionates, in moderately concentrated aqueous solution (millimolar range). The identification of all species present in solution under specific experimental conditions was performed by 1D and 2D NMR, pulsed gradient spin-echo NMR, and dynamic light scattering techniques. Some physical-chemical properties (viscosity, surface tension, and colligative properties) of the aqueous solutions were also determined. Both classes of compounds behave quite similarly: in solution, three distinct species, namely a monomeric species, small and mobile aggregates, and large and stiff aggregates, are observed. The results give insight into a new class of aggregates, held together by pi-pi interactions, which show an unusual associative behavior in water.

  3. The structure of tellurite glass: A combined NMR, neutron diffraction, and x-ray diffraction study

    SciTech Connect

    McLaughlin, J. C.; Tagg, S. L.; Zwanzier, J. W.; Shastri, S. D.; Haeffner, D. R.

    2000-04-04

    Models are presented of sodium tellurite glasses in the composition range (Na{sub 2}0){sub x}-(TeO{sub 2}){sub 1{minus}x}. 0.1 < x < 0.3. The models combine self-consistently data from three different and complementary sources: sodium-23 nuclear magnetic resonance (NMR), neutron diffraction, and x-ray diffraction. The models were generated using the Reverse Monte Carlo algorithm, modified to include NMR data in addition to diffraction data. The presence in the models of all five tellurite polyhedra consistent with the Te{sup +4} oxidation state were found to be necessary to achieve agreement with the data. The distribution of polyhedra among these types varied from a predominance of highly bridged species at low sodium content, to polyhedra with one or zero bridging oxygen at high sodium content. The models indicate that the sodium cations themselves form sodium oxide clusters particularly at the x = 0.2 composition.

  4. Magic-angle-spinning NMR studies of acid sites in zeolite H-ZSM-5

    SciTech Connect

    Brunner, E.; Ernst, H.; Freude, D.; Froehlich, T.; Hunger, M.; Pfeifer, H. )

    1991-01-01

    {sup 1}H, {sup 13}C, {sup 27}Al, and {sup 29}Si magic-angle-spinning (MAS) NMR was used to elucidate the nature of the catalytic activity of zeolite H-ZSM-5. {sup 1}H MAS NMR of sealed samples after mild hydrothermal dealumination shows that the enhanced activity for n-hexane cracking is not due to an enhanced Bronstead acidity. The concentrations of the various OH groups and aluminous species suggest that the reason for the enhanced catalytic activity is the interaction of the n-hexane molecule with a bridging hydroxyl group and with extra-framework aluminium species, which give rise to the enhanced activity, cannot be easily removed from their positions, and are therefore immobilized by the zeolitic framework.

  5. 13C and 1H NMR (Nuclear Magnetic Resonance) studies of solid polyolefines

    NASA Technical Reports Server (NTRS)

    Cudby, M. E. A.; Harris, R. K.; Metcalfe, K.; Packer, K. J.; Smith, P. W. R.

    1983-01-01

    The basis of H-1 and C-13 high-resolution NMR investigations of solid polymers is outlined. The C-13 NMR spectra of solid syndiotactic and isotactic polypropene are discussed and their interpretation in terms of conformation and chain-packing effects are reviewed. The effects of decreasing temperature on the C-13 high-resolution spectrum of an annealed sample of isotactic polypropene is described and interpreted in terms of the crystal structure. The question of the proportion of the sample giving rise to C-13 signals is addressed and some results reported. The main cause for observing only part of the total sample is shown to be the H-1 rotating frame spin-lattice relaxation behavior. The H-1 spin-lattice relaxation and spectral characteristics of a number of polyolefin samples are summarized and the role of spin-diffusion discussed.

  6. CD and 31P NMR studies of tachykinin and MSH neuropeptides in SDS and DPC micelles

    NASA Astrophysics Data System (ADS)

    Schneider, Sydney C.; Brown, Taylor C.; Gonzalez, Javier D.; Levonyak, Nicholas S.; Rush, Lydia A.; Cremeens, Matthew E.

    2016-02-01

    Secondary structural characteristics of substance P (SP), neurokinin A (NKA), neurokinin B (NKB), α-melanocyte stimulating hormone peptide (α-MSH), γ1-MSH, γ2-MSH, and melittin were evaluated with circular dichroism in phosphite buffer, DPC micelles, and SDS micelles. CD spectral properties of γ1-MSH and γ2-MSH as well as 31P NMR of DPC micelles with all the peptides are reported for the first time. Although, a trend in the neuropeptide/micelle CD data appears to show increased α-helix content for the tachykinin peptides (SP, NKA, NKB) and increased β-sheet content for the MSH peptides (α-MSH, γ1-MSH, γ2-MSH) with increasing peptide charge, the lack of perturbed 31P NMR signals for all neuropeptides could suggest that the reported antimicrobial activity of SP and α-MSH might not be related to a membrane disruption mode of action.

  7. Rotational energy barrier of 2-(2',6'-dihydroxyphenyl)benzoxazole: a case study by NMR.

    PubMed

    Chen, Weihua; Twum, Eric B; Li, Linlin; Wright, Brian D; Rinaldi, Peter L; Pang, Yi

    2012-01-01

    2-(2'-Hydroxyphenyl)benzoxazole (HBO) derivatives represent an important class of luminescent materials, as they can undergo excited state intramolecular proton transfer (ESIPT). The material's ESIPT properties are dependent on the ratio of two different rotamers, whose interconversion is poorly understood. By using HBO derivative 4, the rotational energy barrier of 2- (2',6'-hydroxyphenyl)benzoxazole is determined to be 10.5 kcal/mol by variable-temperature NMR. Although a HBO derivative typically exhibits two rotamers with O···H-O (e.g., 1a) and N···H-O bonding (e.g., 1b), correlation of NMR with fluorescence data reveals that the rotamer with N···H-O bonding is predominant in the solution.

  8. NMR Studies of Texture in the B-like Phase of 3He in Aerogel

    SciTech Connect

    Dmitriev, V. V.; Zavjalov, V. V.; Zmeev, D. E.; Mulders, N.

    2006-09-07

    Continuous wave NMR experiments have been performed in the B-like phase of 3He in a 98% open aerogel. The results allow us to get information about the texture of the 3He order parameter inside the aerogel. We conclude that in the B-like phase the boundary between the bulk 3He and the aerogel orients the vector of orbital anisotropy (L) parallel to it. Two stable textures and textural transition between them were observed in our sample.

  9. NMR spectroscopic study of the complexation behaviors of deuterated cyclodextrins and [60]fullerene.

    PubMed

    Ikeda, Atsushi; Hida, Tomohiro; Kikuchi, Jun-ichi; Nobusawa, Kazuyuki; Matsuo, Takashi

    2013-12-20

    Cyclodextrins (CDxs) have been selectively deuterated using a Ru/C-catalyzed H-D exchange reaction in D2O. The structures of the deuterated CDxs barely changed and their (1)H NMR spectra became very simple, which made it possible for the deuterated CDxs to be applied to the analysis of CDx complexes. Furthermore, the deuterated CDxs allowed for the existence of the equilibrium between free and complexed CDx to be confirmed, even at rt. PMID:24266835

  10. Metal corrosion in bones implanted with Zinalco--a SAXS and NMR study.

    PubMed

    Lima, E; Bosch, P; Lara, V; Villarreal, E; Piña, C; Torres, G; Martín, S; León, B

    2006-01-01

    The composition and morphology of bones implanted with stainless steel (316L-SS) and a metal alloy made of zinc, aluminum, and copper (Zinalco) are compared. Small-angle X-ray scattering (SAXS) and nuclear magnetic resonance (NMR) results show that with time Zinalco is corroded and zinc, aluminum, and copper diffuse into the osseous tissue, promoting nonhomogeneous bone. Instead, 316L-SS does not incorporate into bone, and the bone recovers homogeneously at a lower speed.

  11. Molecular dynamics studies on the NMR and X-ray structures of rabbit prion proteins.

    PubMed

    Zhang, Jiapu; Zhang, Yuanli

    2014-02-01

    Prion diseases, traditionally referred to as transmissible spongiform encephalopathies (TSEs), are invariably fatal and highly infectious neurodegenerative diseases that affect a wide variety of mammalian species, manifesting as scrapie in sheep and goats, bovine spongiform encephalopathy (BSE or mad-cow disease) in cattle, chronic wasting disease in deer and elk, and Creutzfeldt-Jakob diseases, Gerstmann-Sträussler-Scheinker syndrome, fatal familial insomnia, and kulu in humans, etc. These neurodegenerative diseases are caused by the conversion from a soluble normal cellular prion protein (PrP(C)) into insoluble abnormally folded infectious prions (PrP(Sc)), and the conversion of PrP(C) to PrP(Sc) is believed to involve conformational change from a predominantly α-helical protein to one rich in β-sheet structure. Such a conformational change may be amenable to study by molecular dynamics (MD) techniques. For rabbits, classical studies show that they have a low susceptibility to be infected by PrP(Sc), but recently it was reported that rabbit prions can be generated through saPMCA (serial automated Protein Misfolding Cyclic Amplification) in vitro and the rabbit prion is infectious and transmissible. In this paper, we first do a detailed survey on the research advances of rabbit prion protein (RaPrP) and then we perform MD simulations on the NMR and X-ray molecular structures of rabbit prion protein wild-type and mutants. The survey shows to us that rabbits were not challenged directly in vivo with other known prion strains and the saPMCA result did not pass the test of the known BSE strain of cattle. Thus, we might still look rabbits as a prion resistant species. MD results indicate that the three α-helices of the wild-type are stable under the neutral pH environment (but under low pH environment the three α-helices have been unfolded into β-sheets), and the three α-helices of the mutants (I214V and S173N) are unfolded into rich β-sheet structures under

  12. NMR studies of multiple conformations in complexes of Lactobacillus casei dihydrofolate reductase with analogues of pyrimethamine

    SciTech Connect

    Birdsall, B.; Tendler, S.J.B.; Feeney, J.; Carr, M.D. ); Arnold, J.R.P.; Thomas, J.A.; Roberts, G.C.K. ); Griffin, R.J.; Stevens, M.F.G. )

    1990-10-01

    {sup 1}H and {sup 19}F NMR signals from bound ligands have been assigned in one- and two-dimensional NMR spectra of complexes of Lactobacillus casei dihydrofolate reductase with various pyrimethamine analogues. The signals were identified mainly by correlating signals from bound and free ligands by using 2D exchange experiments. Analogues with symmetrically substituted phenyl rings give rise to {sup 1}H signals from four nonequivalent aromatic protons, clearly indicating the presence of hindered rotation about the pyrimidine-phenyl bond. Analogues with symmetrically substituted phenyl rings give rise to {sup 1}H signals from four nonequivalent aromatic protons, clearly indicating the presence of hindered rotation about the pyrimidine-phenyl bond. Analogues containing asymmetrically substituted aromatic rings exist as mixtures of two rotational isomers (an enantiomeric pair) because of this hindered rotation and the NMR spectra revealed that both isomers (forms A and B) bind to the enzyme with comparable, though unequal, binding energies. In this case two complete sets of bound proton signals were observed. The relative orientations of the two forms have been determined from NOE through-space connections between protons on the ligand and protein. Ternary complexes with NADP{sup {plus}} were also examined.

  13. Combined experimental and computational NMR study of crystalline and amorphous zeolitic imidazolate frameworks.

    PubMed

    Baxter, Emma F; Bennett, Thomas D; Mellot-Draznieks, Caroline; Gervais, Christel; Blanc, Frédéric; Cheetham, Anthony K

    2015-10-14

    Zeolitic imidazolate frameworks (ZIFs) have attracted great interest in recent years due to their high chemical and thermal stability with promising applications in gas storage and separations. We investigate the structures of three different crystalline ZIFs - ZIF-4, ZIF-8, ZIF-zni - and their amorphous counterparts using high field (13)C and (15)N CP MAS NMR. The high field (20 T) allows for the observation of all crystallographically independent carbon and nitrogen atoms in the crystalline ZIFs. Combining our experimental results with density functional theory calculations enabled the assignment of all chemical shifts. The crystalline spectra reveal the potential of high field NMR to distinguish between two ZIF polymorphs, ZIF-4 and ZIF-zni, with identical [Zn(C3H3N2)2] chemical compositions. (13)C and (15)N CP MAS NMR data obtained for the amorphous ZIFs clearly showed signal broadening upon amorphization, confirming the retention of chemical composition and the structural similarity of amorphous ZIF-4 and ZIF-zni. In the case of amorphous ZIF-8, we present evidence for the partial de-coordination of the 2-methyl imidazole linker.

  14. Study of conformation and dynamic of surfactant molecules in graphite oxide via NMR

    NASA Astrophysics Data System (ADS)

    Ai, X. Q.; Ma, L. G.

    2016-08-01

    The conformation and dynamic of surfactant in graphite oxide (GO) was investigated by solid-state 13C magic-angle-spinning NMR and 1H-13C cross-polarization/magic-angle-spinning NMR spectra. The conformation ordering of the alkyl chains in the confined system shows strong dependence on its orientation. While the alkyl chains parallel to the GO layer in lateral monolayer arrangement are in gauche conformation in addition to a small amount of all-trans conformation, those with orientation radiating away from the GO in paraffin bilayer arrangement is in all-trans conformation in addition to some gauche conformation even though high-order diffraction peaks appears. NMR results suggest that the least mobile segment is located at the GO-surfactant interface corresponding to the N-methylene group. Further from it, the mobility of the alkyl chain increases. The terminal methyl and N-methyl carbon groups have the highest mobile. The chains in all-trans conformational state are characterized as more rigid than chains with gauche conformation; each segment of the confined alkyl chains with the lateral monolayer arrangement exhibits less mobility as compared to that with the paraffin bilayer arrangement.

  15. Aggregation properties and structural studies of anticancer drug Irinotecan in DMSO solution based on NMR measurements

    NASA Astrophysics Data System (ADS)

    D'Amelio, N.; Aroulmoji, V.; Toraldo, A.; Sundaraganesan, N.; Anbarasan, P. M.

    2012-04-01

    Irinotecan is an antitumor drug mostly used in the treatment of colorectal cancer. Its efficacy is influenced by the chemical state of the molecule undergoing chemical equilibria, metabolic changes and photodegradation. In this work, we describe the chemical equilibria of the drug in dimethyl sulfoxide (DMSO). The energetic barrier for hindered rotation around the bond connecting the piperidino—piperidino moiety with the camptothecin-like fragment was evaluated. Furthermore, we showed how the molecule aggregates in DMSO solution forming dimeric species able to prevent its degradation. The equilibrium constant for self-aggregation was determined by NMR based on the assumption of the isodesmic model. The formation of a dimer was highlighted by NMR diffusion ordered spectroscopy (NMR-DOSY) experiments at the concentrations used. Structural features of the complex were inferred by NOE and 13C chemical shift data. Molecular modelling of the complex driven by experimental data, lead to a structure implying the formation of two hydrogen bonds involving the lactone ring whose opening is one of the main causes of drug degradation. This species is probably responsible for the improved stability of the drug at concentrations higher than 1 mM.

  16. Conformation of eight-membered benzoannulated lactams by combined NMR and DFT studies.

    PubMed

    Witosińska, Agnieszka; Musielak, Bogdan; Serda, Paweł; Owińska, Maria; Rys, Barbara

    2012-11-01

    The title compounds were synthesized, and their structure and conformational behavior in solution (NMR and DFT), in the gas phase (DFT), and, for some of them, in the solid state (X-ray) were investigated. The variable-temperature NMR spectra were employed to determine the conformational equilibria and the activation energy of the conformational changes of the eight-membered ring. The coalescence effects are assigned to racemization of the chiral ground-state conformation with a ring inversion barrier in the range of 38-100 kJ mol(-1) depending on the relative setting of the two strong conformational constraints: benzoannulation and the amide function. The second conformational process, interconversion between two different conformers, in the molecules of benzo[c]azocin-3-one, benzo[d]azocin-2-one, and benzo[d]azocin-4-one was observed. The natures of the conformers observed in solution were elucidated by analysis of experimental and calculated NMR data. The present results are discussed in conjunction with previous experimental and theoretical data on (Z,Z)-cyclooctadienes and their benzo analogues.

  17. Solution deuterium NMR quadrupolar relaxation study of heme mobility in myoglobin

    SciTech Connect

    Johnson, R.D.; La Mar, G.N.; Smith, K.M.; Parish, D.W.; Langry, K.C. )

    1989-01-18

    NMR spectroscopy has been used to monitor the quadrupolar relaxation and motional dynamics of {sup 2}H selectively incorporated into skeletal and side chain positions of the heme in sperm whale myoglobin. The hyperfine shifts of the heme resonances in paramagnetic states of myoglobin allow resolution of the signals of interest, and paramagnetic contributions to the observed line widths are shown to be insignificant. The {sup 2}H line widths for the skeletal positions of deuterohemin-reconstituted myoglobin yield a correlation time identical with that of overall protein tumbling (9 ns at 30{degree}C) and hence reflect an immobile heme group. The {sup 2}H NMR line widths of heme methyl groups exhibit motional narrowing indicative of very rapid internal rotation. Hence the methyl rotation is effectively decoupled from the overall protein tumbling, and the residual quadrupolar line width can be used directly to determine the protein tumbling rate. The {sup 2}H NMR lines from heme vinyl groups were found narrower than those from the heme skeleton. However, the range of quadrupolar coupling constants for sp{sup 2} hybridized C-{sup 2}H bonds does not permit an unequivocal interpretation in terms of mobility. 48 refs., 4 figs.

  18. Environmentally friendly flame retardants. A detailed solid-state NMR study of melamine orthophosphate.

    PubMed

    Brinkmann, Andreas; Litvinov, Victor M; Kentgens, Arno P M

    2007-12-01

    We used solid-state NMR spectroscopy to gain detailed information about the proton positions, proximities and the hydrogen-bonding network in the environmentally friendly flame retardant melamine orthophosphate (MP). High-resolution proton one- and two-dimensional solid-state NMR spectra were obtained at high external magnetic field in combination with fast magic angle spinning of the sample. Furthermore, we recorded homo- and heteronuclear correlation spectra of types (15)N–(15)N, (1)H–(13)C, (1)H–(15)N and (1)H–(31)P. In addition, we determined the geometry of the NH and NH(2) groups in MP by (15)N–(1)H heteronuclear recoupling experiments.We were able to completely assign the different isotropic chemical shifts in MP. Furthermore, we could identify the protonation of the melamine and orthophosphate moieties. The experimental results are discussed in connection with the structural model obtained by powder X-ray diffraction together with a combined molecular modeling-Rietveld refinement approach (De Ridder et al. Helv. Chim. Acta 2004; 87: 1894). We show that the geometry of the NH2 groups can only be successfully estimated by solid-state NMR. PMID:18157843

  19. Combined experimental and computational NMR study of crystalline and amorphous zeolitic imidazolate frameworks.

    PubMed

    Baxter, Emma F; Bennett, Thomas D; Mellot-Draznieks, Caroline; Gervais, Christel; Blanc, Frédéric; Cheetham, Anthony K

    2015-10-14

    Zeolitic imidazolate frameworks (ZIFs) have attracted great interest in recent years due to their high chemical and thermal stability with promising applications in gas storage and separations. We investigate the structures of three different crystalline ZIFs - ZIF-4, ZIF-8, ZIF-zni - and their amorphous counterparts using high field (13)C and (15)N CP MAS NMR. The high field (20 T) allows for the observation of all crystallographically independent carbon and nitrogen atoms in the crystalline ZIFs. Combining our experimental results with density functional theory calculations enabled the assignment of all chemical shifts. The crystalline spectra reveal the potential of high field NMR to distinguish between two ZIF polymorphs, ZIF-4 and ZIF-zni, with identical [Zn(C3H3N2)2] chemical compositions. (13)C and (15)N CP MAS NMR data obtained for the amorphous ZIFs clearly showed signal broadening upon amorphization, confirming the retention of chemical composition and the structural similarity of amorphous ZIF-4 and ZIF-zni. In the case of amorphous ZIF-8, we present evidence for the partial de-coordination of the 2-methyl imidazole linker. PMID:26351979

  20. Multinuclear NMR study of some organoplatinum complexes containing multifunctional azines as chelating ligands.

    PubMed

    Gudat, Dietrich; Dogan, Akbey; Kaim, Wolfgang; Klein, Axel

    2004-09-01

    1H-detected indirect NMR techniques were used to determine 15N and 195Pt NMR parameters for a series of organoplatinum(IV) complexes and one platinum(II) complex containing nitrogen-based azobispyridine, bispyridyltetrazine, and bipyrimidine ligands. The inverse technique permitted the detection of small 4J(Pt,H) and 5J(Pt,H) long-range couplings and the acquisition of 15N NMR data in natural isotopic abundance via nJ(N,H) intra- and inter-ligand couplings, but failed in cases where coherence transfer is quenched by rapid relaxation of the metal atom. In one case, analysis of satellite patterns in a set of 1H,15N, 1H,195Pt and 1H,13C correlation spectra allowed a positive sign to be determined for 1J(Pt,15N). Qualitative arguments are presented to explain the observed 15N coordination shifts in complexes with different azine ligands in terms of azine-M dative bond formation and LnM-azine back-donation. PMID:15307061

  1. Deuterium NMR study of amino acid coordination to chromium(III)

    SciTech Connect

    Green, C.A.; Place, H.; Willett, R.D.; Legg, J.I.

    1986-12-17

    A series of bis(ethylenediamine)Cr(III)-amino acid complexes, synthesized with deuterium-labeled alanine, glycine, homoserine, leucine, methionine, phenylalanine, serine, and threonine, was characterized by /sup 2/H NMR spectroscopy. The spectra show that these bidentate-coordinated amino acid complexes decompose via monodentate species. In addition, the diastereomeric isomers of alanine and leucine can be distinguished in the spectra. This was confirmed by the isolation of one of the L-leucine isomers. The bis(1,3-propanediamine)Cr(III) complexes of glycine and alanine were also synthesized, and the NMR spectra of these complexes and ..cap alpha..-cis-(Cr(ethylenediaminediacetate)(glycinate)) show changes due to variation in the ligand complement. The crystal structure of ..cap alpha..-cis(Cr(ethylenediaminediacetate)(glycinate)) x 2H/sub 2/O (CrO/sub 6/N/sub 3/C/sub 8/H/sub 14/ x 2H/sub 2/O) was determined and supports the NMR observations. This complex crystallizes in the space group P2/sub 1//c of the monoclinic crystal system with a = 8.9231 (19) A, b = 10.1889 (22) A, c = 15.4180 (30) A, ..beta.. = 102.657 (17)/sup 0/, and Z = 4. An improved method for the synthesis of bis(diamine)Cr(III)-amino acid complexes is also reported. 24 references, 3 figures, 7 tables.

  2. Natural-abundance sup 13 C NMR study of glycogen repletion in human liver and muscle

    SciTech Connect

    Jue, T.; Rothman, D.L.; Tavitian, B.A.; Shulman, R.G. )

    1989-03-01

    Optimizing the surface-coil design and spectral-acquisition parameters has led to the observation of the {sup 13}C NMR natural abundance glycogen signal in man at 2.1 T. Both the human muscle and hepatic glycogen signals can be detected definitively with a time resolution of {approx}13 min. A {sup 1}H/{sup 13}C concentric surface coil was used. The {sup 1}H outer coil was 11 cm in diameter; the {sup 13}C inner coil was 8 cm in diameter. The coils were tuned to 89.3 MHz and 22.4 MHz, respectively. The {sup 1}H coil was used for optimizing field homogeneity (shimming) the magnet and for single-frequency decoupling of the C{sub 1} glycogen signal. Total power deposition from both the transmitter pulse and the continuous wave decoupling did not exceed the Food and Drug Administration guideline of 8 W/kg of tissue. Experiments were done for which healthy subjects returned to the magnets at different times for {sup 13}C NMR measurement. The spectral difference between experiments was within the noise in the C{sub 1} glycogen region. Because of the spectral reproducibility and the signal sensitivity, hepatic glycogen repletion can be followed. Four hours postprandial, hepatic glycogen increases by 3.8 times from the basal fasted state. The hepatic glycogen data correspond directly to previous biopsy results and support the use of {sup 13}C NMR as a noninvasive probe of human metabolism.

  3. Rotational isomerism of some chloroacetamides: Theoretical and experimental studies through calculations, infrared and NMR

    NASA Astrophysics Data System (ADS)

    Santos, Marcela F.; Braga, Carolyne B.; Rozada, Thiago C.; Basso, Ernani A.; Fiorin, Barbara C.

    2014-08-01

    The geometries involved in the conformational equilibria of 2,2-dichloro-N-cyclohexyl-N-methyl-acetamide (DCCMA) and 2-chloro-N,N-dicyclohexylacetamide (CDCA) were investigated. Theoretical calculations at the B3LYP/cc-pVDZ level of theory showed that gauche forms (Clsbnd Csbnd Cdbnd O) are the most stable and the predominant conformers in isolated phase. Both compounds had the conformational behavior in solvents of different polarities estimated from theoretical calculations with the PCM (Polarizable Continuum Model), at the same level of theory, using infrared data from deconvolution of the carbonyl absorption bands and 13C NMR spectra. Their IR spectra showed two carbonyl absorptions and that the conformer with the highest dipole moment had its population increased when the most polar solvents were used, in accordance with the theoretical calculation in solution. 1JCH coupling constants were obtained from their NMR spectra, and revealed that there was population variation of conformers with solvent exchange. Experimental data (NMR and IR) as well as calculations including the solvent effects followed the same trend.

  4. IN SITU MAGIC ANGLE SPINNING NMR FOR STUDYING GEOLOGICAL CO(2) SEQUESTRATION

    SciTech Connect

    Hoyt, David W.; Turcu, Romulus VF; Sears, Jesse A.; Rosso, Kevin M.; Burton, Sarah D.; Kwak, Ja Hun; Felmy, Andrew R.; Hu, Jian Z.

    2011-03-27

    Geological carbon sequestration (GCS) is one of the most promising ways of mitigating atmospheric greenhouse gases (1-3). Mineral carbonation reactions are potentially important to the long-term sealing effectiveness of caprock but remain poorly predictable, particularly in low-water supercritical CO2 (scCO2)-dominated environments where the chemistry has not been adequately explored. In situ probes that provide molecular-level information is desirable for investigating mechanisms and rates of GCS mineral carbonation reactions. MAS-NMR is a powerful tool for obtaining detailed molecular structure and dynamics information of a system regardless whether the system is in a solid, a liquid, a gaseous, or a supercritical state, or a mixture thereof (4,5). However, MAS NMR under scCO2 conditions has never been realized due to the tremendous technical difficulties of achieving and maintaining high pressure within a fast spinning MAS rotor (6,7), where non-metal materials must be used. In this work, we report development of a unique high pressure MAS NMR capability, and its application to mineral carbonation chemistry in scCO2 under geologically relevant temperatures and pressures.

  5. Solid-State NMR Studies of HIV-1 Capsid Protein Assemblies

    SciTech Connect

    Han, Yun; Ahn, Jinwoo; Concel, Jason; Byeon, In-Ja L.; Gronenborn, Angela M.; Yang, Jun; Polenova, Tatyana E.

    2010-02-17

    In mature HIV-1 virions, the 26.6 kDa CA protein is assembled into a characteristic cone-shaped core (capsid) that encloses the RNA viral genome. The assembled capsid structure is best described by a fullerene cone model that is made up from a hexameric lattice containing a variable number of CA pentamers, thus allowing for closure of tubular or conical structures. In this paper, we present a solid-state NMR analysis of the wild-type HIV-1 CA protein, prepared as conical and spherical assemblies that are stable and are not affected by magic angle spinning of the samples at frequencies between 10 and 25 kHz. Multidimensional homo- and heteronuclear correlation spectra of CA assemblies of uniformly 13C,15Nlabeled CA exhibit narrow lines, indicative of the conformational homogeneity of the protein in these assemblies. For the conical assemblies, partial residue-specific resonance assignments were obtained. Analysis of the NMR spectra recorded for the conical and spherical assemblies indicates that the CA protein structure is not significantly different in the different morphologies. The present results demonstrate that the assemblies of CA protein are amenable to detailed structural analysis by solid-state NMR spectroscopy.

  6. Solid-State NMR Studies of HIV-1 Capsid Protein Assemblies

    PubMed Central

    Han, Yun; Ahn, Jinwoo; Concel, Jason; Byeon, In-Ja L.; Gronenborn, Angela M.; Yang, Jun; Polenova, Tatyana

    2010-01-01

    In mature HIV-1 virions, a 26.6 kDa CA protein is assembled into a characteristic cone shaped core (capsid) that encloses the RNA viral genome. The assembled capsid structure is best described by a fullerene cone model that is made up from a hexameric lattice containing a variable number of CA pentamers, thus allowing for closure of tubular or conical structures. In this report, we present a solid-state NMR analysis of the wild type HIV-1 CA protein, prepared as conical and spherical assemblies that are stable and are not affected by magic angle spinning of the samples at frequencies between 10 and 25 kHz. Multidimensional homo- and heteronuclear correlation spectra of CA assemblies of uniformly 13C,15N-labelled CA exhibit narrow lines, indicative of conformational homogeneity of the protein in these assemblies. For the conical assemblies, partial residue-specific resonance assignments were obtained. Analysis of the NMR spectra recorded for the conical and spherical assemblies indicates that the CA protein structure is not significantly different in the different morphologies. The present results demonstrate that the assemblies of CA protein are amenable to detailed structural analysis by solid-state NMR spectroscopy. PMID:20092249

  7. Epitope mapping of antigenic MUC1 peptides to breast cancer antibody fragment B27.29: a heteronuclear NMR study.

    PubMed

    Grinstead, Jeffrey S; Schuman, Jason T; Campbell, A Patricia

    2003-12-01

    MUC1 mucin is a breast cancer-associated transmembrane glycoprotein, of which the extracellular domain is formed by the repeating 20-amino acid sequence GVTSAPDTRPAPGSTAPPAH. In neoplastic breast tissue, the highly immunogenic sequence PDTRPAP (in bold above) is exposed. Antibodies raised directly against MUC1-expressing tumors offer unique access to this neoplastic state, as they represent immunologically relevant "reverse templates" of the tumor-associated mucin. In a previous study [Grinstead, J. S., et al. (2002) Biochemistry 41, 9946-9961], (1)H NMR methods were used to correlate the effects of cryptic glycosylation outside of the PDTRPAP core epitope sequence on the recognition and binding of Mab B27.29, a monoclonal antibody raised against breast tumor cells. In the study presented here, isotope-edited NMR methods, including (15)N and (13)C relaxation measurements, were used to probe the recognition and binding of the PDTRPAP epitope sequence to Fab B27.29. Two peptides were studied: a one-repeat MUC1 16mer peptide of the sequence GVTSAPDTRPAPGSTA and a two-repeat MUC1 40mer peptide of the sequence (VTSAPDTRPAPGSTAPPAHG)(2). (15)N and (13)C NMR relaxation parameters were measured for both peptides free in solution and bound to Fab B27.29. The (13)C(alpha) T(1) values best represent changes in the local correlation time of the peptide epitope upon binding antibody, and demonstrate that the PDTRPAP sequence is immobilized in the antibody-combining site. This result is also reflected in the appearance of the (15)N- and (13)C-edited HSQC spectra, where line broadening of the same peptide epitope resonances is observed. The PDTRPAP peptide epitope expands upon the peptide epitope identified previously in our group as PDTRP by homonuclear NMR experiments [Grinstead, J. S., et al. (2002) Biochemistry 41, 9946-9961], and illustrates the usefulness of the heteronuclear NMR experiments. The implications of these results are discussed within the context of MUC1 breast

  8. Segmental isotope labeling of proteins for NMR structural study using a protein S tag for higher expression and solubility.

    PubMed

    Kobayashi, Hiroshi; Swapna, G V T; Wu, Kuen-Phon; Afinogenova, Yuliya; Conover, Kenith; Mao, Binchen; Montelione, Gaetano T; Inouye, Masayori

    2012-04-01

    A common obstacle to NMR studies of proteins is sample preparation. In many cases, proteins targeted for NMR studies are poorly expressed and/or expressed in insoluble forms. Here, we describe a novel approach to overcome these problems. In the protein S tag-intein (PSTI) technology, two tandem 92-residue N-terminal domains of protein S (PrS(2)) from Myxococcus xanthus is fused at the N-terminal end of a protein to enhance its expression and solubility. Using intein technology, the isotope-labeled PrS(2)-tag is replaced with non-isotope labeled PrS(2)-tag, silencing the NMR signals from PrS(2)-tag in isotope-filtered (1)H-detected NMR experiments. This method was applied to the E. coli ribosome binding factor A (RbfA), which aggregates and precipitates in the absence of a solubilization tag unless the C-terminal 25-residue segment is deleted (RbfAΔ25). Using the PrS(2)-tag, full-length well-behaved RbfA samples could be successfully prepared for NMR studies. PrS(2) (non-labeled)-tagged RbfA (isotope-labeled) was produced with the use of the intein approach. The well-resolved TROSY-HSQC spectrum of full-length PrS(2)-tagged RbfA superimposes with the TROSY-HSQC spectrum of RbfAΔ25, indicating that PrS(2)-tag does not affect the structure of the protein to which it is fused. Using a smaller PrS-tag, consisting of a single N-terminal domain of protein S, triple resonance experiments were performed, and most of the backbone (1)H, (15)N and (13)C resonance assignments for full-length E. coli RbfA were determined. Analysis of these chemical shift data with the Chemical Shift Index and heteronuclear (1)H-(15)N NOE measurements reveal the dynamic nature of the C-terminal segment of the full-length RbfA protein, which could not be inferred using the truncated RbfAΔ25 construct. CS-Rosetta calculations also demonstrate that the core structure of full-length RbfA is similar to that of the RbfAΔ25 construct.

  9. Molecular Mechanics and Variable-Temperature 1H NMR Studies on N,N-Diethyl-m-toluamide. An Undergraduate NMR and Molecular Modeling Experiment

    NASA Astrophysics Data System (ADS)

    Jensen, Bruce L.; Fort, Raymond C., Jr.

    2001-04-01

    A combination of molecular modeling and variable-temperature NMR experiments is used to analyze the barrier to rotation about the amide bond of N,N-diethyl-m-toluamide (DEET). This approach utilizes the ability of computers to calculate the potential energy of a set of conformations obtained from a dihedral drive around the N-CO bond. The results of this experiment demonstrate a substantial barrier of 15.9 kcal/mol. These data are applied to a set of 1H NMR spectra taken over a range of temperatures from 9 to 85 °C. At very low temperatures the conformation is "locked" and the spectrum displays two sets of triplets and two sets of quartets for the two nonequivalent ethyl groups. However, at high temperature the rapid rotation about the amide linkage produces only one quartet and one triplet, characteristic of two indistinguishable ethyl groups. The experiment offers students hands-on experience with two important laboratory instruments and allows for both qualitative and quantitative analysis of the data. This experiment is scheduled to coincide with lecture discussion of NMR spectroscopy, after the fundamentals of bond rotation have been presented.

  10. Dynamics of an integral membrane peptide: a deuterium NMR relaxation study of gramicidin.

    PubMed Central

    Prosser, R S; Davis, J H

    1994-01-01

    Solid state deuterium (2H) NMR inversion-recovery and Jeener-Broekaert relaxation experiments were performed on oriented multilamellar dispersions consisting of 1,2-dilauroyl-sn-glycero-3-phosphatidylcholine and 2H exchange-labeled gramicidin D, at a lipid to protein molar ratio (L/P) of 15:1, in order to study the dynamics of the channel conformation of the peptide in a liquid crystalline phase. Our dynamic model for the whole body motions of the peptide includes diffusion of the peptide around its helix axis and a wobbling diffusion around a second axis perpendicular to the local bilayer normal in a simple Maier-Saupe mean field potential. This anisotropic diffusion is characterized by the correlation times, tau R parallel and tau R perpendicular. Aligning the bilayer normal perpendicular to the magnetic field and graphing the relaxation rate, 1/T1Z, as a function of (1-S2N-2H), where S2N-2H represents the orientational order parameter, wer were able to estimate the correlation time, tau R parallel, for rotational diffusion. Although in the quadrupolar splitting, which varies as (3 cos2 theta D-1), has in general two possible solutions to theta D in the range 0 < or = theta D < or = 90 degrees, the 1/T1Z vs. (1-S2N-2H) curve can be used to determine a single value of theta D in this range. Thus, the 1/T1Z vs. (1-S2N-2H) profile can be used both to define the axial diffusion rate and to remove potential structural ambiguities in the splittings. The T1Z anisotropy permits us to solve for the two correlation times (tau R parallel = 6.8 x 10(-9) s and tau R perpendicular = 6 x 10(-6) s). The simulated parameters were corroborated by a Jeener-Broekaert experiment where the bilayer normal was parallel to the principal magnetic field. At this orientation the ratio, J2(2 omega 0)/J1(omega 0) was obtained in order to estimate the strength of the restoring potential in a model-independent fashion. This measurement yields the rms angle, 1/2 (= 16 +/- 2 degrees at

  11. Thermal decomposition of t-butylamine borane studied by in situ solid state NMR

    SciTech Connect

    Feigerle, J.; Smyrl, N. R.; Morrell, J. S.; Stowe, A. C.

    2010-03-18

    of the amine borane fuel more feasible [22]. In the present study, tert-butylamine borane is investigated by heteronuclear in situ solid state NMR to understand hydrogen release from a hydrocarbon containing amine borane. tbutylamine borane has similar physical properties to amine borane with a melting point of 96 C. A single proton has been replaced with a t-butylamine group resulting in a weakening of the dihydrogen bonding framework. t-butylamine borane has a theoretical gravimetric hydrogen density of 15.1%; however, isobutane can also be evolved rather than hydrogen. If decomposition yields one mole isobutane and two moles hydrogen, 4.5 wt% H2 gas will be evolved. More importantly for the present work, the resulting spent fuel should be comprised of both (BNH)n and (CBNH)n polyimidoboranes.

  12. Isomers and conformers of two push pull hydrazines studied by NMR and vibrational spectroscopy and by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Polovková, J.; Gatial, A.; Milata, V.; Černuchová, P.; Prónayová, N.; Matějka, P.

    2007-05-01

    The isomers and conformers of two push-pull hydrazines: 3- N, N-dimethylhydrazino-2-acetyl propenenitrile [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(COCH 3)] (DMHAP) and 3- N, N-dimethylhydrazino-2-methylsulfonyl propenenitrile [(H 3C) 2N sbnd NH sbnd CH dbnd C(CN)(SO 2CH 3)] (DMHSP) have been studied experimentally by NMR and vibrational spectroscopy and theoretically by the ab initio calculations at MP2 level in 6-31G** basis set. The IR and Raman spectra of both compounds as a solid and solute in various solvents have been recorded. The NMR spectra were obtained in chloroform and DMSO at room temperature. Both compounds have been prepared by the same way. NMR spectra revealed that DMHAP was prepared as a pure Z-isomer whereas in the case of DMHSP a pure E-isomer was obtained. Due to the low barrier for both compounds practically free isomerisation process occurred in the solutions but in opposite directions. Whereas DMHAP exists in the solid state and in the less polar solvent as Z-isomer, in more polar solvents the appearance of next two conformers of E-isomer was observed. On the contrary DMHSP exists in the solid state and in the more polar solvent as E-isomer only but in less polar solvent the presence of Z-isomer was observed as well. Conformational possibilities of both studied compounds are given by the rotation of dimethylhydrazino group with its anti- or syn-orientation towards the olefinic double bond. Moreover, by the rotation of the acetyl group with Z- and E-orientation of carbonyl bond towards olefinic double bond can occur in DMHAP. Vibrational and NMR spectra revealed the existence of single conformer with intramolecular hydrogen bond for Z-isomer in less polar solvent and next two conformers for E-isomer of DMHAP with Z-orientation of acetyl group and anti and syn orientation of dimethylhydrazine group in more polar solvents. For E-isomer of DMHSP two conformers with anti or syn orientations of dimethylhydrazino group have been also confirmed by NMR

  13. Proton NMR study of spin dynamics in the magnetic organic chains M (hfac)3 NITEt (M =Eu3 +,Gd3 + )

    NASA Astrophysics Data System (ADS)

    Mariani, M.; Lascialfari, A.; Caneschi, A.; Ammannato, L.; Gatteschi, D.; Rettori, A.; Pini, M. G.; Cucci, C.; Borsa, F.

    2016-04-01

    In this work, we present a nuclear magnetic resonance (NMR) study of the spin dynamics in the rare-earth-based low-dimensional molecular magnetic chains Eu (hfac) 3NITEt and Gd (hfac) 3NITEt (in short, Eu-Et and Gd-Et). Although both samples are based on the same chemical building block, [(hfac) 3NITEt ] , their magnetic properties change dramatically when the Eu3 + ion, which is nonmagnetic at low temperatures, is substituted by the magnetic Gd3 + ion. The present proton NMR investigation shows that, down to the lowest investigated temperature (T =1.5 K for Gd-Et and T =3 K for Eu-Et), the Eu-Et chain behaves as a one-dimensional Heisenberg model with antiferromagnetic exchange coupling (J =-20 K) between s =1 /2 organic radicals, and has a T -independent exchange frequency (ωe=2.6 ×1012 rad/s). In the Gd-Et chain, in contrast, a competition arises between nearest-neighbor ferromagnetic coupling and next-nearest-neighbor antiferromagnetic coupling; moreover, two phase transitions have previously been found, in agreement with Villain's conjecture: a first transition, at T0=2.2 K, from a high temperature paramagnetic phase to a chiral spin liquid phase, and a second transition, at TN=1.9 K, to a three-dimensional helical spin solid phase. Contrary to the Eu-Et chain (whose three-dimensional ordering temperature is estimated to insurge at very low, TN≈0.3 K), critical spin dynamics effects have been measured in the Gd-Et chain on approaching TN=1.9 K: namely, a divergence of the proton nuclear spin-lattice relaxation rate 1 /T1 , which in turn produces a sudden wipe-out of the NMR signal in a very narrow (Δ T ˜0.04 K) temperature range above TN. Below TN, an inhomogeneous broadening of the NMR line indicates a complete spin freezing. At T0=2.2 K, instead, such critical effects are not observed because NMR measurements probe the two-spin correlation function, while the chiral spin liquid phase transition is associated with a divergence of the four

  14. Experimental studies of hydrogen on boron nitride: II. NMR studies of orientational ordering of H{sub 2}

    SciTech Connect

    Evans, M.D.; Sullivan, N.S.

    1995-09-01

    The authors report the results of NMR studies of thin films of hydrogen adsorbed on hexagonal boron nitride. Orientational ordering is observed below 1 K but the ordering is not complete, and a clear two-component ordering is observed. Molecules are either (i) almost completely ordered with local order parameters {sigma}={l_angle}1{minus}3/2Jz{sup 2}{r_angle} clustered close to a maximum value of {sigma}{congruent}0.94 (comparable to the values for long range ordering in bulk samples at high ortho concentrations), and (ii) a large fraction of the molecules that remain nearly disordered with {sigma}{<=}0.25. The degree of orientational ordering depends on the number of hydrogen layers and on the ortho-hydrogen concentration, and these studies indicate that ordering occurs principally in the first four layers closest to the substrate, with weaker orientational ordering in the outer layers near the free surface even at temperatures as low as 210 mK.

  15. NMR studies of structure and dynamics of liquid molecules confined in extended nanospaces.

    PubMed

    Tsukahara, Takehiko; Mizutani, Wataru; Mawatari, Kazuma; Kitamori, Takehiko

    2009-08-01

    We fabricated an NMR cell equipped with 10-100 nm scale spaces on a glass substrate (called extended nanospaces), and investigated molecular structure and dynamics of water confined in the extended nanospaces by (1)H NMR chemical shift (delta(H)) and (1)H and (2)H NMR spin-lattice relaxation rate ((1)H- and (2)H-1/T(1)), (1)H NMR spin-spin relaxation rate ((1)H-1/T(2)), and (1)H NMR rotating-frame spin-lattice relaxation rate ((1)H-1/T(1rho)) measurements of H(2)O and (2)H(2)O. The delta(H) and (1)H- and (2)H-1/T(1) results showed that size-confinement produces slower translational motions and higher proton mobility of water, but does not affect the hydrogen-bonding structure and rotational motions. Such unique phenomena appeared in the space size of 40 to 800 nm. However, the (1)H-1/T(1) value at 40 nm was still different from that in 4 nm porous nanomaterial, because translational and rotational motions were inhibited for H(2)O molecules in the nanomaterial. By examining temperature- and deuterium-dependence of the (1)H-1/T(1) values, the molecular translational motions of the confined water were found to be controlled by protonic diffusion invoking a proton hopping pathway between adjacent water rather than hydrodynamic translational diffusion. Furthermore, we clarified that proton exchange between adjacent water molecules in extended nanospaces could be enhanced by the chemical exchange of protons between water and SiOH groups on glass surfaces, ( identical with SiO(-)...H(+)...H(2)O) + H(2)O --> triple bond SiO(-) + (H(3)O(+) + H(2)O) --> triple bond SiO(-) + (H(2)O + H(3)O(+)), based on (1)H-1/T(2) measurements. An enhancement of proton exchange rate of water due to the reduction of space sizes was verified from the results of (1)H-1/T(1rho) values, and the rate of water in the 100 nm sized spaces is larger by a factor of more than ten from that of bulk water. Such size-confinement effects were distinctly observed for hydrogen-bond solvents with strong proton

  16. Study of carbohydrate structure and reactivity by modern NMR methods and isotopic labeling

    SciTech Connect

    Snyder, J.R.

    1987-01-01

    Chemical methods are described for preparing unenriched and (1-/sup 13/C)-enriched 5-deoxy- and 5-O-methylpentoses in the D or L configuration. The /sup 1/H and /sup 13/C NMR spectra of these compounds have been interpreted and the carbon spectra assigned with the aid of 2D /sup 13/C-/sup 1/H chemical-shift correlation spectroscopy. The tautomeric composition in /sup 2/H/sub 2/O has been quantitated with the aid of (1-/sup 13/C)-enriched derivatives. The branched-chain pentose, DL-apiose has been synthesized in good yield by a new and simple chemical method that can be adapted to prepare (1-/sup 13/C)-, (2-/sup 13/C)-, (1-/sup 2/H)- and/or (2-/sup 2/H)-enriched derivatives. The solution composition of D-idose in D/sup 2/O has been examined by /sup 13/C NMR spectroscopy using (/sup 13/C)-enriched compounds. In addition to two furanoses and two pyranoses, aldehyde and hydrate forms have been detected and quantified. The solution composition of D-talose has been investigated by /sup 13/C NMR spectroscopy using (1-/sup 13/C)talose. The tautomeric composition has been determined at 28/sup 0/, and the results show equivalent amounts of the acyclic aldehyde and hydrate. Several structurally modified furanose sugars were synthesized to assess the extent the Thorpe-Ingold effect promotes rings formation and enhances rates of ring-closure.

  17. T1BT* structural study of an anti-plasmodial peptide through NMR and molecular dynamics

    PubMed Central

    2013-01-01

    Background T1BT* is a peptide construct containing the T1 and B epitopes located in the 5’ minor repeat and the 3’ major repeat of the central repeat region of the Plasmodium falciparum circumsporozoite protein (CSP), respectively, and the universal T* epitope located in the C-terminus of the same protein. This peptide construct, with B = (NANP)3, has been found to elicit antisporozoite antibodies and gamma-interferon-screening T-cell responses in inbred strains of mice and in outbred nonhuman primates. On the other hand, NMR and CD spectroscopies have identified the peptide B’ = (NPNA)3 as the structural unit of the major repeat in the CSP, rather than the more commonly quoted NANP. With the goal of assessing the structural impact of the NPNA cadence on a proven anti-plasmodial peptide, the solution structures of T1BT* and T1B’T* were determined in this work. Methods NMR spectroscopy and molecular dynamics calculations were used to determine the solution structures of T1BT* and T1B’T*. These structures were compared to determine the main differences and similarities between them. Results Both peptides exhibit radically different structures, with the T1B’T* showing strong helical tendencies. NMR and CD data, in conjunction with molecular modelling, provide additional information about the topologies of T1BT* and T1B’T*. Knowing the peptide structures required to elicit the proper immunogenic response can help in the design of more effective, conformationally defined malaria vaccine candidates. If peptides derived from the CSP are required to have helical structures to interact efficiently with their corresponding antibodies, a vaccine based on the T1B’T* construct should show higher efficiency as a pre-erythrocyte vaccine that would prevent infection of hepatocytes by sporozoites. PMID:23506240

  18. NMR spectroscopy: structure elucidation of cycloelatanene A: a natural product case study.

    PubMed

    Urban, Sylvia; Dias, Daniel Anthony

    2013-01-01

    The structure elucidation of new secondary metabolites derived from marine and terrestrial sources is frequently a challenging task. The hurdles include the ability to isolate stable secondary metabolites of sufficient purity that are often present in <0.5 % of the dry weight of the sample. This usually involves a minimum of several chromatographic purification steps. The second issue is the stability of the compound isolated. It must always be assumed when dealing with the isolation of natural products that the compound may rapidly degrade during and/or after the isolation, due to sensitivity to light, air oxidation, and/or temperature. In this way, precautions need to be taken, as much as possible to avoid any such chemical inter-conversions and/or degradations. Immediately after purification, the next step is to rapidly acquire all analytical spectroscopic data in order to complete the characterization of the isolated secondary metabolite(s), prior to any possible decomposition. The final hurdle in this multiple step process, especially in the acquisition of the NMR spectroscopic and other analytical data (mass spectra, infrared and ultra-violet spectra, optical rotation, etc.), is to assemble the structural moieties/units in an effort to complete the structure elucidation. Often ambiguity with the elucidation of the final structure remains when structural fragments identified are difficult to piece together on the basis of the HMBC NMR correlations or when the relative configuration cannot be unequivocally identified on the basis of NOE NMR enhancements observed. Herein, we describe the methodology used to carry out the structure elucidation of a new C16 chamigrene, cycloelatanene A (5) which was isolated from the southern Australian marine alga Laurencia elata (Rhodomelaceae). The general approach and principles used in the structure determination of this compound can be applied to the structure elucidation of other small molecular weight compounds derived

  19. Solution NMR studies of the plant peptide hormone CEP inform function.

    PubMed

    Bobay, Benjamin G; DiGennaro, Peter; Scholl, Elizabeth; Imin, Nijat; Djordjevic, Michael A; Mck Bird, David

    2013-12-11

    The C-terminally Encoded Peptide (CEP) family of regulatory peptides controls root development in vascular plants. Here, we present the first NMR structures of CEP. We show that root-knot nematode (RKN: Meloidogyne spp.) also encodes CEP, presumably to mimic plant CEP as part of their stereotypic, parasitic interaction with vascular plants. Molecular dynamics simulations of plant- and nematode-encoded CEP displaying known posttranslational modifications (PTM) provided insight into the structural effects of PTM and the conformational plasticity and rigidity of CEP. Potential mechanisms of action are discussed with respect to the structure and sampling of conformational space.

  20. 1H and 13C NMR study on some substituted azolidine derivatives

    NASA Astrophysics Data System (ADS)

    Cerioni, Giovanni; Cristiani, Franco; Devillanova, Francesco A.; Diaz, Angelo; Verani, Gaetano

    The 1H and 13C NMR spectra carried out on R overlineN·CH 2·CH 2·X·C O (where for R = H, X = NH, NMe, NEt, CH 2, S, O; for R = Me, X = NMe, CH 2; for R = Et, X = NEt) are reported. The comparison of these results with those obtained for the thionic and selonic isologues shows that sulphur and selenium have a greater deshielding effect on the ring than oxygen. The resonance of the carbons not involved in the π system have been correlated with the σ charges calculated by the DEL RE method.

  1. Conformational analysis, tautomerization, IR, Raman, and NMR studies of ethyl benzoylacetate

    NASA Astrophysics Data System (ADS)

    Tayyari, Sayyed Faramarz; Chahkandi, Behzad; Mehrani, Sepideh; McClurg, Ryan W.; Keyes, Chad A.; Sammelson, Robert E.

    2012-05-01

    A complete conformational analysis of the keto and enol forms of ethyl benzoylacetate (EBA), a β-ketoester, was carried out by ab initio calculations, at the density functional theory (DFT) level. The relative stabilities of cis-enol and keto forms were calculated in the gas phase and in solution. The intramolecular hydrogen bond characters of the most stable enol forms of EBA are discussed and compared with those of benzoylacetone (BA). Harmonic vibrational frequencies and 1H and 13C NMR chemical shifts of the most stable enol and keto forms were also calculated at the B3LYP/6-311++G** level and compared with the experimental data.

  2. Rb NMR study of the electronic properties of Rb 1C 60

    NASA Astrophysics Data System (ADS)

    Brouet, V.; Yoshinari, Y.; Alloul, H.; Forro, L.

    1994-12-01

    87Rb (and 85Rb) NMR spectra in the orthorhombic phase ( (o) phase) of Rb 1C 60 show up broadening, with respect to the high-T cubic phase and to the quenched phase, which signals change of symmetry of the Rb site. The spin lattice relaxation rate follows a linear T dependence in the (o) phase above 100 K, suggesting that this phase is metallic. The increase of 1/T 1T at low T seems to be correlated with the transition seen by E.S.R.

  3. Barbiturate bearing aroylhydrazine derivatives: Synthesis, NMR investigations, single crystal X-ray studies and biological activity

    NASA Astrophysics Data System (ADS)

    Giziroglu, Emrah; Sarikurkcu, Cengiz; Aygün, Muhittin; Basbulbul, Gamze; Soyleyici, H. Can; Firinci, Erkan; Kirkan, Bulent; Alkis, Ayse; Saylica, Tayfur; Biyik, Halil

    2016-03-01

    A series of barbituric acid aroylhydrazine derivatives have been prepared from their corresponding 1,3-dimethyl-5-acetyl barbituric acid and aroylhydrazines. All compounds have been fully characterized by using FT-IR, multinuclear NMR (1H, 13C) and Mass (MS) spectrometry. We also describe the X-ray crystal structure of 3a, which crystallizes in the monoclinic P21/n space group. The crystal structure is stabilized with infinite linear chains of dimeric units. Furthermore, all compounds were investigated for their tyrosinase inhibition, antioxidative and antimicrobial activies. The results from biological activity assays have shown that all of compounds have excellent antioxidant, significant tyrosinase inhibition and moderate antimicrobial activity.

  4. Vortex lattice disorder in YBa2Cu3O studied with β-NMR

    NASA Astrophysics Data System (ADS)

    Saadaoui, H.; MacFarlane, W. A.; Morris, G. D.; Salman, Z.; Chow, K. H.; Fan, I.; Hossain, M. D.; Liang, R.; Mansour, A. I.; Parolin, T. J.; Smadella, M.; Song, Q.; Wang, D.; Kiefl, R. F.

    2009-04-01

    In this paper, we report Li+8β-NMR measurements in thin Ag films deposited on the surface of YBa2Cu3O (YBCO) in the vortex state. The resonance in the Ag overlayer broadens dramatically below the superconducting transition temperature Tc, as expected from the underlying vortex lattice in the YBCO. However, the lineshape is much broader and more symmetric than expected for an ideal vortex lattice. These results indicate the observed field distribution in the Ag overlayer is dominated by extrinsic, long length scale disorder.

  5. Push-through Direction Injectin NMR Automation

    EPA Science Inventory

    Nuclear magnetic resonance (NMR) and mass spectrometry (MS) are the two major spectroscopic techniques successfully used in metabolomics studies. The non-invasive, quantitative and reproducible characteristics make NMR spectroscopy an excellent technique for detection of endogeno...

  6. Structural and Nutritional Properties of Pasta from Triticum monococcum and Triticum durum Species. A Combined ¹H NMR, MRI, and Digestibility Study.

    PubMed

    Pasini, Gabriella; Greco, Fulvia; Cremonini, Mauro A; Brandolini, Andrea; Consonni, Roberto; Gussoni, Maristella

    2015-05-27

    The aim of the present study was to characterize the structure of two different types of pasta, namely Triticum turgidum ssp. durum (cv. Saragolla) and Triticum monococcum ssp. monococcum (cv. Monlis), under different processing conditions. MRI analysis and NMR spectroscopy (i.e., T1 and T2 NMR relaxation times and diffusion parameters) were conducted on pasta, and (1)H NMR spectroscopic analysis of the chemical compounds released by pasta samples during the cooking process was performed. In addition, starch digestibility (enzimatically determined) was also investigated. The NMR results indicated that Saragolla pasta has a more compact structure, ascribed to pasta network and in particular to different technological gluten properties, that mainly determine the lower ability of Monlis pasta in binding water. These results correlate well with the lower rate of starch hydrolysis measured for Monlis pasta compared to Saragolla when both are dried at high temperature.

  7. Influence of anthraquinone scaffold on E/Z isomer distribution of two thiosemicarbazone derivatives. 2D NMR and DFT studies

    NASA Astrophysics Data System (ADS)

    Marković, Violeta; Joksović, Milan D.; Marković, Svetlana; Jakovljević, Ivan

    2014-01-01

    A distribution of possible isomeric and tautomeric forms of two tautomerizable anthraquinone-thiosemicarbazones with pronounced cytotoxic potential was investigated using 2D NMR and DFT studies. Conformational analysis of the E and Z isomers of both thiosemicarbazones was performed to find out the most stable conformation for each molecule. It was found that superior stability of E-isomers results from ten-membered intramolecular hydrogen bond between thiosemicarbazone N2H and anthraquinone carbonyl group. This hydrogen bond is stronger than that between thiosemicarbazone N2H and ester oxygen, owing to the large partial negative charge on the anthraquinone oxygen.

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

    SciTech Connect

    Mogami, Yuuki; Yamazaki, Satoru; Matsuno, Shinya; Matsui, Kunio; Noda, Yasuto; Takegoshi, K.

    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. Expression, purification, and micelle reconstitution of antimicrobial piscidin 1 and piscidin 3 for NMR studies.

    PubMed

    Chen, Wen; Cotten, Myriam L

    2014-10-01

    Piscidin 1 and piscidin 3, which were discovered in the mast cells of hybrid striped sea bass, are homologous antimicrobial peptides that are active against drug-resistant bacteria. Piscidin 1, the more antimicrobial and hemolytic peptide, also has anti-HIV-1 and anti-cancer properties. To understand the reasons underlying the different biological activities of the two peptides and identify principles to design antimicrobial drugs with improved efficacy and lower toxicity, their atomic-level structures must be obtained under physiologically-relevant conditions. High-resolution backbone structures of both piscidins exist in the presence of hydrated phospholipid bilayers but full structures that include the side chains are missing. Here, the piscidins 1 and 3 genes were cloned into the TrpLE vector. The corresponding TrpLE-piscidin fusion partners were expressed in Escherichiacoli and recovered from inclusion bodies. Following steps that included Ni-NTA chromatography, cyanogen bromide cleavage of the fusion proteins, and reverse-phase HPLC, purified piscidins 1 and 3 were recovered in very good yield and characterized by NMR. High quality (15)N-(1)H HSQC spectra of piscidins 1 and 3 bound to SDS micelles were collected, demonstrating the feasibility of producing and purifying the isotopically-labeled piscidin peptides required to determine their full structures by multidimensional NMR spectroscopy. PMID:25131859

  10. 29Si NMR study of structural ordering in aluminosilicate geopolymer gels.

    PubMed

    Duxson, Peter; Provis, John L; Lukey, Grant C; Separovic, Frances; van Deventer, Jannie S J

    2005-03-29

    A systematic series of aluminosilicate geopolymer gels was synthesized and then analyzed using 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR) in combination with Gaussian peak deconvolution to characterize the short-range ordering in terms of T-O-T bonds (where T is Al or Si). The effect of nominal Na2O/(Na2O + K2O) and Si/Al ratios on short-range network ordering was quantified by deconvolution of the 29Si MAS NMR spectra into individual Gaussian peaks representing different Q4(mAl) silicon centers. The deconvolution procedure developed in this work is applicable to other aluminosilicate gel systems. The short-range ordering observed here indicates that Loewenstein's Rule of perfect aluminum avoidance may not apply strictly to geopolymeric gels, although further analyses are required to quantify the degree of aluminum avoidance. Potassium geopolymers appeared to exhibit a more random Si/Al distribution compared to that of mixed-alkali and sodium systems. This work provides a quantitative account of the silicon and aluminum ordering in geopolymers, which is essential for extending our understanding of the mechanical strength, chemical and thermal stability, and fundamental structure of these systems.

  11. Chalcogen analogues of nicotine lactam studied by NMR, FTIR, DFT and X-ray methods

    NASA Astrophysics Data System (ADS)

    Jasiewicz, Beata; Malczewska-Jaskóła, Karolina; Kowalczyk, Iwona; Warżajtis, Beata; Rychlewska, Urszula

    2014-07-01

    The selenoanalogue of nicotine has been synthesized and characterized by spectroscopic and X-ray diffraction methods. The crystals of selenonicotine are isomorphic with the thionicotine homologue and consist of molecules engaged in columnar π⋯π stacking interactions between antiparallely arranged pyridine moieties. These interactions, absent in other crystals containing nicotine fragments, seem to be induced by the presence of a lactam group. The molecular structures in the vacuum of the oxo-, thio- and selenonicotine homologues have been calculated by the DFT method and compared with the available X-ray data. The delocalized structure of thionicotine is stabilized by intramolecular Csbnd H⋯S hydrogen bond, which becomes weaker in the partial zwitterionic resonance structure of selenonicotine in favor of multiple Csbnd H⋯Se intermolecular hydrogen-bonds. The calculated data allow a complete assignment of vibration modes in the solid state FTIR spectra. The 1H and 13C NMR chemical shifts were calculated by the GIAO method with B3LYP/6-311G(3df) level. A comparison between experimental and calculated theoretical results indicates that the density functional B3LYP method provided satisfactory results for predicting FTIR, 1H, 13C NMR spectra properties.

  12. 13C CPMAS NMR studies and DFT calculations of triterpene xylosides isolated from Actaea racemosa

    NASA Astrophysics Data System (ADS)

    Jamróz, Marta K.; Paradowska, Katarzyna; Gliński, Jan A.; Wawer, Iwona

    2011-05-01

    13C CPMAS NMR spectra of four triterpene glycosides: cimigenol xyloside ( 1), 26-deoxyactein ( 2), cimicifugoside H-1 ( 3) and 24-acethylhydroshengmanol xyloside ( 4) were recorded and analyzed to characterize their solid-state structure. Experimental data were supported by theoretical calculations of NMR shielding constants with the GIAO/6-31G**-su1 approach. A number of methods for the conformational search and a number of functionals for the DFT calculations were applied to ( 1). The best method was proven to be MMFF or MMFFAQ for the conformational search and the PBE1PBE functional for the DFT calculations. Extra calculations simulating C16 dbnd O⋯HOH hydrogen bond yield the isotropic shielding closer to the experimental solid-state value. For all the compounds CP kinetics parameters were calculated using either the I-S or the I-I*-S model. The analysis of CP kinetics data for methyl groups revealed differences in the T2 time constant for two methyl groups (C29 and C30) linked at C4.

  13. In Vivo NMR Studies of the Brain with Hereditary or Acquired Metabolic Disorders.

    PubMed

    Sherry, Erica B; Lee, Phil; Choi, In-Young

    2015-12-01

    Metabolic disorders, whether hereditary or acquired, affect the brain, and abnormalities of the brain are related to cellular integrity; particularly in regard to neurons and astrocytes as well as interactions between them. Metabolic disturbances lead to alterations in cellular function as well as microscopic and macroscopic structural changes in the brain with diabetes, the most typical example of metabolic disorders, and a number of hereditary metabolic disorders. Alternatively, cellular dysfunction and degeneration of the brain lead to metabolic disturbances in hereditary neurological disorders with neurodegeneration. Nuclear magnetic resonance (NMR) techniques allow us to assess a range of pathophysiological changes of the brain in vivo. For example, magnetic resonance spectroscopy detects alterations in brain metabolism and energetics. Physiological magnetic resonance imaging (MRI) detects accompanying changes in cerebral blood flow related to neurovascular coupling. Diffusion and T1/T2-weighted MRI detect microscopic and macroscopic changes of the brain structure. This review summarizes current NMR findings of functional, physiological and biochemical alterations within a number of hereditary and acquired metabolic disorders in both animal models and humans. The global view of the impact of these metabolic disorders on the brain may be useful in identifying the unique and/or general patterns of abnormalities in the living brain related to the pathophysiology of the diseases, and identifying future fields of inquiry.

  14. Solid-State 17O NMR Study of Benzoic Acid Adsorption On Metal Oxide Surfaces

    SciTech Connect

    Hagaman, Edward {Ed} W; Chen, Banghao; Jiao, Jian; Parsons, Williams

    2012-01-01

    Solid-state 17O NMR spectra of 17O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry-mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the 17O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. 27Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

  15. NMR study of the supramolecular structure of dual drug-loaded poly(butylcyanoacrylate) nanoparticles.

    PubMed

    Simeonova, Margarita; Rangel, Maria; Ivanova, Galya

    2013-10-21

    Nuclear magnetic resonance (NMR) spectroscopy has been used for structural characterization of 5-fluorouracil (5FU) & daunorubicin (DAU) co-loaded poly(butylcyanoacrylate) nanoparticles (PBCN), prepared by an anionic polymerization of n-butylcyanoacrylate, probing two different drug loading approaches. Diffusion ordered spectroscopy, obtained through pulsed field gradient NMR experiments, has been performed to determine the overall structure of the 5FU & DAU co-loaded PBCN and to clarify the mechanisms of drug immobilization and location in the polymer matrix of PBCN. Physicochemical properties such as composition, size, surface chemistry and shape have been defined. All data obtained have been referred to the dual drug-loading procedures employed. The results show that 5FU & DAU co-loaded PBCN can be designed to exhibit different properties, composition and overall structure, depending on the method of preparation. The structural attributes relate to the drug efficacy and reactivity characteristics such as capacity for sustained drug release, targeted drug delivery, drug penetration, retention in and transport through bio-membranes. The design of nanoparticle platforms to deliver multiple drugs for combination therapy offers the opportunity for novel strategies in an effort to increase the efficacy of cancer therapy.

  16. Advanced NMR characterization of zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Welsh, L. B.

    1985-04-01

    The program discussed in this report is a two-year two-phase joint UOP-University of Illinois study of the application of improved high resolution solid state nuclear magnetic resonance (NMR) techniques to the characterization of zeolite catalysts. During the first phase of this program very pure, and in some cases isotopically enriched faujasites will be prepared and studied by magic angle sample spinning NMR (MASS NMR) and variable engine sample spinning NMR (VASS NMR) on 500 and 360 MHz (proton frequency) NMR spectrometers. The NMR techniques that will be emphasized are the measurement and analysis of the (17)O NMR properties, (27)Al NMR intensity quantitation, and (27)Al and (29)Si NMR relaxation rates. During the second phase of this program these NMR techniques will be used to study the effects of impurity concentration, dealumination treatments and cation exchange on the NMR properties of faujasites. The initial emphasis of this program during Phase I is on the preparation and measurement of the NMR properties of (17)O enriched Na-Y faujasties.

  17. Tortuosity measurement and the effects of finite pulse widths on xenon gas diffusion NMR studies of porous media

    NASA Technical Reports Server (NTRS)

    Mair, R. W.; Hurlimann, M. D.; Sen, P. N.; Schwartz, L. M.; Patz, S.; Walsworth, R. L.

    2001-01-01

    We have extended the utility of NMR as a technique to probe porous media structure over length scales of approximately 100-2000 microm by using the spin 1/2 noble gas 129Xe imbibed into the system's pore space. Such length scales are much greater than can be probed with NMR diffusion studies of water-saturated porous media. We utilized Pulsed Gradient Spin Echo NMR measurements of the time-dependent diffusion coefficient, D(t), of the xenon gas filling the pore space to study further the measurements of both the pore surface-area-to-volume ratio, S/V(p), and the tortuosity (pore connectivity) of the medium. In uniform-size glass bead packs, we observed D(t) decreasing with increasing t, reaching an observed asymptote of approximately 0.62-0.65D(0), that could be measured over diffusion distances extending over multiple bead diameters. Measurements of D(t)/D(0) at differing gas pressures showed this tortuosity limit was not affected by changing the characteristic diffusion length of the spins during the diffusion encoding gradient pulse. This was not the case at the short time limit, where D(t)/D(0) was noticeably affected by the gas pressure in the sample. Increasing the gas pressure, and hence reducing D(0) and the diffusion during the gradient pulse served to reduce the previously observed deviation of D(t)/D(0) from the S/V(p) relation. The Pade approximation is used to interpolate between the long and short time limits in D(t). While the short time D(t) points lay above the interpolation line in the case of small beads, due to diffusion during the gradient pulse on the order of the pore size, it was also noted that the experimental D(t) data fell below the Pade line in the case of large beads, most likely due to finite size effects.

  18. Tortuosity measurement and the effects of finite pulse widths on xenon gas diffusion NMR studies of porous media.

    PubMed

    Mair, R W; Hürlimann, M D; Sen, P N; Schwartz, L M; Patz, S; Walsworth, R L

    2001-01-01

    We have extended the utility of NMR as a technique to probe porous media structure over length scales of approximately 100-2000 microm by using the spin 1/2 noble gas 129Xe imbibed into the system's pore space. Such length scales are much greater than can be probed with NMR diffusion studies of water-saturated porous media. We utilized Pulsed Gradient Spin Echo NMR measurements of the time-dependent diffusion coefficient, D(t), of the xenon gas filling the pore space to study further the measurements of both the pore surface-area-to-volume ratio, S/V(p), and the tortuosity (pore connectivity) of the medium. In uniform-size glass bead packs, we observed D(t) decreasing with increasing t, reaching an observed asymptote of approximately 0.62-0.65D(0), that could be measured over diffusion distances extending over multiple bead diameters. Measurements of D(t)/D(0) at differing gas pressures showed this tortuosity limit was not affected by changing the characteristic diffusion length of the spins during the diffusion encoding gradient pulse. This was not the case at the short time limit, where D(t)/D(0) was noticeably affected by the gas pressure in the sample. Increasing the gas pressure, and hence reducing D(0) and the diffusion during the gradient pulse served to reduce the previously observed deviation of D(t)/D(0) from the S/V(p) relation. The Pade approximation is used to interpolate between the long and short time limits in D(t). While the short time D(t) points lay above the interpolation line in the case of small beads, due to diffusion during the gradient pulse on the order of the pore size, it was also noted that the experimental D(t) data fell below the Pade line in the case of large beads, most likely due to finite size effects. PMID:11445310

  19. (19)F-labeling of the adenine H2-site to study large RNAs by NMR spectroscopy.

    PubMed

    Sochor, F; Silvers, R; Müller, D; Richter, C; Fürtig, B; Schwalbe, H

    2016-01-01

    In comparison to proteins and protein complexes, the size of RNA amenable to NMR studies is limited despite the development of new isotopic labeling strategies including deuteration and ligation of differentially labeled RNAs. Due to the restricted chemical shift dispersion in only four different nucleotides spectral resolution remains limited in larger RNAs. Labeling RNAs with the NMR-active nucleus (19)F has previously been introduced for small RNAs up to 40 nucleotides (nt). In the presented work, we study the natural occurring RNA aptamer domain of the guanine-sensing riboswitch comprising 73 nucleotides from Bacillus subtilis. The work includes protocols for improved in vitro transcription of 2-fluoroadenosine-5'-triphosphat (2F-ATP) using the mutant P266L of the T7 RNA polymerase. Our NMR analysis shows that the secondary and tertiary structure of the riboswitch is fully maintained and that the specific binding of the cognate ligand hypoxanthine is not impaired by the introduction of the (19)F isotope. The thermal stability of the (19)F-labeled riboswitch is not altered compared to the unmodified sequence, but local base pair stabilities, as measured by hydrogen exchange experiments, are modulated. The characteristic change in the chemical shift of the imino resonances detected in a (1)H,(15)N-HSQC allow the identification of Watson-Crick base paired uridine signals and the (19)F resonances can be used as reporters for tertiary and secondary structure transitions, confirming the potential of (19)F-labeling even for sizeable RNAs in the range of 70 nucleotides.

  20. Investigation of structure, vibrational and NMR spectra of oxycodone and naltrexone: A combined experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Tavakol, Hossein; Esfandyari, Maryam; Taheri, Salman; Heydari, Akbar

    2011-08-01

    In this work, two important opioid antagonists, naltrexone and oxycodone, were prepared from thebaine and were characterized by IR, 1H NMR and 13C NMR spectroscopy. Moreover, computational NMR and IR parameters were obtained using density functional theory (DFT) at B3LYP/6-311++G** level of theory. Complete NMR and vibrational assignment were carried out using the observed and calculated spectra. The IR frequencies and NMR chemical shifts, determined experimentally, were compared with those obtained theoretically from DFT calculations, showed good agreements. The RMS errors observed between experimental and calculated data for the IR absorptions are 85 and 105 cm -1, for the 1H NMR peaks are 0.87 and 0.17 ppm and for those of 13C NMR are 5.6 and 5.3 ppm, respectively for naltrexone and oxycodone.

  1. High-resolution solid-state NMR in liquids. 2. sup 27 Al NMR study of AlF sub 3 ultrafine particles

    SciTech Connect

    Satoh, Naoki ); Kimura, Keisaku )

    1990-06-06

    High-resolution {sup 27}Al nuclear magnetic resonance spectra of AlF{sub 3} ultrafine particles (UFPs) were obtained by means of motional narrowing caused by Brownian motion of UFPs in a liquid phase. The NMR observed spectra can be resolved in five signals at 10, {minus}5, {minus}8, {minus}12, and {minus}16 ppm with respect to an Al{sup 3+}(H{sub 2}O){sub 6} standard. The UFPs were fractionated according to their sizes by using an ultrafiltration technique. From the NMR measurements of fractionated colloidal solutions, the five peaks were classified into three groups by their origins, viz. the peak at {minus}16 ppm is from larger UFPs (diameter D; 9 nm), those at {minus}5, {minus}8, and {minus}12 ppm from smaller UFPs (1 < D < 3 nm), while that at 10 ppm from free ions. Line widths of the larger and smaller UFPs were about 10 and 4 ppm (i.e., 1 and 0.4 kHz), respectively.

  2. The isomers and conformers of some push pull enamines studied by vibrational and NMR spectroscopy and by ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pigošová, J.; Gatial, A.; Milata, V.; Černuchová, P.; Prónayová, N.; Liptaj, T.; Matějka, P.

    2005-06-01

    The isomers and conformers of six push-pull enamines: 3-dimethylamino-, 3-methylamino- and 3-amino-2-acetyl propenenitrile [(H 3C) 2N-CH dbnd6 C(CN)(COCH 3), H 3C-NH-CH dbnd6 C(CN)(COCH 3) and H 2N-CH dbnd6 C(CN)(COCH 3)] and 3-dimethylamino-, 3-methylamino- and 3-amino-2-methylsulfonyl propenenitrile [(H 3C) 2N-CH dbnd6 C(CN)(SO 2CH 3), H 3C-NH-CH dbnd6 C(CN)(SO 2CH 3) and H 2N-CH dbnd6 C(CN)(SO 2CH 3)] have been studied experimentally by vibrational and NMR spectroscopy and theoretically by the ab initio calculations at MP2 level in 6-31G** basis set. The IR and Raman spectra of all compounds as a solid and solute in various solvents have been recorded in the region 4000-50 cm -1. The NMR spectra were obtained in chloroform and DMSO at room temperature. All six compounds have been prepared by the same way. NMR spectra revealed that both dimethylamino compounds were prepared as a pure E isomers whereas in the case of methylamino compounds the 3-methylamino-2-methylsulfonyl propenenitrile was prepared also as a pure E isomer but 3-methylamino-2-acetyl propenenitrile as a pure Z isomer. Also 3-amino-2-methylsulfonyl propenenitrile was obtained as a pure the E isomer, but 3-amino-2-acetyl propenenitrile as a mixture of both E and Z isomers. Confomational possibilities of studied compounds are given only by the rotation of the acetyl and methylamino groups. Vibrational spectra revealed existence of two conformers with Z and E orientation of acetyl group for 3-dimethylamino-2-acetyl propenenitrile. Two conformers with anti or syn orientation of methylamino group for 3-methylamino-2-methylsulfonyl propenenitrile have been confirmed by vibrational and NMR spectra, but only one conformer with anti orientation of methylamino group for 3-methylamino-2-acetyl propenenitrile in chloroform solution and in solid phase was found. For latter compound the additional isomer/conformer was detected in more polar solvents (acetonitrile/DMSO). These experimental findings have been

  3. Cadmium(II) Complex Formation with Selenourea and Thiourea in Solution: An XAS and 113Cd NMR Study

    PubMed Central

    Jalilehvand, Farideh; Amini, Zahra; Parmar, Karnjit

    2012-01-01

    The complexes formed in methanol solutions of Cd(CF3SO3)2 with selenourea (SeU) or thiourea (TU), for thiourea also in aqueous solution, were studied by combining 113Cd NMR and X-ray absorption spectroscopy. At low temperature (~200 K) distinct 113Cd NMR signals were observed, corresponding to CdLn2+ species (n = 0 - 4, L = TU or SeU) in slow ligand exchange. Peak integrals were used to obtain the speciation in the methanol solutions, allowing stability constants to be estimated. For cadmium(II) complexes with thione (C=S) or selone (C=Se) groups coordinated in Cd(S/Se)O5 or Cd(S/Se)2O4 (O from MeOH or CF3SO3-) environments the 113Cd chemical shifts were quite similar, within 93-97 ppm and 189 – 193 ppm, respectively. However, the difference in the chemical shift for the Cd(SeU)42+ (578 pm) and Cd(TU)42+ (526 ppm) species, with CdSe4 and CdS4 coordination, respectively, shows less chemical shielding for the coordinated Se atoms than for S, in contrast to the common trend with increasing shielding in the order: O > N > Se >S. In solutions dominated by mono- and tetra-thiourea / selenourea complexes, their coordination and bond distances could be evaluated by Cd K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. At ~200 K and high excess of thiourea a minor amount (up to ~30%) of [Cd(TU)5-6]2+ species was detected by an upfield shift of the 113Cd NMR signal (up to 423 ppm) and an amplitude reduction of the EXAFS oscillation. The amount was estimated by fitting linear combinations of simulated EXAFS spectra for [Cd(TU)4]2+ and [Cd(TU)6]2+ complexes. At room temperature, [Cd(TU)4]2+ was the highest complex formed, also in aqueous solution. Cd L3-edge X-ray absorption near edge structure (XANES) spectra of cadmium(II) thiourea solutions in methanol were used to follow changes in the CdSxOy coordination at room temperature. The correlations found from the current and previous studies between 113Cd NMR chemical shifts and different Cd(II) coordination

  4. 17O NMR study of the doped electrons in lightly oxygen-deficient cubic SrMnO3 -x

    NASA Astrophysics Data System (ADS)

    Trokiner, A.; Verkhovskii, S.; Volkova, Z.; Gerashenko, A.; Mikhalev, K.; Germov, A.; Yakubovskii, A.; Korolev, A.; Dabrowski, B.; Tyutyunnik, A.

    2016-05-01

    The spin susceptibility of the localized Mn (t2 g) electrons, χs, and the spatially distributed spin density of the doped electrons were investigated by 17O nuclear magnetic resonance (NMR) in the paramagnetic (PM) and antiferromagnetic (AF) phases of electron-doped SrMnO3 -x ceramics with the cubic structure. Three lightly doped samples (2 x <0.015 ) were studied with TN=220 K-240 K. In the PM state χs increases gradually from TN and reaches a broad maximum above ˜1.5 TN . The gapped behavior of χs indicates a low-dimensional short-range spin order persisting above TN. These short-range one-dimensional correlations are consistent with 17O NMR results obtained at room temperature, which show that Mn magnetic moments are aligned along the edges of the cubic unit cell. Above 350 K all doped electrons are fast-moving eg electrons. They provide the uniform polarization of the localized spins which increases χs and the increasing doping shifts the oxygen-deficient SrMnO3 -x oxide towards a ferromagnetic (FM) metallic state. At lower T the doped electrons are heterogeneously distributed in the oxide: The fraction of the fast-moving electrons diminishes and vanishes below 100 K, while the remaining doped electrons slow down their hopping and each of them creates a FM domain. These FM domains which are detected below 10 K by 55Mn NMR can be considered as small-size magnetic polarons. Their T -activated hopping in the G-type AF lattice was probed by 17O spin-echo experiments. The energy barrier of hopping shows a trend to grow with increasing doping, indicating that the de Gennes metallic ground state cannot be achieved in oxygen-deficient SrMnO3 -x oxides, probably due to detrimental oxygen vacancy defects.

  5. Metabolic profiling studies on the toxicological effects of realgar in rats by {sup 1}H NMR spectroscopy

    SciTech Connect

    Wei Lai; Liao Peiqiu; Wu Huifeng; Li Xiaojing Pei Fengkui Li Weisheng; Wu Yijie

    2009-02-01

    The toxicological effects of realgar after intragastrical administration (1 g/kg body weight) were investigated over a 21 day period in male Wistar rats using metabonomic analysis of {sup 1}H NMR spectra of urine, serum and liver tissue aqueous extracts. Liver and kidney histopathology examination and serum clinical chemistry analyses were also performed. {sup 1}H NMR spectra and pattern recognition analyses from realgar treated animals showed increased excretion of urinary Kreb's cycle intermediates, increased levels of ketone bodies in urine and serum, and decreased levels of hepatic glucose and glycogen, as well as hypoglycemia and hyperlipoidemia, suggesting the perturbation of energy metabolism. Elevated levels of choline containing metabolites and betaine in serum and liver tissue aqueous extracts and increased serum creatine indicated altered transmethylation. Decreased urinary levels of trimethylamine-N-oxide, phenylacetylglycine and hippurate suggested the effects on the gut microflora environment by realgar. Signs of impairment of amino acid metabolism were supported by increased hepatic glutamate levels, increased methionine and decreased alanine levels in serum, and hypertaurinuria. The observed increase in glutathione in liver tissue aqueous extracts could be a biomarker of realgar induced oxidative injury. Serum clinical chemistry analyses showed increased levels of lactate dehydrogenase, aspartate aminotransferase, and alkaline phosphatase as well as increased levels of blood urea nitrogen and creatinine, indicating slight liver and kidney injury. The time-dependent biochemical variations induced by realgar were achieved using pattern recognition methods. This work illustrated the high reliability of NMR-based metabonomic approach on the study of the biochemical effects induced by traditional Chinese medicine.

  6. Solid-state NMR Study of the YadA Membrane-Anchor Domain in the Bacterial Outer Membrane.

    PubMed

    Shahid, Shakeel A; Nagaraj, Madhu; Chauhan, Nandini; Franks, Trent W; Bardiaux, Benjamin; Habeck, Michael; Orwick-Rydmark, Marcella; Linke, Dirk; van Rossum, Barth-J

    2015-10-19

    MAS-NMR was used to study the structure and dynamics at ambient temperatures of the membrane-anchor domain of YadA (YadA-M) in a pellet of the outer membrane of E. coli in which it was expressed. YadA is an adhesin from the pathogen Yersinia enterocolitica that is involved in interactions with the host cell, and it is a model protein for studying the autotransport process. Existing assignments were sucessfully transferred to a large part of the YadA-M protein in the E. coli lipid environment by using (13) C-(13) C DARR and PDSD spectra at different mixing times. The chemical shifts in most regions of YadA-M are unchanged relative to those in microcrystalline YadA-M preparations from which a structure has previously been solved, including the ASSA region that is proposed to be involved in transition-state hairpin formation for transport of the soluble domain. Comparisons of the dynamics between the microcrystalline and membrane-embedded samples indicate greater flexibility of the ASSA region in the outer-membrane preparation at physiological temperatures. This study will pave the way towards MAS-NMR structure determination of membrane proteins, and a better understanding of functionally important dynamic residues in native membrane environments. PMID:26332158

  7. NBO, conformational, NLO, HOMO-LUMO, NMR and electronic spectral study on 1-phenyl-1-propanol by quantum computational methods.

    PubMed

    Xavier, S; Periandy, S; Ramalingam, S

    2015-02-25

    In this study, FT-IR, FT-Raman, NMR and UV spectra of 1-phenyl-1-propanol, an intermediate of anti-depressant drug fluoxetine, has been investigated. The theoretical vibrational frequencies and optimized geometric parameters have been calculated by using HF and density functional theory with the hybrid methods B3LYP, B3PW91 and 6-311+G(d,p)/6-311++G(d,p) basis sets. The theoretical vibrational frequencies have been found in good agreement with the corresponding experimental data. (1)H and (13)C NMR spectra were recorded and chemical shifts of the molecule were compared to TMS by using the Gauge-Independent Atomic Orbital (GIAO) method. A study on the electronic and optical properties, absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies are performed using HF and DFT methods. The thermodynamic properties (heat capacity, entropy and enthalpy) at different temperatures are also calculated. NBO analysis is carried out to picture the charge transfer between the localized bonds and lone pairs. The local reactivity of the molecule has been studied using the Fukui function. NLO properties related to polarizability and hyperpolarizability are also discussed.

  8. NMR studies of bent DNA using {sup 13}C-enriched samples

    SciTech Connect

    Zimmer, D.P.; Crothers, D.M.

    1994-12-01

    Bending of the DNA double helix can be brought about by introducing runs of adenines (A-tracts) in phase with the helical repeat of the DNA. The requirements for bending of DNA by A-tracts are that the length of the A-tract be greater than 3 base pairs and that the A-tracts must be in phase with the helical repeat (every 10 or 11 bp). Other factors, such as the number of adenines in the run, flanking sequences, and whether the A-tracts are phased with respect to the 5{prime}A or the 3{prime}A, have effects upon the degree of bending as assayed by electrophoretic mobility on native polyacrylamide gels. There are a number of models for bending A-tract DNA. The junction-bending model postulates that the structure of A-tracts is similar to the fiber diffraction structure of poly A, in which there is a significant degree of base pair tilt with respect to the helix axis. In this model, bending occurs at the junction between the A-tract and the B-form helix to allow favorable stacking interactions to occur. The bend of the helix could arise as a result of some other perturbation of B-form DNA by A-tracts, such as propeller twist; bending also could be due to a combination of factors. Our goal is to find the structural features of A-tracts responsible for bending of the helix by performing NMR on oligonucleotides containing A-tracts to obtain higher resolution structural data. One of the problems encountered in NMR structure determination of nucleic acids and other macromolecules is the assignment of resonances to nuclei. This procedure can be greatly facilitated through the use of {sup 13}C-enriched nucleic acid samples. We are developing a technique for the enzymatic synthesis of labeled DNA for NMR. The technique we are developing is similar to RNA labeling techniques already in use. The technique involves growth of methylotrophic bacteria on {sup 13}CH{sub 3}OH.

  9. Torsion sensitivity in NMR of aligned molecules: study on various substituted biphenyls.

    PubMed

    Sahakyan, Aleksandr B; Shahkhatuni, Aleksan G; Shahkhatuni, Astghik A; Panosyan, Henry A

    2008-02-01

    To estimate the torsion sensitivity of dipolar coupling, biphenylic molecules were chosen as probes due to their relatively simple structure and the surprisingly high ambiguity of the only flexible parameter-the interring torsion angle. Solution structures of 4,4'-dibromobiphenyl and 4,4'-diiodobiphenyl are reported for the first time in two liquid crystals I52 and ZLI 1695. The comparison of NMR structures of various para-substituted biphenyls (BPs), calculated by the additive potential maximum entropy (APME) approach, shows that the small spread of torsion angle values in case of different solvents and para-substituents is in good agreement with theoretical expectations from hybrid density functional theory (DFT) methods. Furthermore, the real structural changes of interring torsion and the prevalence of solvent effects over para-halosubstitution can be correctly revealed from these small fluctuations. PMID:18095265

  10. Pseudogap and anharmonic phonon behavior in Ba8Ga16Ge30: An NMR study

    NASA Astrophysics Data System (ADS)

    Sirusi, Ali A.; Ross, Joseph H.

    2016-08-01

    We have performed 69Ga, 71Ga, and 137Ba NMR on Ba8Ga16Ge30, a clathrate semiconductor which has been of considerable interest due to its large figure of merit for thermoelectric applications. In measurements from 4 K to 450 K, we used measurements on the two Ga nuclei to separate the magnetic and electric quadrupole hyperfine contributions and thereby gain information about the metallic and phonon behavior. The results show the presence of a pseudogap in the Ga electronic states within the conduction band, superposed upon a large Ba contribution to the conduction band. Meanwhile the phonon contributions to the Ga relaxation rates are large and increase more rapidly with temperature than typical semiconductors. These results provide evidence for enhanced anharmonicity of the propagative phonon modes over a wide range, providing experimental evidence for enhanced phonon-phonon scattering as a mechanism for the reduced thermal conductivity.

  11. A 13C-NMR study of exopolysaccharide synthesis in Rhizobium meliloti Su47 strain

    NASA Astrophysics Data System (ADS)

    Tavernier, P.; Portais, J.-C.; Besson, I.; Courtois, J.; Courtois, B.; Barbotin, J.-N.

    1998-02-01

    Metabolic pathways implied in the synthesis of succinoglycan produced by the Su47 strain of R. meliloti were evaluated by 13C-NMR spectroscopy after incubation with [1{-}13C] or [2{-}13C] glucose. The biosynthesis of this polymer by R. meliloti from glucose occurred by a direct polymerisation of the introduced glucose and by the pentose phosphate pathway. Les voies métaboliques impliquées dans la synthèse du succinoglycane produit par la souche Su47 de R. meliloti ont été évaluées par la spectroscopie de RMN du carbone 13 après incubation des cellules avec du [1{-}13C] ou [2{-}13C] glucose. La biosynthèse de ce polymère à partir du glucose se produit par polymérisation directe du glucose et par la voie des pentoses phosphate.

  12. A 13C NMR study of the structure of four cinnamic acids and their methyl esters

    NASA Astrophysics Data System (ADS)

    Silva, A. M. S.; Alkorta, I.; Elguero, J.; Silva, V. L. M.

    2001-09-01

    The 13C NMR spectra, both in DMSO solution and in the solid state of four cinnamic acids ( p-methoxy, p-hydroxy, p-methyl, p-chloro) and their corresponding methyl esters have been recorded. The two main results in the solid state are: (i) the only significant difference between acids and esters chemical shifts concerns the CO group which, on average, appears at 173 ppm in the acids and 168 ppm in the esters; (ii) the signals of the ortho and meta carbons both in the acids and the esters are splitted. The two 'anomalies' disappear in DMSO solution. These observations can be rationalized using simple GIAO/B3LYP/6-31G ∗ calculations.

  13. Structural studies of methyl brevifolincarboxylate in solid state by means of NMR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Wolniak, Michał; Tomczyk, Michał; Gudej, Jan; Wawer, Iwona

    2006-12-01

    Methyl brevifolincarboxylate isolated from the herb of Potentilla argentea L. (Rosaceae) is a representative of the naturally occurring polyphenols. The compound is of pharmaceutical interest mainly because of its antiviral and antioxidant properties. 13C NMR spectra were recorded for solution and solid phase. 13C CPMAS spectra were assigned by comparison with solution data, dipolar dephasing and short contact time experiments. The correctness of assignments was verified by GIAO DFT calculations of shielding constants. The differences between the solution and solid state chemical shift values were explained in terms of orientation of OH groups and intramolecular hydrogen bonds. The splitting of the C1 dbnd O resonance shows that there exists a polymorphism in the solid phase, which might be due to the formation of intramolecular hydrogen bond involving carbonyl or methoxy oxygen (i.e. C10 sbnd OH⋯O dbnd C or C10 sbnd OH⋯OCH 3).

  14. Metallic Li colloids studied by Li-7 MAS NMR in electron-irradiated LiF

    NASA Astrophysics Data System (ADS)

    Zogal, O. J.; Beuneu, F.; Vajda, P.; Florian, P.; Massiot, D.

    Li-7 MAS NMR spectra of 2.5 MeV electron-irradiated LiF crystals have been measured in a field of 9.4 T. Besides the resonance line of the ionic compound, a second well-separated spectrum is observed in the region of the Knight shift value for metallic lithium. At room temperature, the latter can be decomposed into two components with different Knight shift and linewidth values. When the temperature is increased, line narrowing takes place at first, indicating shortening of correlation times for self-diffusion, independently in both components. Above 370 K, both lines broaden and approach each other before collapsing into a single line. The high ppm component disappears after crossing the melting temperature of metallic lithium (454 K). The two lines are attributed to different types of metallic Li: one to bulk-like metal, the other to Li present initially under pressure and relaxing to the former under thermal treatment.

  15. Pseudogap and anharmonic phonon behavior in Ba8Ga16Ge30: An NMR study.

    PubMed

    Sirusi, Ali A; Ross, Joseph H

    2016-08-01

    We have performed (69)Ga, (71)Ga, and (137)Ba NMR on Ba8Ga16Ge30, a clathrate semiconductor which has been of considerable interest due to its large figure of merit for thermoelectric applications. In measurements from 4 K to 450 K, we used measurements on the two Ga nuclei to separate the magnetic and electric quadrupole hyperfine contributions and thereby gain information about the metallic and phonon behavior. The results show the presence of a pseudogap in the Ga electronic states within the conduction band, superposed upon a large Ba contribution to the conduction band. Meanwhile the phonon contributions to the Ga relaxation rates are large and increase more rapidly with temperature than typical semiconductors. These results provide evidence for enhanced anharmonicity of the propagative phonon modes over a wide range, providing experimental evidence for enhanced phonon-phonon scattering as a mechanism for the reduced thermal conductivity. PMID:27497567

  16. NMR- and GC/MS-based metabolomics of sulfur mustard exposed individuals: a pilot study.

    PubMed

    Nobakht, B Fatemeh; Aliannejad, Rasoul; Rezaei-Tavirani, Mostafa; Arefi Oskouie, Afsaneh; Naseri, Mohammad Taghi; Parastar, Hadi; Aliakbarzadeh, Ghazaleh; Fathi, Fariba; Taheri, Salman

    2016-09-01

    Sulfur mustard (SM) is a potent alkylating agent and its effects on cells and tissues are varied and complex. Due to limitations in the diagnostics of sulfur mustard exposed individuals (SMEIs) by noninvasive approaches, there is a great necessity to develop novel techniques and biomarkers for this condition. We present here the first nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC/MS) metabolic profiling of serum from and healthy controls to identify novel biomarkers in blood serum for better diagnostics. Of note, SMEIs were exposed to SM 30 years ago and that differences between two groups could still be found. Pathways in which differences between SMEIs and healthy controls are observed are related to lipid metabolism, ketogenesis, tricarboxylic acid (TCA) cycle and amino acid metabolism. PMID:26984270

  17. Solid-state NMR study of geopolymer prepared by sol-gel chemistry

    SciTech Connect

    Tsai, Yi-Ling; Hanna, John V.; Lee, Yuan-Ling; Smith, Mark E.; Chan, Jerry C.C.

    2010-12-15

    Geopolymers are a new class of materials formed by the condensation of aluminosilicates and silicates obtained from natural minerals or industrial wastes. In this work, the sol-gel method is used to synthesize precursor materials for the preparation of geopolymers. The geopolymer samples prepared by our synthetic route have been characterized by a series of physical techniques, including Fourier-transform infrared, X-ray diffraction, and multinuclear solid-state NMR. The results are very similar to those obtained for the geopolymers prepared from natural kaolinite. We believe that our synthetic approach can offer a good opportunity for the medical applications of geopolymer. -- Graphical abstract: Geopolymer prepared by the sol-gel route has the same spectroscopic properties as the sample prepared from the natural kaolinite. Display Omitted

  18. NMR- and GC/MS-based metabolomics of sulfur mustard exposed individuals: a pilot study.

    PubMed

    Nobakht, B Fatemeh; Aliannejad, Rasoul; Rezaei-Tavirani, Mostafa; Arefi Oskouie, Afsaneh; Naseri, Mohammad Taghi; Parastar, Hadi; Aliakbarzadeh, Ghazaleh; Fathi, Fariba; Taheri, Salman

    2016-09-01

    Sulfur mustard (SM) is a potent alkylating agent and its effects on cells and tissues are varied and complex. Due to limitations in the diagnostics of sulfur mustard exposed individuals (SMEIs) by noninvasive approaches, there is a great necessity to develop novel techniques and biomarkers for this condition. We present here the first nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC/MS) metabolic profiling of serum from and healthy controls to identify novel biomarkers in blood serum for better diagnostics. Of note, SMEIs were exposed to SM 30 years ago and that differences between two groups could still be found. Pathways in which differences between SMEIs and healthy controls are observed are related to lipid metabolism, ketogenesis, tricarboxylic acid (TCA) cycle and amino acid metabolism.

  19. Degradation of black phosphorus: a real-time 31P NMR study

    NASA Astrophysics Data System (ADS)

    Wang, Yue; Yang, Bingchao; Wan, Bensong; Xi, Xuekui; Zeng, Zhongming; Liu, Enke; Wu, Guangheng; Liu, Zhongyuan; Wang, Wenhong

    2016-09-01

    In this work, degradation behaviors and mechanisms of black phosphorus (BP) crystals in air under ambient conditions were investigated by nuclear magnetic resonance spectroscopy. It has been found that the 31P NMR line intensity for BP decreases exponentially during aging even at the very first several hours, suggesting the origin of the degradation of transport properties. In addition to phosphoric acid, new phosphorous acid was also well resolved in the final aging products. Moreover, BP has been found to be stable in water without the presence of oxygen molecules. These findings are relevant for better understanding of degradation behaviors of BP upon aging and should be helpful for overcoming a barrier that might hamper progress toward applications of BP as a 2D material.

  20. Water interactions with varying molecular states of bovine casein: 2H NMR relaxation studies

    SciTech Connect

    Kumosinski, T.F.; Pessen, H.; Prestrelski, S.J.; Farrell, H.M. Jr.

    1987-09-01

    The caseins occur in milk as spherical colloidal complexes of protein and salts with an average diameter of 1200 A, the casein micelles. Removal of Ca2+ is thought to result in their dissociation into smaller protein complexes stabilized by hydrophobic interactions and called submicelles. Whether these submicelles actually occur within the micelles as discrete particles interconnected by calcium phosphate salt bridges has been the subject of much controversy. A variety of physical measurements have shown that casein micelles contain an inordinately high amount of trapped water (2 to 7 g H/sub 2/O/g protein). With this in mind it was of interest to determine if NMR relaxation measurements could detect the presence of this trapped water within the micelles, and to evaluate whether it is a continuum with picosecond correlation times or is associated in part with discrete submicellar structures with nanosecond motions. For this purpose the variations in /sup 2/H NMR longitudinal and transverse relaxation rates of water with protein concentration were determined for bovine casein at various temperatures, under both submicellar and micellar conditions. D/sub 2/O was used instead of H/sub 2/O to eliminate cross-relaxation effects. From the protein concentration dependence of the relaxation rates, the second virial coefficient of the protein was obtained by nonlinear regression analysis. Using either an isotropic tumbling or an intermediate asymmetry model, degrees of hydration, v, and correlation times, tau c, were calculated for the caseins; from the latter parameter the Stokes radius, r, was obtained. Next, estimates of molecular weights were obtained from r and the partial specific volume. Values were in the range of those published from other methodologies for the submicelles.