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Sample records for proton nmr study

  1. Proton NMR studies of functionalized nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Tataurova, Yulia Nikolaevna

    in high-resolution NMR spectra. This technique is selective for protons on the surface organic functional groups due to their motional averaging in solution. In this study, 1H solution NMR spectroscopy was used to investigate the interface of the organic functional groups in D2O. The pKa for these functional groups covalently bound to the surface of nanoparticles was determined using an NMR-pH titration method based on the variation in the proton chemical shift for the alkyl group protons closest to the amine group with pH. The adsorption of toxic contaminants (chromate and arsenate anions) on the surface of functionalized silicalite-1 and mesoporous silica nanoparticles has been studied by 1H solution NMR spectroscopy. With this method, the surface bound contaminants are detected. The analysis of the intensity and position of these peaks allows quantitative assessment of the relative amounts of functional groups with adsorbed metal ions. These results demonstrate the sensitivity of solution NMR spectroscopy to the electronic environment and structure of the surface functional groups on porous nanomaterials.

  2. 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.

  3. Proton-NMR study on chemisorption of ethylene on platinum powder

    NASA Astrophysics Data System (ADS)

    Takashi Shibanuma; Toshiji Matsui

    1985-05-01

    The high-temperature phase of ethylene on surfaces of Pt powder has been studied by proton-NMR in order to decide whether the surface species is the ethylidyne species (CH 3C) proposed by Kesmodel et al. or the multiple-bonded species (CH 2CH) proposed by Demuth. The observed NMR spectrum is not attributable to CH 3-groups on the surfaes, but can be interpreted as the superposition of two signals, one originating from CH 2-groups and the other from CH-groups. In other words, the results suggest that the surface species is the multiple-bonded species.

  4. Proton-NMR study on chemisorption of ethylene on platinum powder

    NASA Astrophysics Data System (ADS)

    Shibanuma, Takashi; Matsui, Toshiji

    The high-temperature phase of ethylene on surfaces of Pt powder has been studied by proton-NMR in order to decide whether the surface species is the ethylidyne species (CH 3-C≡) proposed by Kesmodel et al. or the multiple-bonded species (-CH 2-CH=) proposed by Demuth. The observed NMR spectrum is not attributable to CH 3-groups on the surfaces, but can be interpreted as the superposition of two signals, one originating from CH 2-groups and the other from CH-groups. In other words, the results suggest that the surface species is the multiple-bonded species.

  5. NMR study of seed hydration with deuterated water: Dependence of proton signals on hydration level

    SciTech Connect

    Di Nola, A.; D'Ubaldo, A.; Fracassi, M.; Brosio, E. )

    1991-01-01

    Proton NMR signals in seeds are shown to depend on hydration level. In fact at low water amount, as it occurs in many native seeds, protons can have a restricted mobility and are not detectable. A NMR method for measuring the dependence of proton signals on hydration is reported. The method also allows the separation of the contributions of water and non-water protons in a low-resolution NMR experiment. It is based on successive hydrations (with deuterated water) - desiccation steps and on the analysis of the transverse magnetization decay curves.

  6. Water exchange in plant tissue studied by proton NMR in the presence of paramagnetic centers.

    PubMed

    Bacić, G; Ratković, S

    1984-04-01

    The proton NMR relaxation of water in maize roots in the presence of paramagnetic centers, Mn2+, Mn- EDTA2 -, and dextran-magnetite was measured. It was shown that the NMR method of Conlon and Outhred (1972, Biochem. Biophys. Acta. 288:354-361) can be applied to a heterogenous multicellular system, and the water exchange time between cortical cells and the extracellular space can be calculated. The water exchange is presumably controlled by the intracellular unstirred layers. The Mn- EDTA2 - complex is a suitable paramagnetic compound for complex tissue, while the application of dextran-magnetite is probably restricted to studies of water exchange in cell suspensions. The water free space of the root and viscosity of the cells cytoplasm was estimated with the use of Mn- EDTA2 -. The convenience of proton NMR for studying the multiphase uptake of paramagnetic ions by plant root as well as their transport to leaves is demonstrated. A simple and rapid NMR technique (spin-echo recovery) for continuous measurement of the uptake process is presented.

  7. Water exchange in plant tissue studied by proton NMR in the presence of paramagnetic centers.

    PubMed Central

    Bacić, G; Ratković, S

    1984-01-01

    The proton NMR relaxation of water in maize roots in the presence of paramagnetic centers, Mn2+, Mn- EDTA2 -, and dextran-magnetite was measured. It was shown that the NMR method of Conlon and Outhred (1972, Biochem. Biophys. Acta. 288:354-361) can be applied to a heterogenous multicellular system, and the water exchange time between cortical cells and the extracellular space can be calculated. The water exchange is presumably controlled by the intracellular unstirred layers. The Mn- EDTA2 - complex is a suitable paramagnetic compound for complex tissue, while the application of dextran-magnetite is probably restricted to studies of water exchange in cell suspensions. The water free space of the root and viscosity of the cells cytoplasm was estimated with the use of Mn- EDTA2 -. The convenience of proton NMR for studying the multiphase uptake of paramagnetic ions by plant root as well as their transport to leaves is demonstrated. A simple and rapid NMR technique (spin-echo recovery) for continuous measurement of the uptake process is presented. PMID:6426539

  8. 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.

  9. NMR and IR spectroscopic study of proton exchange between o-nitrophenol and methanol in CCl/sub 4/

    SciTech Connect

    Bureiko, S.F.; Golubev, N.S.; Lange, I.Y.

    1982-08-01

    The kinetics of proton exchange in solution between o-nitrophenol and methanol have been studied by dynamic NMR and IR spectroscopy, and a method has been developed for the simultaneous determination of the rate constants for H-H, H-D, and D-H exchange from /sup 1/H NMR spectra.

  10. 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.

  11. Synthesis and proton-NMR studies of oligonucleotides containing an apurinic (AP) site

    SciTech Connect

    Raap, J.; Dreef, C.E.; van der Marel, G.A.; van Boom, J.H.; Hilbers, C.W. )

    1987-10-01

    In order to elucidate the conformational properties of base-deleted oligodeoxyribonucleotides, the molecules d-CpS(pCpG)n (n = 1,2; S = sugar) were synthesized by the phosphotriester method and characterized by 1H-NMR spectroscopy. Complete assignment of all non-exchangeable proton resonances of both compounds was obtained by 1D- and 2D-NMR techniques. In combination with computer simulation, these spectra yielded proton-proton and proton-phosphorus coupling constants of high accuracy. These data provide valuable information about the sugar and the backbone conformation. It appears that d-Cp1Sp2Cp3G4 does not form a duplex under any of the conditions studied. On the contrary, the base-deleted hexamer d-Cp1Sp2Cp3Gp4Cp5G6 occurs as a right-handed' staggered' DNA duplex at 280 K: the core of this duplex is formed by the residues C(3)-G(6); two 'dangling' residues C(1) and S(2) are located at the two 5'-ends of the duplex. The assignment of the corresponding imino proton resonances for (d-CpS(pCpG)2)2 was based on their thermal behavior: the line broadening of these resonances was studied as a function of temperature. The chemical shift and the number of imino proton resonances accord well with the number and type of Watson-Crick base pairs which can be formed in the staggered duplex described above. Thermodynamic parameters of duplex formation were obtained from an analysis of the chemical shift versus temperature profiles of aromatic base and H-1' protons. It is suggested that the cytosine ring of C(1) stacks, at least part of the time, with the guanine ring on the nucleotide residue, G(6), situated in the complementary strand. The binding of Lys-Trp-Lys to (d-CpS(pCpG)2)2 as well as to (d-CpGpCpG)1 was investigated.

  12. 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. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  13. Bacteriophage Tail-Tube Assembly Studied by Proton-Detected 4D Solid-State NMR

    DOE PAGES

    Zinke, Maximilian; Fricke, Pascal; Samson, Camille; ...

    2017-07-07

    Obtaining unambiguous resonance assignments remains a major bottleneck in solid-state NMR studies of protein structure and dynamics. Particularly for supramolecular assemblies with large subunits (>150 residues), the analysis of crowded spectral data presents a challenge, even if three-dimensional (3D) spectra are used. Here, we present a proton-detected 4D solid-state NMR assignment procedure that is tailored for large assemblies. The key to recording 4D spectra with three indirect carbon or nitrogen dimensions with their inherently large chemical shift dispersion lies in the use of sparse non-uniform sampling (as low as 2 %). As a proof of principle, we acquired 4D (H)COCANH,more » (H)CACONH, and (H)CBCANH spectra of the 20 kDa bacteriophage tail-tube protein gp17.1 in a total time of two and a half weeks. These spectra were sufficient to obtain complete resonance assignments in a straightforward manner without use of previous solution NMR data.« less

  14. Characterization of filter extractables by proton NMR spectroscopy: studies on intact filters with process buffers.

    PubMed

    Kao, Y H; Bender, J; Hagewiesche, A; Wong, P; Huang, Y; Vanderlaan, M

    2001-01-01

    Studies were conducted to characterize potential extractables from sterilizing grade filters. The focus of this report is the 0.22 micron Durapore (hydrophilic modified PVDF) filter which is used throughout our recovery processes. The objectives of this study are (1) to identify potential filter extractables from the hydrophilic PVDF filters; (2) to show that NMR spectroscopy may be used to detect filter extractables in the presence of product and excipients; and (3) to establish levels of filter extractables obtained by extraction with a variety of buffers. The data show that the primary source of filter extractables is the hydrophilic modification of the PVDF membrane surface. Extractables from the modified hydrophilic PVDF filter include propylene glycol (PG) and soluble oligomers of the hydroxypropyl acrylate and cross-linker. Propylene glycol, arising from the hydrolysis of the hydroxypropyl acrylate, appears to be the primary extractable in buffers above pH 11. Since the 1H-NMR method can easily detect the methyl proton signals of PG, an NMR assay was developed to detect PG in the presence of buffer excipients and final product. Propylene glycol can be used as a marker for the extractables from Durapore hydrophilic PVDF filters. Although numerous buffers were used to generate extractables from the PVDF filter, significant extractables (PG and soluble oligomers) were found only in high pH extraction buffers. As a result of this finding, only a limited number of new buffers or new PVDF filters will require testing for future validation studies. Process validation studies have shown that neither PG nor soluble oligomers are at levels that impact the quality or safety of the product.

  15. The use of 1H NMR microscopy to study proton-exchange membrane fuel cells.

    PubMed

    Feindel, Kirk W; Bergens, Steven H; Wasylishen, Roderick E

    2006-01-16

    To understand proton-exchange membrane fuel cells (PEMFCs) better, researchers have used several techniques to visualize their internal operation. This Concept outlines the advantages of using 1H NMR microscopy, that is, magnetic resonance imaging, to monitor the distribution of water in a working PEMFC. We describe what a PEMFC is, how it operates, and why monitoring water distribution in a fuel cell is important. We will focus on our experience in constructing PEMFCs, and demonstrate how 1H NMR microscopy is used to observe the water distribution throughout an operating hydrogen PEMFC. Research in this area is briefly reviewed, followed by some comments regarding challenges and anticipated future developments.

  16. Proton NMR studies of PECVD hydrogenated amorphous silicon films and HWCVD hydrogenated amorphous silicon films

    NASA Astrophysics Data System (ADS)

    Herberg, Julie Lynn

    This dissertation discusses a new understanding of the internal structure of hydrogenated amorphous silicon. Recent research in our group has included nuclear spin echo double resonance (SEDOR) measurements on device quality hydrogenated amorphous silicon photovoltaic films. Using the SEDOR pulse sequence with and without the perturbing 29Si pulse, we obtain Fourier transform spectra for film at 80K that allows us to distinguish between molecular hydrogen and hydrogen bonded to silicon. Using such an approach, we have demonstrated that high quality a-Si:H films produced by Plasma Enhanced Chemical Vapor Deposition (PECVD) from SiH 4 contains about ten atomic percent hydrogen, nearly 40% of which is molecular hydrogen, individually trapped in the amorphous equivalent of tetragonal sites (T-sites). The main objective of this dissertation is to examine the difference between a-Si:H made by PECVD techniques and a-Si:H made by Hot Wire Chemical Vapor Deposition (HWCVD) techniques. Proton NMR and 1H- 29Si SEDOR NMR are used to examine the hydrogen structure of HWCVD a-Si:H films prepared at the University of Utrecht and at the National Renewable Energy Laboratory (NREL). Past NMR studies have shown that high quality PECVD a-Si:H films have geometries in which 40% of the contained hydrogen is present as H2 molecules individually trapped in the amorphous equivalent of T-sites. A much smaller H2 fraction sometimes is physisorbed on internal surfaces. In this dissertation, similar NMR methods are used to perform structural studies of the two HWCVD aSi:H samples. The 3kHz resonance line from T-site-trapped H2 molecules shows a hole-burn behavior similar to that found for PECVD a-Si:H films as does the 24kHz FWHM line from clustered hydrogen bonded to silicon. Radio frequency hole-burning is a tool to distinguish between inhomogenous and homogeneous broadening. In the hole-burn experiments, the 3kHz FWHM resonance line from T-site-trapped H2 molecules shows a hole

  17. NMR studies of the protonation states of pyridoxal-5‧-phosphate in water

    NASA Astrophysics Data System (ADS)

    Chan-Huot, Monique; Niether, Christiane; Sharif, Shasad; Tolstoy, Peter M.; Toney, Michael D.; Limbach, Hans-Heinrich

    2010-07-01

    We have measured the 13C NMR spectra of the cofactor pyridoxal-5'-phosphate (vitamin B 6, PLP) at 278 K in aqueous solution as a function of pH. By 13C enrichment of PLP in the C-4' and C-5' positions we were able to measure spectra down to pH 1. From the dependence of the 13C chemical shifts on pH, the p Ka values of PLP could be determined. In particular, the heretofore uncharacterized protonation state of PLP, in which the phosphate group as well as the pyridine ring and the phenolic groups are fully protonated, has been analyzed. The corresponding p Ka value of 2.4 indicates that the phosphate group is solely involved in the first deprotonation step. The 15N chemical shifts of the pyridine ring of PLP published previously are in good agreement with the new results. These shifts contain information about the tautomerism of the different protonation states of PLP. The implications of these findings for the biological function of PLP are discussed.

  18. Oligomerization of protegrin-1 in the presence of DPC micelles. A proton high-resolution NMR study.

    PubMed

    Roumestand, C; Louis, V; Aumelas, A; Grassy, G; Calas, B; Chavanieu, A

    1998-01-16

    Protegrins are members of a family of five Cys-rich naturally occurring cationic antimicrobial peptides. The NMR solution structure of protegrin-1 (PG-1) has been previously determined as a monomeric beta-hairpin both in water and in dimethylsulfoxide solution. Protegrins are bactericidal peptides but their mechanism of action is still unknown. In order to investigate the structural basis of their cytotoxicity, we studied the effect of lipid micelles on the structure of PG-1. The NMR study reported in the present work indicates that PG-1 adopts a dimeric structure when it binds to dodecylphosphocholine micelles. Moreover, the amide proton exchange study suggests the possibility of an association between several dimers.

  19. The local order of supercooled water in solution with LiCl studied by NMR proton chemical shift

    NASA Astrophysics Data System (ADS)

    Corsaro, C.; Mallamace, D.; Vasi, S.; Cicero, N.; Dugo, G.; Mallamace, F.

    2016-05-01

    We study by means of Nuclear Magnetic Resonance (NMR) spectroscopy the local order of water molecules in solution with lithium chloride at eutectic concentration. In particular, by measuring the proton chemical shift as a function of the temperature in the interval 203{ K}NMR peak allows the investigation of the mutual difference between the chemical shift of water solvating lithium and chlorine individually. The thermal behavior of this quantity confirms previous results about the role of the temperature in the solvation mechanisms down to about 225K. This temperature coincides with that of the so-called Widom line for water supporting the liquid-liquid transition hypothesis.

  20. 1H-NMR study of diamagnetic cytochrome P450cam: assignment of heme resonances and substrate dependance of one cysteinate beta proton.

    PubMed

    Mouro, C; Bondon, A; Simonneaux, G; Jung, C

    1997-09-08

    The 1H-NMR study of diamagnetic cytochrome P450cam FeII-CO has been performed for the first time. Chemical shifts of the cysteinate fifth ligand protons and of several heme protons have been assigned through 1- and 2-dimensional spectra at 500 MHz. A substrate dependance has been observed for the resonance of the cysteinate proton detected in the high-field region.

  1. Proton and tritium NMR relaxation studies of peptide inhibitor binding to bacterial collagenase: Conformation and dynamics

    SciTech Connect

    Dive, V.; Lai, A.; Valensin, G.; Saba, G.; Yiotakis, A.; Toma, F. )

    1991-02-15

    The interaction of succinyl-Pro-Ala, a competitive inhibitor of Achromobacter iophagus collagenase, with the enzyme was studied by longitudinal proton and tritium relaxation. Specific deuterium and tritium labeling of the succinyl part at vicinal positions allowed the measurement of the cross-relaxation rates of individual proton or tritium spin pairs in the inhibitor-enzyme complex as well as in the free inhibitor. Overall correlation times, internuclear distances, and qualitative information on the internal mobility in Suc1 (as provided by the generalized order parameter S2) could be deduced by the comparison of proton and tritium cross-relaxation of spin pairs at complementary positions in the -CH2- CH2- moiety as analyzed in terms of the model-free approach by Lipari and Szabo. The conformational and motional parameters of the inhibitor in the free and enzyme-bound state were directly compared by this method. The measurement of proton cross-relaxation in the Ala residue provided additional information on the inhibitor binding. The determination of the order parameter in different parts of the inhibitor molecule in the bound state indicates that the succinyl and alanyl residues are primarily involved in the interaction with the enzyme activity site. The succinyl moiety, characterized in solution by the conformational equilibrium among the three staggered rotamers--i.e., trans: 50%; g+: 20%; g-: 30%--adopted in the bound state the unique trans conformation.

  2. Interactions of hydrogen with alkali promoted Ru/SiO2 catalysts: A proton NMR study

    SciTech Connect

    Uner, Denis Ozbay

    1994-05-10

    Role of H spillover to the silica support was studied using chemisorption; a strongly bound component of spilled over H was found in the silica support which interfered with accurate measurements of active metal sites via volumetric strong H chemisorption. The volumetric chemisorption technique was modified so that measurement times were reduced from 12--36 h to 1 h. The active Ru surface was characterized means of changes in proton spin counts and NMR Knight shifts vs alkali loading. Na, K blocked the active surface of Ru metal, but Cs was pushed off by H chemisorption. The alkali promoters restricted H mobility on both metal surface and at the metal support interfaces; this is consistent with effects on Fischer-Tropsch synthesis. 1H NMR was used to study the effect of the active metal and promoter on support hydroxyl groups. The OH group density in the silica support decreased with metal and/or promoter loading, but not on a one-to-one basis; the exchange efficiency of the hydroxyls decreased with atomic size of the alkali metal. An additional downfield proton resonance was detected which was assigned to the alkali hydroxide species in the support.

  3. 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

  4. Proton NMR spectral study of UV treated live Escherichia coli Bacteria

    NASA Astrophysics Data System (ADS)

    Sorokopud, Michael

    The lethal effects of ultraviolet radiation on microorganisms have been known and utilized for many years. In sufficiently high photon fluences, light and in particular, UV light, is an effective and subtle means of killing or at least immobilizing most, if not all cells and micro-organisms. Because of their small size, light can penetrate the enclosing protective walls and enter the inner volumes where it can break organic bonds in components that are vital to cell function. Despite the fact that a very low dose of UV light (1-9 mJ/cm2) has been shown to inactivate many micro-organisms, there remains a dearth of biological information about light induced effects in molecules and their interactions within living microbial systems. The use of 1H NMR as a spectroscopic tool was chosen to undertake an examination of the possible effects resulting from exposing E. coli to lethal fluencies of UV radiation. Once sample preparation, treatment, and NMR mounting methods were optimized, the high sensitivity and high resolution capabilities of the method produced reproducible results for a series of experiments. These results reveal significant changes in the ratio of the 1H NMR spectra of the treated to untreated E.coli samples when the treated sample was exposed to a lethal fluence of 275nm light. Photons at the 275nm wavelength, used in this study, have enough energy to break all of the principle bonds in an organic molecule. The difference spectrum between treated to untreated samples appears to be fitted well using specific component spectra from these groups of compounds. Increases in NMR peak amplitudes are observed and appear to be correlated with the spectral locations of several amino acids, membrane components and several sugars/saccharides. Increases in peak intensities of 4-8% were observed in the 0.8-1.1 ppm chemical shift region, characteristic of lipid and amino acid groups. A 3.5-4% increase was observed in the 2 ppm and 3.4-4 ppm region characteristic of

  5. Isotope-edited proton NMR study on the structure of a pepsin/inhibitor complex

    SciTech Connect

    Fesik, S.W.; Luly, J.R.; Erickson, J.W.; Abad-Zapatero, C.

    1988-11-01

    A general approach is illustrated for providing detailed structural information on large enzyme/inhibitor complexes using NMR spectroscopy. The method involves the use of isotopically labeled ligands to simplify two-dimensional NOE spectra of large molecular complexes by isotope-editing techniques. With this approach, the backbone and side-chain conformations (at the P/sub 2/ and P/sub 3/ sites) of a tightly bound inhibitor of porcine pepsin have bene determined. In addition, structural information on the active site of pepsin has been obtained. Due to the sequence homology between porcine pepsin and human renin, this structural information may prove useful for modeling renin/inhibitor complexes with the ultimate goal of designing more effective renin inhibitors. Moreover, this general approach can be applied to study other biological systems of interest such as other enzyme/inhibitor complexes, ligands bound to soluble receptors, and enzyme/substrate interactions.

  6. Structural features of the protophorphyrin-apomyoglobin complex. A proton NMR spectroscopy study

    SciTech Connect

    Lecomte, J.T.J.; Cocco, M.J. )

    1990-12-01

    The structural properties of the complex formed by apomyoglobin and protoporphyrin IX (des-iron myoglobin) were studied to probe the influence of iron-to-histidine coordination on the native myoglobin fold and the heme binding site geometry. Standard two-dimensional proton nuclear magnetic resonance spectroscopy methods were applied to identify porphyrin and protein signals. A pronounced spectral resemblance between carbonmonoxymyoglobin and des-iron myogobin was noticed that could be exploited to assign a number of resonances by nuclear Overhauser spectroscopy. Protoporphyrin IX was determined to bind in the same orientation as the heme. Most residues in contact with the prosthetic group were found in the holomyoglobin conformation. Several tertiary structure features were also characterized near the protein termini. It was concluded that the protoporphyrin-apomyoglobin interactions are capable of organizing the binding site and the unfolded region of the apoprotein into the native holoprotein structure.

  7. Characterization of hydrophobic cores in apomyoglobin: A proton NMR spectroscopy study

    SciTech Connect

    Cocco, M.J.; Lecomte, J.T.L. )

    1990-12-01

    A proton nuclear magnetic resonance spectroscopic study of horse apomyoglobin was undertaken in order to define the regions of myoglobin that are and that are not structurally affected by the binding of the prosthetic group. It was found that, in spite of the poor spectral resolution, a number of spin systems could be identified by using standard correlated methods. Four clusters consisting mostly of hydrophobic residues were detected by nuclear Overhauser spectroscopy, two of which involved the tryptophan side chains. Extensive similarities to nuclear Overhauser spectroscopy data collected on the carbonmonoxy form of holomyoglobin suggested tentative assignments for several residues. It appeared that distinct cores of side chains on the distal side of the binding pocket and between the A, B, G, and H helices maintain the same packing as they do in holomyoglobin and apomyoglobin reconstituted with protoporphyrin IX.

  8. Hydrogen bond geometries and proton tautomerism of homoconjugated anions of carboxylic acids studied via H/D isotope effects on 13C NMR chemical shifts.

    PubMed

    Guo, Jing; Tolstoy, Peter M; Koeppe, Benjamin; Golubev, Nikolai S; Denisov, Gleb S; Smirnov, Sergei N; Limbach, Hans-Heinrich

    2012-11-26

    Ten formally symmetric anionic OHO hydrogen bonded complexes, modeling Asp/Glu amino acid side chain interactions in nonaqueous environment (CDF(3)/CDF(2)Cl solution, 200-110 K) have been studied by (1)H, (2)H, and (13)C NMR spectroscopy, i.e. intermolecularly H-bonded homoconjugated anions of acetic, chloroacetic, dichloroacetic, trifluoroacetic, trimethylacetic, and isobutyric acids, and intramolecularly H-bonded hydrogen succinate, hydrogen rac-dimethylsuccinate, hydrogen maleate, and hydrogen phthalate. In particular, primary H/D isotope effects on the hydrogen bond proton signals as well as secondary H/D isotope effects on the (13)C signals of the carboxylic groups are reported and analyzed. We demonstrate that in most of the studied systems there is a degenerate proton tautomerism between O-H···O(-) and O(-)···H-O structures which is fast in the NMR time scale. The stronger is the proton donating ability of the acid, the shorter and more symmetric are the H-bonds in each tautomer of the homoconjugate. For the maleate and phthalate anions exhibiting intramolecular hydrogen bonds, evidence for symmetric single well potentials is obtained. We propose a correlation between H/D isotope effects on carboxylic carbon chemical shifts and the proton transfer coordinate, q(1) = ½(r(OH) - r(HO)), which allows us to estimate the desired OHO hydrogen bond geometries from the observed (13)C NMR parameters, taking into account the degenerate proton tautomerism.

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

    ERIC Educational Resources Information Center

    Smith, Robert L.; And Others

    1988-01-01

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

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

    ERIC Educational Resources Information Center

    Smith, Robert L.; And Others

    1988-01-01

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

  11. NMR studies of protonation and hydrogen bond states of internal aldimines of pyridoxal 5'-phosphate acid-base in alanine racemase, aspartate aminotransferase, and poly-L-lysine.

    PubMed

    Chan-Huot, Monique; Dos, Alexandra; Zander, Reinhard; Sharif, Shasad; Tolstoy, Peter M; Compton, Shara; Fogle, Emily; Toney, Michael D; Shenderovich, Ilya; Denisov, Gleb S; Limbach, Hans-Heinrich

    2013-12-04

    Using (15)N solid-state NMR, we have studied protonation and H-bonded states of the cofactor pyridoxal 5'-phosphate (PLP) linked as an internal aldimine in alanine racemase (AlaR), aspartate aminotransferase (AspAT), and poly-L-lysine. Protonation of the pyridine nitrogen of PLP and the coupled proton transfer from the phenolic oxygen (enolimine form) to the aldimine nitrogen (ketoenamine form) is often considered to be a prerequisite to the initial step (transimination) of the enzyme-catalyzed reaction. Indeed, using (15)N NMR and H-bond correlations in AspAT, we observe a strong aspartate-pyridine nitrogen H-bond with H located on nitrogen. After hydration, this hydrogen bond is maintained. By contrast, in the case of solid lyophilized AlaR, we find that the pyridine nitrogen is neither protonated nor hydrogen bonded to the proximal arginine side chain. However, hydration establishes a weak hydrogen bond to pyridine. To clarify how AlaR is activated, we performed (13)C and (15)N solid-state NMR experiments on isotopically labeled PLP aldimines formed by lyophilization with poly-L-lysine. In the dry solid, only the enolimine tautomer is observed. However, a fast reversible proton transfer involving the ketoenamine tautomer is observed after treatment with either gaseous water or gaseous dry HCl. Hydrolysis requires the action of both water and HCl. The formation of an external aldimine with aspartic acid at pH 9 also produces the ketoenamine form stabilized by interaction with a second aspartic acid, probably via a H-bond to the phenolic oxygen. We postulate that O-protonation is an effectual mechanism for the activation of PLP, as is N-protonation, and that enzymes that are incapable of N-protonation employ this mechanism.

  12. Dynamics of benzimidazole ethylphosphonate: a solid-state NMR study of anhydrous composite proton-conducting electrolytes.

    PubMed

    Yan, Z Blossom; De Almeida, Nicole E; Traer, Jason W; Goward, Gillian R

    2013-11-07

    Imidazole phosphate and phosphonate solid acids model the hydrogen-bonding networks and dynamics of the anhydrous electrolyte candidate for proton exchange membrane fuel cells. Solid-state NMR reveals that phosphate and phosphonate anion dynamics dominate the rate of long-range proton transport, and that the presence of a membrane host facilitates proton mobility, as evidenced by a decreased correlation time of the composites (80 ± 15 ms) relative to the pristine salt (101 ± 5 ms). Benzimidazole ethylphosphonate (Bi-ePA) is chosen as a model salt to investigate the membrane system. The hydrogen-bonding structure of Bi-ePA is established using X-ray diffraction coupled with solid-state (1)H-(1)H DQC NMR. The anion dynamics has been determined using solid-state (31)P CODEX NMR. By comparing the dynamics of ethylphosphonate groups in pristine salt and membrane-salt composites, it is clear that the rotation process involves three-site exchange. Through data interpretation, a stretched exponential function is introduced with the stretching exponent, β, ranging 0 < β ≤ 1. The (31)P CODEX data for pristine salt are fitted with single exponential decay where β = 1; however, the data for the membrane-salt composites are fitted with stretched exponential functions, where β has a constant value of 0.5. This β value suggests a non-Gaussian distribution of the dynamic systems in the composite sample, which is introduced by the membrane host.

  13. Efficacy of Withania somnifera on seminal plasma metabolites of infertile males: a proton NMR study at 800 MHz.

    PubMed

    Gupta, Ashish; Mahdi, Abbas Ali; Shukla, Kamla Kant; Ahmad, Mohammad Kaleem; Bansal, Navneeta; Sankhwar, Pushplata; Sankhwar, Satya Narain

    2013-08-26

    Traditional Indian systems of medicine use roots of Withania somnifera for impotence, infertility treatment, stress, and the aging process. Although Withania somnifera improves semen quality by regulating reproductive hormone levels and oxidative stress, the molecular mechanism is not clear. Our study uses high-resolution Nuclear Magnetic Resonance (NMR) spectroscopy to explore the scientific basis to reveal the pre- and post-treatment efficacy of Withania somnifera on seminal plasma of infertile men-which remains unexplored to date. A total of 180 infertile male patients were administered Withania somnifera root powder at the rate of 5 g/d for a 3-month period. The study included age-matched, healthy men as a control (n=50) group. Proton NMR spectroscopy was used to measure lactate, alanine, glutamate, glutamine, citrate, lysine, choline, glycerophosphocholine (GPC), glycine, tyrosine, histidine, phenylalanine, and uridine in all seminal plasma samples. To appraise infertility levels, we also measured sperm concentration, motility, lipid peroxide, and hormonal perturbation. Withania somnifera therapy repairs the disturbed concentrations of lactate, alanine, citrate, GPC, histidine, and phenylalanine in seminal plasma and recovers the quality of semen of post-treated compared to pre-treated infertile men. Serum biochemistry was also improved over post-therapy in infertile men. Our findings reveal that Withania somnifera not only reboots enzymatic activity of metabolic pathways and energy metabolism but also invigorates the harmonic balance of seminal plasma metabolites and reproductive hormones in infertile men. The results suggest that Withania somnifera may be used as an empirical therapy for clinical management and treatment of infertility. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  14. A proton NMR relaxation study of water dynamics in bovine serum albumin nanoparticles.

    PubMed

    Belotti, Monica; Martinelli, Andrea; Gianferri, Raffaella; Brosio, Elvino

    2010-01-14

    Water dynamics and compartmentation in glutaraldehyde cross-linked bovine serum albumin nanoparticles have been investigated by an integrated nuclear magnetic resonance (NMR) protocol based on water relaxation times and self-diffusion coefficients measurements. Multi-exponentially of water relaxation curves has been accounted for according to a diffusive and chemical exchange model (see B. P. Hills, S. F. Takacs and P. S. Belton, Mol. Phys., 1989, 67(4), 903, and Mol. Phys., 1989, 67(4), 913; E. Brosio, M. Belotti and R. Gianferri, in Food Science and Technology: New Research, ed. L. V. Greco and M. N. Bruno, Nova Science Publishers, Hauppauge (NY), 2008) that made it possible to single out water molecules in the molecular spaces in the interior of albumin nanoparticles, in the meso-cavities formed by packed nanoparticles and in the meniscus on top of the nanoparticles suspension. A quantitative rationalization of T(2) values of water different components allowed morphological information to be acquired as for the size of water filled compartments, while self-diffusion coefficient measurements of water excess or fluxed packed nanoparticles suspensions are describers of transport properties of soft biomaterials. The paper reports an NMR approach that can be seen as a general and relevant method to characterize excess-water-swollen soft biomaterials.

  15. High resolution NMR study of T{sub 1} magnetic relaxation dispersion. IV. Proton relaxation in amino acids and Met-enkephalin pentapeptide

    SciTech Connect

    Pravdivtsev, Andrey N.; Yurkovskaya, Alexandra V.; Ivanov, Konstantin L.; Vieth, Hans-Martin

    2014-10-21

    Nuclear Magnetic Relaxation Dispersion (NMRD) of protons was studied in the pentapeptide Met-enkephalin and the amino acids, which constitute it. Experiments were run by using high-resolution Nuclear Magnetic Resonance (NMR) in combination with fast field-cycling, thus enabling measuring NMRD curves for all individual protons. As in earlier works, Papers I–III, pronounced effects of intramolecular scalar spin-spin interactions, J-couplings, on spin relaxation were found. Notably, at low fields J-couplings tend to equalize the apparent relaxation rates within networks of coupled protons. In Met-enkephalin, in contrast to the free amino acids, there is a sharp increase in the proton T{sub 1}-relaxation times at high fields due to the changes in the regime of molecular motion. The experimental data are in good agreement with theory. From modelling the relaxation experiments we were able to determine motional correlation times of different residues in Met-enkephalin with atomic resolution. This allows us to draw conclusions about preferential conformation of the pentapeptide in solution, which is also in agreement with data from two-dimensional NMR experiments (rotating frame Overhauser effect spectroscopy). Altogether, our study demonstrates that high-resolution NMR studies of magnetic field-dependent relaxation allow one to probe molecular mobility in biomolecules with atomic resolution.

  16. Proton NMR studies of the electronic structure of ZrH/sub x/

    NASA Technical Reports Server (NTRS)

    Attalla, A.; Bowman, R. C., Jr.; Craft, B. D.; Venturini, E. L.; Rhim, W. K.

    1982-01-01

    The proton spin lattice relaxation times and Knight shifts were measured in f.c.c. (delta-phase) and f.c.t. (epsilon-phase) ZrH/sub x/ for 1.5 or = to x or = to 2.0. Both parameters indicate that N(E/sub F/) is very dependent upon hydrogen content with a maximum occurring at ZrH1 83. This behavior is ascribed to modifications in N(E/sub F/) through a fcc/fct distortion in ZrH/sub x/ associated with a Jahn-Teller effect.

  17. Proton NMR Study of Room Temperature Aging in Isotactic Polypropylene and Ethylene/Octene Copolymers

    NASA Astrophysics Data System (ADS)

    Vanderhart, David; Snyder, Chad; Alamo, Rufina

    2003-03-01

    The Bloch-decay proton spectra of 2 isotactic polypropylenes (iPP) and 2 ethylene/octene (EO) copolymers have been monitored as a function of room-temperature aging time, t_age, from 10 min to 4 d. Conditions for initiating aging were air-quench from the melt for EO and 6 min annealing near 90 ^oC for iPP. We focused on elucidating the nature of aging, both morphologically and via concepts like secondary crystallization. To this end, some multiple-pulse experiments were also conducted. Aging always reduced the population of the most mobile species. It was linear in log(t_age)and the (minimum) amount of motionally transformed material was only a few percent. In iPP, aging was dominated by secondary crystallization rather than a general densification of the amorphous region. Aging-induced crystallization in EO is less well defined. The iPP samples had significant contrast in defect content, mass dispersion, and amorphous content; however, the contrast in aging amounts was only modest. No definitive morphological placement of the aging structures formed could be deduced; but possibilites consistent with the data will be discussed.

  18. NMR study of CHN hydrogen bond and proton transfer in 1,1-dinitroethane complex with 2,4,6-trimethylpyridine.

    PubMed

    Tupikina, Elena Yu; Denisov, Gleb S; Tolstoy, Peter M

    2015-01-29

    The intermolecular complex with a CHN hydrogen bond formed by 1,1-dinitroethane (DNE) and 2,4,6-trimethylpyridine (collidine) dissolved in CD2Cl2 was studied experimentally by (1)H NMR spectroscopy at 180-300 K. Equilibrium between the molecular CH···N form and the zwitterionic C(-)/HN(+) form was detected in the slow exchange regime in the NMR time scale. No sign of a direct C(-)···HN(+) bond was observed; the ion pair is likely to be held by Coulomb interactions. Moreover, there are indications that the protonated base is involved in the formation of homoconjugated (NHN)(+) collidine-collidinium hydrogen bonded complexes. The reaction pathway of proton transfer in the DNE-pyiridine complex in a vacuum was studied computationally at the B3LYP/6-31++G(d,p) level of theory. NMR chemical shifts and coupling constants were calculated for a series of snapshots along the proton transfer coordinate. While the central carbon atom has a pyramidal (sp(3)) configuration in DNE, it is flat (sp(2)) in the DNE carbanion. As a result, the most indicative computed NMR parameter reflecting hybridization of a carbon atom appeared to be (1)JCC, which starts to change rapidly as soon as a structure with a quasi-symmetric C··H··N bond is reached. Couplings within the hydrogen bridge, (1)JCH, (1h)JHN, and (2)JCN, can serve as good indicators of the degree of proton transfer.

  19. Proton clouds to measure long-range contacts between nonexchangeable side chain protons in solid-state NMR.

    PubMed

    Sinnige, Tessa; Daniëls, Mark; Baldus, Marc; Weingarth, Markus

    2014-03-26

    We show that selective labeling of proteins with protonated amino acids embedded in a perdeuterated matrix, dubbed 'proton clouds', provides general access to long-range contacts between nonexchangeable side chain protons in proton-detected solid-state NMR, which is important to study protein tertiary structure. Proton-cloud labeling significantly improves spectral resolution by simultaneously reducing proton line width and spectral crowding despite a high local proton density in clouds. The approach is amenable to almost all canonical amino acids. Our method is demonstrated on ubiquitin and the β-barrel membrane protein BamA.

  20. 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

  1. Magnetic susceptibility and spin dynamics of a polyoxovanadate cluster: A proton NMR study of a model spin tetramer

    NASA Astrophysics Data System (ADS)

    Procissi, D.; Shastri, A.; Rousochatzakis, I.; Al Rifai, M.; Kögerler, P.; Luban, M.; Suh, B. J.; Borsa, F.

    2004-03-01

    We report susceptibility and nuclear magnetic resonance (NMR) measurements in a polyoxovanadate compound with formula (NHEt)3[VIV8VV4As8O40(H2O)]ṡH2O≡{V12}. The magnetic properties can be described by considering only the central square of localized V4+ ions and treated by an isotropic Heisenberg Hamiltonian of four intrinsic spins 1/2 coupled by nearest-neighbor antiferromagnetic interaction with J˜17.6 K. In this simplified description the ground state is nonmagnetic with ST=0. The 1H NMR linewidth (full width at half maximum) data depend on both the magnetic field and temperature, and are explained by the dipolar interaction between proton nuclei and V4+ ion spins. The behavior of the nuclear spin-lattice relaxation rate T-11 in the temperature range (4.2 300 K) is similar to that of χT vs T and it does not show any peak at low temperatures contrary to previous observations in antiferromagnetic rings with larger intrinsic spins. The results are explained by using the general features of the Moriya formula and by introducing a single T-independent broadening parameter for the electronic spin system. From the exponential T dependence of T-11 at low T (2.5 KNMR=Δ0-gμBH, with the gap Δ0˜17.6 K in agreement with the susceptibility data. Below 2.5 K the proton T-11 deviates from the exponential decrease indicating the presence of a small, almost temperature independent, but strongly field dependent, nuclear relaxation contribution, which we will investigate in detail in the near future.

  2. Proton-coupled 15N NMR spectra of neutral and protonated ethenoadenosine and ethenocytidine.

    PubMed Central

    Sierzputowska-Gracz, H; Wiewiórowski, M; Kozerski, L; von Philipsborn, W

    1984-01-01

    The 15N chemical shifts and 15N, 1H spin coupling constants were determined in the title compounds using the INEPT pulse sequence and assigned with the aid of selective proton decoupling. The delta/15N/ and J/N, H/ values are discussed in terms of involvement of the imidazole ring created by ethenobridging in the electronic structure of the whole molecule. Both spectral parameters indicate that the diligant nitrogen in this ring is the primary site of protonation in these modified nucleosides. It is concluded that 15N NMR of nucleoside bases can be largely a complementary method to 1H and 13C NMR studies and, in addition, can serve as a direct probe for studies of nitrogen environment in oligomeric fragments of nucleic acids even at moderately strong magnetic fields due to the higher spectral dispersion compared with 1H and 13C NMR spectra. PMID:6473107

  3. Experimental study of resolution of proton chemical shifts in solids: Combined multiple pulse NMR and magic-angle spinning

    SciTech Connect

    Ryan, L.M.; Taylor, R.E.; Paff, A.J.; Gerstein, B.C.

    1980-01-01

    High-resolution nuclear magnetic resonance spectra of protons in rigid, randomly oriented solids have been measured using combined homonuclear dipolar decoupling (via multiple pulse techniques) and attenuation of chemical shift anisotropies (via magic-angle sample spinning). Under those conditions, isotropic proton chemical shifts were recorded for a variety of chemical species, with individual linewidths varying from about 55 to 110 Hz (1--2 ppm). Residual line broadening was due predominately to (i) magnetic-field instability and inhomogeneity, (ii) unresolved proton--proton spin couplings, (iii) chemical shift dispersion, (iv) residual dipolar broadening, and (v) lifetime broadening under the multiple pulse sequences used. The magnitudes of those effects and the current limits of resolution for this experiment in our spectrometer have been investigated. The compounds studied included organic solids (4, 4'-dimethylbenzophenone, 2, 6-dimethylbenzoic acid, and aspirin), polymers (polystyrene and polymethylmethacrylate), and the vitrain portion of a bituminous coal.

  4. NMR study of conformational exchange and double-well proton potential in intramolecular hydrogen bonds in monoanions of succinic acid and derivatives.

    PubMed

    Guo, Jing; Tolstoy, Peter M; Koeppe, B; Denisov, Gleb S; Limbach, Hans-Heinrich

    2011-09-08

    We present a (1)H, (2)H, and (13)C NMR study of the monoanions of succinic (1), meso- and rac-dimethylsuccinic (2, 3), and methylsuccinic (4) acids (with tetraalkylammonium as the counterion) dissolved in CDF(3)/CDF(2)Cl at 300-120 K. In all four monoanions, the carboxylic groups are linked by a short intramolecular OHO hydrogen bond revealed by the bridging-proton chemical shift of about 20 ppm. We show that the flexibility of the carbon skeleton allows for two gauche isomers in monoanions 1, 2, and 4, interconverting through experimental energy barriers of 10-15 kcal/mol (the process itself and the energy barrier are also reproduced in MP2/6-311++G** calculations). In 3, one of the gauche forms is absent because of the steric repulsion of the methyl groups. In all four monoanions, the bridging proton is located in a double-well potential and subject, at least to some extent, to proton tautomerism, for which we estimate the two proton positions to be separated by ca. 0.2 Å. In 1 and 3, the proton potential is symmetric. In 2, slowing the conformational interconversion introduces an asymmetry to the proton potential, an effect that might be strong enough even to synchronize the proton tautomerism with the interconversion of the two gauche forms. In 4, the asymmetry of the proton potential is due to the asymmetric substitution. The intramolecular H-bond is likely to remain intact during the interconversion of the gauche forms in 1, 3, and 4, whereas the situation in 2 is less clear.

  5. The Effect of Antitumor Glycosides on Glioma Cells and Tissues as Studied by Proton HR-MAS NMR Spectroscopy

    PubMed Central

    García-Álvarez, Isabel; Garrido, Leoncio; Romero-Ramírez, Lorenzo; Nieto-Sampedro, Manuel; Fernández-Mayoralas, Alfonso; Campos-Olivas, Ramón

    2013-01-01

    The effect of the treatment with glycolipid derivatives on the metabolic profile of intact glioma cells and tumor tissues, investigated using proton high resolution magic angle spinning (1H HR-MAS) nuclear magnetic resonance (NMR) spectroscopy, is reported here. Two compounds were used, a glycoside and its thioglycoside analogue, both showing anti-proliferative activity on glioma C6 cell cultures; however, only the thioglycoside exhibited antitumor activity in vivo. At the drug concentrations showing anti-proliferative activity in cell culture (20 and 40 µM), significant increases in choline containing metabolites were observed in the 1H NMR spectra of the same intact cells. In vivo experiments in nude mice bearing tumors derived from implanted C6 glioma cells, showed that reduction of tumor volume was associated with significant changes in the metabolic profile of the same intact tumor tissues; and were similar to those observed in cell culture. Specifically, the activity of the compounds is mainly associated with an increase in choline and phosphocholine, in both the cell cultures and tumoral tissues. Taurine, a metabolite that has been considered a biomarker of apoptosis, correlated with the reduction of tumor volume. Thus, the results indicate that the mode of action of the glycoside involves, at least in part, alteration of phospholipid metabolism, resulting in cell death. PMID:24194925

  6. Polar solvent fluctuations drive proton transfer in hydrogen bonded complexes of carboxylic acid with pyridines: NMR, IR and ab initio MD study.

    PubMed

    Koeppe, B; Pylaeva, S A; Allolio, C; Sebastiani, D; Nibbering, E T J; Denisov, G S; Limbach, H-H; Tolstoy, P M

    2017-01-04

    We study a series of intermolecular hydrogen-bonded 1 : 1 complexes formed by chloroacetic acid with 19 substituted pyridines and one aliphatic amine dissolved in CD2Cl2 at low temperature by (1)H and (13)C NMR and FTIR spectroscopy. The hydrogen bond geometries in these complexes vary from molecular (O-HN) to zwitterionic (O(-)H-N(+)) ones, while NMR spectra show the formation of short strong hydrogen bonds in intermediate cases. Analysis of C[double bond, length as m-dash]O stretching and asymmetric CO2(-) stretching bands in FTIR spectra reveal the presence of proton tautomerism. On the basis of these data, we construct the overall proton transfer pathway. In addition to that, we also study by use of ab initio molecular dynamics the complex formed by chloroacetic acid with 2-methylpyridine, surrounded by 71 CD2Cl2 molecules, revealing a dual-maximum distribution of hydrogen bond geometries in solution. The analysis of the calculated trajectory shows that the proton jumps between molecular and zwitterionic forms are indeed driven by dipole-dipole solvent-solute interactions, but the primary cause of the jumps is the formation/breaking of weak CHO bonds from solvent molecules to oxygen atoms of the carboxylate group.

  7. α-Substituted Bis(octabutoxyphthalocyaninato)Terbium(III) Double-Decker Complexes: Preparation and Study of Protonation by NMR and DFT.

    PubMed

    Damjanović, Marko; Horie, Yusuke; Morita, Takaumi; Horii, Yoji; Katoh, Keiichi; Yamashita, Masahiro; Enders, Markus

    2015-12-21

    Synthesis of the anionic, α-substituted, bis(phthalocyaninato)Tb(III) complex [Tb(α-obPc)2](-) ([1](-)) (obPc = α-octabutoxyphthalocyaninato) leads to the isolation of its protonated form [1H](0). This complex was characterized by X-ray diffraction (XRD), mass spectroscopy (MS), infrared (IR) and ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy. Crystal structure analysis did not allow localization of the additional proton, which is probably attached to the meso-N atom or isoindole-N atom of the phthalocyaninato ligand. [1H](0) can easily be deprotonated or protonated, giving the corresponding anionic and cationic complexes. The three compounds [1H](0), [1](-), and [1HH](+) were studied by a combination of paramagnetic NMR experiments ((1)H, (13)C, variable-temperature measurements, two-dimensional nuclear magnetic resonance and DFT calculations (done on Y(III) analogues with octamethoxyphthalocyaninato ligands), for the purpose of elucidating the positions of the acidic protons and for understanding the structural changes of the coordination environment of the Tb ion induced by protonation.

  8. Lactonization and protonation of gluconic acid: a thermodynamicand kinetic study by potentiometry, nmr and esi-ms

    SciTech Connect

    Zhang, Z.; Gibson, P.; Clark, S.B.; Tian, G.; Zanonato, P.; Rao, L.

    2007-01-10

    In acidic aqueous solutions, gluconate protonation is coupled with lactonization of gluconic acid. With the decrease of pC{sub H}, two lactones ({delta}/{gamma}) are sequentially formed. The {delta}-lactone forms more readily than the {gamma}-lactone. In 0.1 M gluconate solutions, if pC{sub H} is above 2.5, only the {delta}-lactone is generated. When pC{sub H} is decreased below 2.0, the formation of the {gamma}-lactone is observable although the {delta}-lactone predominates. At I = 0.1 M NaClO{sub 4} and room temperature, the deprotonation constant of the carboxylic group, using the NMR technique, was determined to be log K{sub a} = 3.30 {+-} 0.02; the {delta}-lactonization constant, by the batch potentiometric titrations, was obtained to be log K{sub L} = - (0.54 {+-} 0.04). Using ESI-MS, the rate constants of the {delta}-lactonization and the hydrolysis at pC{sub H} {approx} 5.0 were estimated to be k{sub 1} = 3.2 x 10{sup -5} s{sup -1} and k{sup -1} = 1.1 x 10{sup -4} s{sup -1}, respectively.

  9. Complete Thermodynamic Characterization of the Multiple Protonation Equilibria of the Aminoglycoside Antibiotic Paromomycin: A Calorimetric and Natural Abundance 15N NMR Study

    PubMed Central

    Barbieri, Christopher M.; Pilch, Daniel S.

    2006-01-01

    The binding of aminoglycoside antibiotics to a broad range of macromolecular targets is coupled to protonation of one or more of the amino groups that typify this class of drugs. Determining how and to what extent this linkage influences the energetics of the aminoglycoside-macromolecule binding reaction requires a detailed understanding of the thermodynamics associated with the protonation equilibria of the aminoglycoside amino groups. In recognition of this need, a calorimetric- and NMR-based approach for obtaining the requisite thermodynamic information is presented using paromomycin as the model aminoglycoside. Temperature- and pH-dependent 15N NMR studies provide pKa values for the five paromomycin amino groups, as well as the temperature dependence of these pKa values. These studies also indicate that the observed pKa values associated with the free base form of paromomycin are lower in magnitude than the corresponding values associated with the sulfate salt form of the drug. This difference in pKa is due to drug interactions with the sulfate counterions at the high drug concentrations (≥812 mM) used in the 15N NMR studies. Isothermal titration calorimetry studies conducted at drug concentrations ≤45 μM reveal that the extent of paromomycin protonation linked to the binding of the drug to its pharmacologically relevant target, the 16 S rRNA A-site, is consistent with the pKa values of the free base and not the sulfate salt form of the drug. Temperature- and pH-dependent isothermal titration calorimetry studies yield exothermic enthalpy changes (ΔH) for protonation of the five paromomycin amino groups, as well as positive heat capacity changes (ΔCp) for three of the five amino groups. Regarded as a whole, the results presented here represent an important first step toward establishing a thermodynamic database that can be used to predict how aminoglycoside-macromolecule binding energetics will be influenced by conditions such as temperature, pH, and

  10. NMR and DFT study on media effects on proton transfer in hydrogen bonding: concept of molecular probe with an application to ionic and super-polar liquids.

    PubMed

    Balevicius, Vytautas; Gdaniec, Zofia; Aidas, Kestutis

    2009-10-14

    Media effects of ionic and super-polar liquids on the state of H-bonding were studied by NMR and DFT methods. The proton sharing (positioning) in the H-bond was monitored following the chemical shifts of picolinic acid N-oxide (PANO) used as the molecular probe. The relationships between PANO 1H and 13C chemical shifts and proton position in the O-H...O bridge were calibrated using traditional organic solvents and other H-bond complexes of pyridine N-oxide with acids to increase the H-bond strength. A reliable parameter for H-bond monitoring was proposed. The state of the H-bond in ionic liquid media is largely governed by the dielectric properties of the bulk media. A drastic fall-out of PANO/[BuMePyr][TfO] from the general dielectric scheme built using solvents with increasing dielectric constant (from chloroform to water and culminating with formamide) was observed. On a molecular level this effect indicates that the ionic liquid [BuMePyr][TfO] can act on H-bonded systems as a stimulant of proton transfer. In 'super-polar' media (formamide) the intramolecular H-bond system converts into an intermolecular one forming a neutral H-bond complex of PANO with the formamide molecule.

  11. Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)(-) bonded system.

    PubMed

    Pylaeva, Svetlana; Allolio, Christoph; Koeppe, Benjamin; Denisov, Gleb S; Limbach, Hans-Heinrich; Sebastiani, Daniel; Tolstoy, Peter M

    2015-02-14

    We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature (1)H and (13)C NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH···(-)OAc and PhO(-)···HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free" carbonyl group of the acid plays the major role in the OHO bond geometry and causes proton "jumps", i.e. interconversion of PhOH···(-)OAc and PhO(-)···HOAc tautomers. Weak H-bonds between CH(CD) groups of the solvent and the oxygen atom of carbonyl stabilize the PhOH···(-)OAc type of structures. Breaking of CH···O bonds shifts the equilibrium towards PhO(-)···HOAc form.

  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. Joint neutron crystallographic and NMR solution studies of Tyr residue ionization and hydrogen bonding: Implications for enzyme-mediated proton transfer

    SciTech Connect

    Michalczyk, Ryszard; Unkefer, Clifford J.; Bacik, John -Paul; Schrader, Tobias E.; Ostermann, Andreas; Kovalevsky, Andrey Y.; McKenna, Robert; Fisher, Suzanne Zoe

    2015-05-05

    Human carbonic anhydrase II (HCA II) uses a Zn-bound OH-/H2O mechanism to catalyze the reversible hydration of CO2. This catalysis also involves a separate proton transfer step, mediated by an ordered solvent network coordinated by hydrophilic residues. One of these residues, Tyr7, was previously shown to be deprotonated in the neutron crystal structure at pH 10. This observation indicated that Tyr7 has a perturbed pKa compared with free tyrosine. To further probe the pKa) of this residue, NMR spectroscopic measurements of [13C] Tyr-labeled holo HCA II (with active-site Zn present) were preformed to titrate all Tyr residues between pH 5.4-11.0. In addition, neutron studies of apo HCA II (with Zn removed from the active site) at pH 7.5 and holo HCA II at pH 6 were conducted. This detailed interrogation of tyrosines in HCA II by NMR and neutron crystallography revealed a significantly lowered pKa of Tyr7 and how pH and Tyr proximity to Zn affect hydrogen-bonding interactions.

  14. Joint neutron crystallographic and NMR solution studies of Tyr residue ionization and hydrogen bonding: Implications for enzyme-mediated proton transfer

    DOE PAGES

    Michalczyk, Ryszard; Unkefer, Clifford J.; Bacik, John -Paul; ...

    2015-05-05

    Human carbonic anhydrase II (HCA II) uses a Zn-bound OH-/H2O mechanism to catalyze the reversible hydration of CO2. This catalysis also involves a separate proton transfer step, mediated by an ordered solvent network coordinated by hydrophilic residues. One of these residues, Tyr7, was previously shown to be deprotonated in the neutron crystal structure at pH 10. This observation indicated that Tyr7 has a perturbed pKa compared with free tyrosine. To further probe the pKa) of this residue, NMR spectroscopic measurements of [13C] Tyr-labeled holo HCA II (with active-site Zn present) were preformed to titrate all Tyr residues between pH 5.4-11.0.more » In addition, neutron studies of apo HCA II (with Zn removed from the active site) at pH 7.5 and holo HCA II at pH 6 were conducted. This detailed interrogation of tyrosines in HCA II by NMR and neutron crystallography revealed a significantly lowered pKa of Tyr7 and how pH and Tyr proximity to Zn affect hydrogen-bonding interactions.« less

  15. Joint neutron crystallographic and NMR solution studies of Tyr residue ionization and hydrogen bonding: Implications for enzyme-mediated proton transfer

    PubMed Central

    Michalczyk, Ryszard; Unkefer, Clifford J.; Bacik, John-Paul; Schrader, Tobias E.; Ostermann, Andreas; Kovalevsky, Andrey Y.; McKenna, Robert; Fisher, Suzanne Zoë

    2015-01-01

    Human carbonic anhydrase II (HCA II) uses a Zn-bound OH−/H2O mechanism to catalyze the reversible hydration of CO2. This catalysis also involves a separate proton transfer step, mediated by an ordered solvent network coordinated by hydrophilic residues. One of these residues, Tyr7, was previously shown to be deprotonated in the neutron crystal structure at pH 10. This observation indicated that Tyr7 has a perturbed pKa compared with free tyrosine. To further probe the pKa of this residue, NMR spectroscopic measurements of [13C]Tyr-labeled holo HCA II (with active-site Zn present) were preformed to titrate all Tyr residues between pH 5.4–11.0. In addition, neutron studies of apo HCA II (with Zn removed from the active site) at pH 7.5 and holo HCA II at pH 6 were conducted. This detailed interrogation of tyrosines in HCA II by NMR and neutron crystallography revealed a significantly lowered pKa of Tyr7 and how pH and Tyr proximity to Zn affect hydrogen-bonding interactions. PMID:25902526

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

    NASA Astrophysics Data System (ADS)

    Mori, Yukie; Masuda, Yuichi

    2015-09-01

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

  17. A proton NMR study of the effect of a new intravasal injectable male contraceptive RISUG on seminal plasma metabolites.

    PubMed

    Sharma, U; Chaudhury, K; Jagannathan, N R; Guha, S K

    2001-09-01

    Nuclear magnetic resonance (NMR) spectroscopy was used to quantify citrate, glucose, lactate, glycerophosphorylcholine and choline in seminal plasma from subjects injected with a new male contraceptive RISUG, a copolymer of styrene maleic anhydride dissolved in dimethyl sulphoxide, and in seminal plasma from normal ejaculates. No significant difference in the concentration of citrate was observed between the groups, indicating that the prostate is not affected by the contraceptive. The concentrations of glucose, lactate, glycerophosphorylcholine and choline were significantly lower (P < 0.01) in subjects injected with RISUG compared with controls. In addition, metabolite ratios such as choline:citrate, citrate:lactate, choline:lactate and glycerophosphorylcholine:choline were calculated. Citrate:lactate and glycerophosphorylcholine:choline ratios were significantly lower in RISUG-injected subjects than in controls (P < 0.01), thereby indicating the occurrence of partial obstructive azoospermia. The most important finding of the present study was that the intervention of RISUG in the vas deferens even for a period as long as 8 years is absolutely safe and does not lead to prostatic diseases.

  18. NMR spectroscopy of hydroxyl protons in aqueous solutions of peptides and proteins.

    PubMed

    Liepinsh, E; Otting, G; Wüthrich, K

    1992-09-01

    Hydroxyl groups of serine and threonine, and to some extent also tyrosine are usually located on or near the surface of proteins. NMR observations of the hydroxyl protons is therefore of interest to support investigations of the protein surface in solution, and knowledge of the hydroxyl NMR lines is indispensable as a reference for studies of protein hydration in solution. In this paper, solvent suppression schemes recently developed for observation of hydration water resonances were used to observe hydroxyl protons of serine, threonine and tyrosine in aqueous solutions of small model peptides and the protein basic pancreatic trypsin inhibitor (BPTI). The chemical shifts of the hydroxyl protons of serine and threonine were found to be between 5.4 and 6.2 ppm, with random-coil shifts at 4 degrees C of 5.92 ppm and 5.88 ppm, respectively, and those of tyrosine between 9.6 and 10.1 ppm, with a random-coil shift of 9.78 ppm. Since these spectral regions are virtually free of other polypeptide 1H NMR signals, cross peaks with the hydroxyl protons are usually well separated even in homonuclear two-dimensional 1H NMR spectra. To illustrate the practical use of hydroxyl proton NMR in polypeptides, the conformations of the side-chain hydroxyl groups in BPTI were characterized by measurements of nuclear Overhauser effects and scalar coupling constants involving the hydroxyl protons. In addition, hydroxyl proton exchange rates were measured as a function of pH, where simple first-order rate processes were observed for both acid- and base-catalysed exchange of all but one of the hydroxyl-bearing residues in BPTI. For the conformations of the individual Ser, Thr and Tyr side chains characterized in the solution structure with the use of hydroxyl proton NMR, both exact coincidence and significant differences relative to the corresponding BPTI crystal structure data were observed.

  19. Effect of a new injectable male contraceptive on the seminal plasma amino acids studied by proton NMR spectroscopy.

    PubMed

    Chaudhury, Koel; Sharma, Uma; Jagannathan, N R; Guha, Sujoy K

    2002-09-01

    Effect of RISUG, a newly developed male contraceptive, on various amino acids of seminal plasma ejaculates was studied by proton magnetic resonance spectroscopy at 400 MHz. Levels of amino acids were compared with the seminal plasma of obstructive azoospermia and controls. Glutamic acid, glutamine, and arginine were found to be high in concentration in human seminal plasma. The concentration of aromatic amino acids such as tyrosine, histidine, and phenylalanine in RISUG-injected subjects showed no significant difference compared to controls (p > 0.1); however, there was a statistically significant decrease in the concentration of these amino acids in obstructive azoospermia. The concentration of some prominent amino acids that showed overlapping resonances, such as isoleucine+leucine+valine (p < 0.01), alanine+isoleucine+lysine (p < 0.01), arginine+lysine+leucine (p < 0.01), and glutamic acid+glutamine (p < 0.01), showed a statistically significant decrease in RISUG-injected subjects compared to controls. Overlap of these amino acid resonances were noticed even at 600 MHz. In general, the total amino acids concentration in RISUG-injected subjects was found to be higher than in azoospermic subjects, confirming the occurrence of 'partial' obstructive azoospermia in subjects injected with this contraceptive.

  20. Mixed micelles of polyethylene glycol (23) lauryl ether with ionic surfactants studied by proton 1D and 2D NMR.

    PubMed

    Gao, Hong-Chang; Zhao, Sui; Mao, Shi-Zhen; Yuan, Han-Zhen; Yu, Jia-Yong; Shen, Lian-Fang; Du, You-Ru

    2002-05-01

    (1)H NMR chemical shift, spin-lattice relaxation time, spin-spin relaxation time, self-diffusion coefficient, and two-dimensional nuclear Overhauser enhancement (2D NOESY) measurements have been used to study the nonionic-ionic surfactant mixed micelles. Cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) were used as the ionic surfactants and polyethylene glycol (23) lauryl ether (Brij-35) as the nonionic surfactant. The two systems are both with varying molar ratios of CTAB/Brij-35 (C/B) and SDS/Brij-35 (S/B) ranging from 0.5 to 2, respectively, at a constant concentration of 6 mM for Brij-35 in aqueous solutions. Results give information about the relative arrangement of the surfactant molecules in the mixed micelles. In the former system, the trimethyl groups attached to the polar heads of the CTAB molecules are located between the first oxy-ethylene groups next to the hydrophobic chains of Brij-35 molecules. These oxy-ethylene groups gradually move outward from the hydrophobic core of the mixed micelle with an increase in C/B in the mixed solution. In contrast to the case of the CTAB/Triton X-100 system, the long flexible hydrophilic poly oxy-ethylene chains, which are in the exterior part of the mixed micelles, remain coiled, but looser, surrounding the hydrophobic core. There is almost no variation in conformation of the hydrophilic chains of Brij-35 molecules in the mixed micelles of the SDS/Brij-35 system as the S/B increases. The hydrophobic chains of both CTAB and SDS are co-aggregated with Brij-35, respectively, in their mixed micellar cores.

  1. Mechanism of binding of the radiosensitizers metronidazole and misonidazole (RO-07-0582) to bovine and human serum albumin: a proton NMR study

    SciTech Connect

    Sulkowska, A.; Lubas, B.; Wilczok, T.

    1981-01-01

    High-resolution proton NMR spectra of the radiosensitizer metronidazole and its derivative misonidazole (RO-07-0582) were measured in D/sub 2/O at resonance frequency 60 MHz and interpreted in the aliphatic and aromatic regions. The linewidths of the NMR peaks attributed to individual fragments of nitroimidazole molecules were then analyzed in the presence of bovine and human serum albumin. With increasing concentration of serum albumin, a selectively larger broadening of the lines attributable to the protons of the aliphatic moieties than of those of the imidazole rings was observed for both compounds. This broadening for misonidazole strongly depends on the ionic strength of the solution. The results indicate a specific immobilization of the molecules of both radiosensitizers during their interaction with serum albumin and the involvement of the aliphatic chains of misonidazole and metronidazole as the primary binding sites.

  2. 1H-19F spin-lattice relaxation spectroscopy: proton tunnelling in the hydrogen bond studied by field-cycling NMR.

    PubMed

    Noble, D L; Aibout, A; Horsewill, A J

    2009-12-01

    Proton tunnelling in the hydrogen bonds of two fluorine substituted benzoic acid dimers has been investigated using field-cycling NMR relaxometry. The close proximity of the (19)F nuclei to the hydrogen bond protons introduces heteronuclear (19)F-(1)H dipolar interactions into the spin-lattice relaxation processes. This renders the (1)H magnetisation-recovery biexponential and introduces multiple spectral density components into the relaxation matrix characterised by frequencies that are sums and differences of the (19)F and (1)H Larmor frequencies. Using field-cycling NMR pulse sequences that measure the spin-lattice relaxation and cross-relaxation rates we demonstrate how some of these multiple spectral density components can be separately resolved. This leads to an accurate determination of the correlation times that characterise the proton tunnelling motion. A broad spectrum of relaxation behaviour is illustrated and explored in the chosen samples and the investigation is used to explore the theory and practise of field-cycling NMR relaxometry in cases where heteronuclear interactions are significant.

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

    SciTech Connect

    Zilm, K.W.

    1989-01-01

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

  4. Kinetic isotope effects and tunneling in cyclic double and triple proton transfer between acetic acid and methanol in tetrahydrofuran studied by dynamic /sup 1/H and /sup 2/H NMR spectroscopy

    SciTech Connect

    Gerritzen, D.; Limbach, H.H.

    1984-02-22

    Previous studies of proton exchange and hydrogen bonding between acetic acid (A) and methanol (B) in tetrahydrofuran-d/sub 8/ have been extended to the study of the primary kinetic H/D isotope effects of the exchange. For this purpose a new combination of dynamic /sup 1/H and /sup 2/H NMR spectroscopy has been used to perform an ''NMR proton inventory''. The following rate law was obtained at deuterium fractions D=0 and D=1 of the exchangeable protonic sites: NU=k/sup LL/ C/sub A/C/sub B/+k/sub LLL/C/sub A//sup 2/C/sub B/ (L=H,D). This was attributed to a superposition of cyclic double and triple proton exchange involving one and two molecules of acetic acid and one molecule of methanol. Additional experiments were carried out at intermediate deuterium fractions. Thus, the kinetic HH/HD/DD and HHH/HHD/DDD isotope effects of the exchange as a function of the temperature was measured successfully. This has been achieved for the first time for well-defined intermolecular multiple-proton-transfer reactions. The possibility of determining the number of protons transferred in a chemical reaction by performing an NMR proton inventory is discussed. The rule of the geometric mean (RGM) is fulfilled for the kinetic isotope effects of the LLL process, which are almost independent of temperature within the margin of error. By contrast, the RGM is not fullfilled for the LL process, and the kinetic isotope effects depend strongly on the temperature. The energies of activation and frequency factors fit Bell's criteria of tunneling. The kinetic results are in good agreement with predictions of transition-state theory but can be explained by an intermolecular tunneling model. The results are proof that acetic acid and methanol form cyclic hydrogen-bonded 1:1 and 2:1 complexes which have very low concentration in tetrahydrofuran.

  5. NMR studies of the stability, protonation States, and tautomerism of (13)C- AND (15)N-labeled aldimines of the coenzyme pyridoxal 5'-phosphate in water.

    PubMed

    Chan-Huot, Monique; Sharif, Shasad; Tolstoy, Peter M; Toney, Michael D; Limbach, Hans-Heinrich

    2010-12-28

    We have measured the pH-dependent (1)H, (13)C, and (15)N NMR spectra of pyridoxal 5'-phosphate ((13)C(2)-PLP) mixed with equal amounts of either doubly (15)N-labeled diaminopropane, (15)N(α)-labeled l-lysine, or (15)N(ε)-labeled l-lysine as model systems for various intermediates of the transimination reaction in PLP-dependent enzymes. At low pH, only the hydrate and aldehyde forms of PLP and the free protonated diamines are present. Above pH 4, the formation of single- and double-headed aldimines (Schiff bases) with the added diamines is observed, and their (13)C and (15)N NMR parameters have been characterized. For 1:1 mixtures the single-headed aldimines dominate. In a similar way, the NMR parameters of the geminal diamine formed with diaminopropane at high pH are measured. However, no geminal diamine is formed with l-lysine. In contrast to the aldimine formed with the ε-amino group of lysine, the aldimine formed with the α-amino group is unstable at moderately high pH but dominates slightly below pH 10. By analyzing the NMR data, both the mole fractions of the different PLP species and up to 6 different protonation states including their pK(a) values were obtained. Furthermore, the data show that all Schiff bases are subject to a proton tautomerism along the intramolecular OHN hydrogen bond, where the zwitterionic form is favored before deprotonation occurs at high pH. This observation, as well as the observation that around pH 7 the different PLP species are present in comparable amounts, sheds new light on the mechanism of the transimination reaction.

  6. Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions

    PubMed Central

    Wang, Xue Lu; Liu, Wenqing; Yu, Yan-Yan; Song, Yanhong; Fang, Wen Qi; Wei, Daxiu; Gong, Xue-Qing; Yao, Ye-Feng; Yang, Hua Gui

    2016-01-01

    Proton transfer (PT) processes in solid–liquid phases play central roles throughout chemistry, biology and materials science. Identification of PT routes deep into the realistic catalytic process is experimentally challenging, thus leaving a gap in our understanding. Here we demonstrate an approach using operando nuclear magnetic resonance (NMR) spectroscopy that allows to quantitatively describe the complex species dynamics of generated H2/HD gases and liquid intermediates in pmol resolution during photocatalytic hydrogen evolution reaction (HER). In this system, the effective protons for HER are mainly from H2O, and CH3OH evidently serves as an outstanding sacrificial agent reacting with holes, further supported by our density functional theory calculations. This results rule out controversy about the complicated proton sources for HER. The operando NMR method provides a direct molecular-level insight with the methodology offering exciting possibilities for the quantitative studies of mechanisms of proton-involved catalytic reactions in solid–liquid phases. PMID:27311326

  7. Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions.

    PubMed

    Wang, Xue Lu; Liu, Wenqing; Yu, Yan-Yan; Song, Yanhong; Fang, Wen Qi; Wei, Daxiu; Gong, Xue-Qing; Yao, Ye-Feng; Yang, Hua Gui

    2016-06-17

    Proton transfer (PT) processes in solid-liquid phases play central roles throughout chemistry, biology and materials science. Identification of PT routes deep into the realistic catalytic process is experimentally challenging, thus leaving a gap in our understanding. Here we demonstrate an approach using operando nuclear magnetic resonance (NMR) spectroscopy that allows to quantitatively describe the complex species dynamics of generated H2/HD gases and liquid intermediates in pmol resolution during photocatalytic hydrogen evolution reaction (HER). In this system, the effective protons for HER are mainly from H2O, and CH3OH evidently serves as an outstanding sacrificial agent reacting with holes, further supported by our density functional theory calculations. This results rule out controversy about the complicated proton sources for HER. The operando NMR method provides a direct molecular-level insight with the methodology offering exciting possibilities for the quantitative studies of mechanisms of proton-involved catalytic reactions in solid-liquid phases.

  8. 14N NQR and proton NMR study of ferroelectric phase transition and proton exchange in organic ferroelectric (H2-TPPZ)(Hca)2.

    PubMed

    Seliger, Janez; Zagar, Veselko; Asaji, Tetsuo; Hasegawa, Yumi

    2010-04-07

    The complete (14)N nuclear quadrupole resonance spectrum has been measured in ferroelectric (H(2)-TPPZ)(Hca)(2) using nuclear quadrupole double resonance. The quadrupole coupling tensors are assigned to various nitrogen positions in the crystal structure. Two types of asymmetric N-H(+)...N hydrogen bonds are observed in the ferroelectric phase. A slow dynamics influencing the (14)N NQR spectrum and relaxation has been observed in the paraelectric phase. The analysis of the (14)N NQR spectra in the paraelectric phase shows that above T(c) each hydrogen bond exchanges between the two types observed in the ferroelectric phase. The change of the type of hydrogen bond is associated with the transfer of protons within the bond.

  9. NMR analysis, protonation equilibria and decomposition kinetics of tolperisone.

    PubMed

    Orgován, Gábor; Tihanyi, Károly; Noszál, Béla

    2009-12-05

    The rate constants of spontaneous and hydroxide-catalyzed decomposition and the tautomer-specific protonation constants of tolperisone, a classical muscle relaxant were determined. A solution NMR method without any separation techniques was elaborated to quantitate the progress of decomposition. All the rate and equilibrium constants were determined at four different temperatures and the activation parameters were calculated. The molecular mechanism of decomposition is proposed.

  10. Positional Enrichment by Proton Analysis (PEPA): A One-Dimensional (1) H-NMR Approach for (13) C Stable Isotope Tracer Studies in Metabolomics.

    PubMed

    Vinaixa, Maria; Rodríguez, Miguel A; Aivio, Suvi; Capellades, Jordi; Gómez, Josep; Canyellas, Nicolau; Stracker, Travis H; Yanes, Oscar

    2017-03-20

    A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of (13) C-satellite peaks using 1D-(1) H-NMR spectra. In comparison with (13) C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of (13) C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of (1) H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts.

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

    SciTech Connect

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

    1987-09-30

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

  12. Site selectivity in the protonation of a phosphinito bridged Pt(I)-Pt(I) complex: a combined NMR and density-functional theory mechanistic study.

    PubMed

    Latronico, Mario; Polini, Flavia; Gallo, Vito; Mastrorilli, Piero; Calmuschi-Cula, Beatrice; Englert, Ulli; Re, Nazzareno; Repo, Timo; Räisänen, Minna

    2008-11-03

    The protonation of the dinuclear phosphinito bridged complex [(PHCy2)Pt(mu-PCy2){kappa(2)P,O-mu-P(O)Cy2}Pt(PHCy2)] (Pt-Pt) (1) by Brønsted acids affords hydrido bridged Pt-Pt species the structure of which depends on the nature and on the amount of the acid used. The addition of 1 equiv of HX (X = Cl, Br, I) gives products of formal protonation of the Pt-Pt bond of formula syn-[(PHCy2)(X)Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappaP-P(O)Cy2}] (Pt-Pt) (5, X = Cl; 6, X = Br; 8, X = I), containing a Pt-X bond and a dangling kappa P-P(O)Cy2 ligand. Uptake of a second equivalent of HX results in the protonation of the P(O)Cy2 ligand with formation of the complexes [(PHCy2)(X)Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappaP-P(OH)Cy2}]X (Pt-Pt) (3, X = Cl; 4, X = Br; 9, X = I). Each step of protonation is reversible, thus reactions of 3, 4, with NaOH give, first, the corresponding neutral complexes 5, 6, and then the parent compound 1. While the complexes 3 and 4 are indefinitely stable, the iodine analogue 9 transforms into anti-[(PHCy2)(I)Pt(mu-PCy2)(mu-H)Pt(PHCy2)(I)] (Pt-Pt) (7) deriving from substitution of an iodo group for the P(OH)Cy2 ligand. Complexes 3 and 4 are isomorphous crystallizing in the triclinic space group P1 and show an intramolecular hydrogen bond and an interaction between the halide counteranion and the POH hydrogen. The occurrence of such an interaction also in solution was ascertained for 3 by (35)Cl NMR. Multinuclear NMR spectroscopy (including (31)P-(1)H HOESY) and density-functional theory calculations indicate that the mechanism of the reaction starts with a prior protonation of the oxygen with formation of an intermediate (12) endowed with a six membered Pt(1)-X...H-O-P-Pt(2) ring that evolves into thermodynamically stable products featuring the hydride ligand bridging the Pt atoms. Energy profiles calculated for the various steps of the reaction between 1 and HCl showed very low barriers for the proton transfer and the subsequent rearrangement to 12, while a barrier

  13. Positional Enrichment by Proton Analysis (PEPA): A One‐Dimensional 1H‐NMR Approach for 13C Stable Isotope Tracer Studies in Metabolomics

    PubMed Central

    Rodríguez, Miguel A.; Aivio, Suvi; Capellades, Jordi; Gómez, Josep; Canyellas, Nicolau; Stracker, Travis H.

    2017-01-01

    Abstract A novel metabolomics approach for NMR‐based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of 13C‐satellite peaks using 1D‐1H‐NMR spectra. In comparison with 13C‐NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of 13C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high‐throughput of 1H‐NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D‐NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts. PMID:28220994

  14. Binding of oxytocin and 8-arginine-vasopressin to neurophysin studied by /sup 15/N NMR using magnetization transfer and indirect detection via protons

    SciTech Connect

    Live, D.H.; Cowburn, D.

    1987-10-06

    NMR was used to monitor the binding to neurophysin of oxytocin and 8-arginine-vasopressin, /sup 15/N labeling being used to identify specific backbone /sup 15/N and /sup 1/H signals. The most significant effects of binding were large downfield shifts in the amino nitrogen resonance of Phe-3 of vasopressin and in its associated proton, providing evidence that the peptide bond between residues 2 and 3 of the hormones is hydrogen-bonded to the protein within hormone-neurophysin complexes. Suggestive evidence for hydrogen bonding of the amino nitrogen of Tyr-2 was also obtained in the form of decreased proton exchange rates on binding; however, the chemical shift changes of this nitrogen and its associated proton indicated that such hydrogen bonding, if present, is probably weak. Shifts in the amino nitrogen of Asn-5 and in the -NH protons of both Asn-5 and Cys-6 demonstrated that these residues are significantly perturbed by binding, suggesting conformational changes of the ring on binding and/or the presence of binding sites on the hormone outside the 1-3 region. No support was obtained for the thesis that there is a significant second binding site for vasopressin on each neutrophysin chain. The behavior of both oxytocin and vasopressin on binding was consistent with formation of 1:1 complexes in slow exchange with the free state under most pH conditions. At low pH there was evidence of an increased exchange rate. Additionally, broadening of /sup 15/N resonances in the bound state at low pH occurred without a corresponding change in the resonances of equilibrating free hormone. The results suggest significant conformational alteration in neurophysin-hormone complexes at low pH possibly associated with protonation of the carboxyl group of the hormone-protein salt bridge.

  15. 224} studied by NMR

    SciTech Connect

    Furukawa, Y; Fang, X; Kögerler, P

    2014-05-14

    7Li nuclear magnetic resonance (NMR) studies have been performed to investigate magnetic properties and spin dynamics of Mn3+ (S = 2) spins in the giant polyoxometalate molecule {Mn40W224}. The 7Li-NMR line width is proportional to the external magnetic field H as expected in a paramagnetic state above 3 K. Below this temperature the line width shows a sudden increase and is almost independent of H, which indicates freezing of the local Mn3+ spins. The temperature dependence of T1 for both 1H and 7Li reveals slow spin dynamics at low temperatures, consistent with spin freezing. The slow spin dynamics is also evidenced by the observation of a peak of 1/T2 around 3 K, where the fluctuation frequency of spins is of the order of ~200 kHz. An explicit form of the temperature dependence of the fluctuation frequency of Mn3+ spins is derived from the nuclear relaxation data.

  16. Binding of oxytocin and 8-arginine-vasopressin to neurophysin studied by 15N NMR using magnetization transfer and indirect detection via protons.

    PubMed

    Live, D H; Cowburn, D; Breslow, E

    1987-10-06

    NMR was used to monitor the binding to neurophysin of oxytocin and 8-arginine-vasopressin, 15N labeling being used to identify specific backbone 15N and 1H signals. The most significant effects of binding were large downfield shifts in the amino nitrogen resonance of Phe-3 of vasopressin and in its associated proton, providing evidence that the peptide bond between residues 2 and 3 of the hormones is hydrogen-bonded to the protein within hormone-neurophysin complexes. Suggestive evidence of hydrogen bonding of the amino nitrogen of Tyr-2 was also obtained in the form of decreased proton exchange rates on binding; however, the chemical shift changes of this nitrogen and its associated proton indicated that such hydrogen bonding, if present, is probably weak. Shifts in the amino nitrogen of Asn-5 and in the -NH protons of both Asn-5 and Cys-6 demonstrated that these residues are significantly perturbed by binding, suggesting conformational changes of the ring on binding and/or the presence of binding sites on the hormone outside the 1-3 region. No support was obtained for the thesis that there is a significant second binding site for vasopressin on each neurophysin chain. The behavior of both oxytocin and vasopressin on binding was consistent with formation of 1:1 complexes in slow exchange with the free state under most pH conditions. At low pH there was evidence of an increased exchange rate. Additionally, broadening of 15N resonances in the bound state at low pH occurred without a corresponding change in the resonances of equilibrating free hormone.(ABSTRACT TRUNCATED AT 250 WORDS)

  17. Development and application of proton NMR methodology to lipoprotein analysis

    NASA Astrophysics Data System (ADS)

    Korhonen, Ari Juhani

    1998-11-01

    The present thesis describes the development of 1H NMR spectroscopy and its applications to lipoprotein analysis in vitro, utilizing biochemical prior knowledge and advanced lineshape fitting analysis in the frequency domain. A method for absolute quantification of lipoprotein lipids and proteins directly from the terminal methyl-CH3 resonance region of 1H NMR spectra of human blood plasma is described. Then the use of NMR methodology in time course studies of the oxidation process of LDL particles is presented. The function of the cholesteryl ester transfer protein (CETP) in lipoprotein mixtures was also assessed by 1H NMR, which allows for dynamic follow-up of the lipid transfer reactions between VLDL, LDL, and HDL particles. The results corroborated the suggestion that neutral lipid mass transfer among lipoproteins is not an equimolar heteroexchange. A novel method for studying lipoprotein particle fusion is also demonstrated. It is shown that the progression of proteolytically (α- chymotrypsin) induced fusion of LDL particles can be followed by 1H NMR spectroscopy and, moreover, that fusion can be distinguished from aggregation. In addition, NMR methodology was used to study the changes in HDL3 particles induced by phospholipid transfer protein (PLTP) in HDL3 + PLTP mixtures. The 1H NMR study revealed a gradual production of enlarged HDL particles, which demonstrated that PLTP-mediated remodeling of HDL involves fusion of the HDL particles. These applications demonstrated that the 1H NMR approach offers several advantages both in quantification and in time course studies of lipoprotein-lipoprotein interactions and of enzyme/lipid transfer protein function.

  18. 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.

  19. 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.

  20. Structure of fully protonated proteins by proton-detected magic-angle spinning NMR.

    PubMed

    Andreas, Loren B; Jaudzems, Kristaps; Stanek, Jan; Lalli, Daniela; Bertarello, Andrea; Le Marchand, Tanguy; Cala-De Paepe, Diane; Kotelovica, Svetlana; Akopjana, Inara; Knott, Benno; Wegner, Sebastian; Engelke, Frank; Lesage, Anne; Emsley, Lyndon; Tars, Kaspars; Herrmann, Torsten; Pintacuda, Guido

    2016-08-16

    Protein structure determination by proton-detected magic-angle spinning (MAS) NMR has focused on highly deuterated samples, in which only a small number of protons are introduced and observation of signals from side chains is extremely limited. Here, we show in two fully protonated proteins that, at 100-kHz MAS and above, spectral resolution is high enough to detect resolved correlations from amide and side-chain protons of all residue types, and to reliably measure a dense network of (1)H-(1)H proximities that define a protein structure. The high data quality allowed the correct identification of internuclear distance restraints encoded in 3D spectra with automated data analysis, resulting in accurate, unbiased, and fast structure determination. Additionally, we find that narrower proton resonance lines, longer coherence lifetimes, and improved magnetization transfer offset the reduced sample size at 100-kHz spinning and above. Less than 2 weeks of experiment time and a single 0.5-mg sample was sufficient for the acquisition of all data necessary for backbone and side-chain resonance assignment and unsupervised structure determination. We expect the technique to pave the way for atomic-resolution structure analysis applicable to a wide range of proteins.

  1. Structure of fully protonated proteins by proton-detected magic-angle spinning NMR

    PubMed Central

    Jaudzems, Kristaps; Stanek, Jan; Lalli, Daniela; Bertarello, Andrea; Le Marchand, Tanguy; Cala-De Paepe, Diane; Kotelovica, Svetlana; Akopjana, Inara; Knott, Benno; Wegner, Sebastian; Engelke, Frank; Lesage, Anne; Emsley, Lyndon; Tars, Kaspars; Herrmann, Torsten; Pintacuda, Guido

    2016-01-01

    Protein structure determination by proton-detected magic-angle spinning (MAS) NMR has focused on highly deuterated samples, in which only a small number of protons are introduced and observation of signals from side chains is extremely limited. Here, we show in two fully protonated proteins that, at 100-kHz MAS and above, spectral resolution is high enough to detect resolved correlations from amide and side-chain protons of all residue types, and to reliably measure a dense network of 1H-1H proximities that define a protein structure. The high data quality allowed the correct identification of internuclear distance restraints encoded in 3D spectra with automated data analysis, resulting in accurate, unbiased, and fast structure determination. Additionally, we find that narrower proton resonance lines, longer coherence lifetimes, and improved magnetization transfer offset the reduced sample size at 100-kHz spinning and above. Less than 2 weeks of experiment time and a single 0.5-mg sample was sufficient for the acquisition of all data necessary for backbone and side-chain resonance assignment and unsupervised structure determination. We expect the technique to pave the way for atomic-resolution structure analysis applicable to a wide range of proteins. PMID:27489348

  2. Non-destructive ripeness sensing by using proton NMR (Nuclear Magnetic Resonance)

    SciTech Connect

    Cho, Seong In; Krutz, G.W.; Stroshine, R.L. . Dept. of Agricultural Engineering); Bellon, V. , 34 - Montpellier )

    1990-01-01

    More than 80 kinds of fruits and vegetables are available in the United States. But only about 6 of them have their quality standards (Dull, 1986). In the 1990 Fresh Trends survey (Zind, 1990), consumers were asked to rate 16 characteristics important to their decision to purchase fresh produce. The four top ranking factors were ripeness/freshness, taste/flavor, appearance/condition and nutritional value. Of these surveyed, 96% rated ripeness/freshness as extremely important or very important. Therefore, the development of reliable grading or sorting techniques for fresh commodities is essential. Determination of fruit quality often involves cutting and tasting. Non-destructive quality control in fruit and vegetables is a goal of growers and distributors, as well as the food processing industry. Many nondestructive techniques have been evaluated including soft x-ray, optical transmission, near infrared radiation, and machine vision. However, there are few reports of successful non-destructive measurement of sugar content directly in fruit. Higher quality fruit could be harvested and available to consumers if a nondestructive sensor that detects ripeness level directly by measuring sugar content were available. Using proton Nuclear Magnetic Resonance (NMR) principle is the possibility. A nondestructive ripeness (or sweetness) sensor for fruit quality control can be developed with the proton NMR principle (Cho, 1989). Several feasibility studies were necessary for the ripeness sensor development. Main objectives in this paper was to investigate the feasibilities (1) to detect ripeness (or sweetness level) of raw fruit tissue with an high resolution proton NMR spectroscopy (200 MHz) and (2) to measure sugar content of intact fruit with a low resolution proton NMR spectroscopy (10 MHz). 7 refs., 4 figs.

  3. Non-destructive Ripeness Sensing by Using Proton NMR [Nuclear Magnetic Resonance

    DOE R&D Accomplishments Database

    Cho, Seong In; Krutz, G. W.; Stroshine, R. L.; Bellon, V.

    1990-01-01

    More than 80 kinds of fruits and vegetables are available in the United States. But only about 6 of them have their quality standards (Dull, 1986). In the 1990 Fresh Trends survey (Zind, 1990), consumers were asked to rate 16 characteristics important to their decision to purchase fresh produce. The four top ranking factors were ripeness/freshness, taste/flavor, appearance/condition and nutritional value. Of these surveyed, 96% rated ripeness/freshness as extremely important or very important. Therefore, the development of reliable grading or sorting techniques for fresh commodities is essential. Determination of fruit quality often involves cutting and tasting. Non-destructive quality control in fruit and vegetables is a goal of growers and distributors, as well as the food processing industry. Many nondestructive techniques have been evaluated including soft x-ray, optical transmission, near infrared radiation, and machine vision. However, there are few reports of successful non-destructive measurement of sugar content directly in fruit. Higher quality fruit could be harvested and available to consumers if a nondestructive sensor that detects ripeness level directly by measuring sugar content were available. Using proton Nuclear Magnetic Resonance (NMR) principle is the possibility. A nondestructive ripeness (or sweetness) sensor for fruit quality control can be developed with the proton NMR principle (Cho, 1989). Several feasibility studies were necessary for the ripeness sensor development. Main objectives in this paper was to investigate the feasibilities (1) to detect ripeness (or sweetness level) of raw fruit tissue with an high resolution proton NMR spectroscopy (200 MHz) and (2) to measure sugar content of intact fruit with a low resolution proton NMR spectroscopy (10 MHz).

  4. Proton NMR T1, T2, and T1 rho relaxation studies of native and reconstituted sarcoplasmic reticulum and phospholipid vesicles.

    PubMed Central

    Deese, A J; Dratz, E A; Hymel, L; Fleischer, S

    1982-01-01

    The phospholipids protons of native and reconstituted sarcoplasmic reticulum (SR) membrane vesicles yield well-resolved nuclear magnetic resonance (NMR) spectra. Resonance area measurements, guided by the line shape theory of Bloom and co-workers, imply that we are observing a large fraction of the lipid intensity and that the protein does not appear to reduce the percent of the signal that is well resolved. We have measured the spin-lattice (T1) and spin-spin (T2) relaxation rates of the choline, methylene, and terminal methyl protons at 360 MHz and the spin-lattice relaxation rate in the rotating frame (T1 rho) at 100 MHz. Both the T1 and T2 relaxation rates are single exponential processes for all of the resonances if the residual water proton signal is thoroughly eliminated by selective saturation. The T1 and T2 relaxation rates increase as the protein concentration increases, and T2 rate decrease with increasing temperature. This implies that the protein is reducing both high frequency (e.g., trans-gauche methylene isomerizations) and low frequency (e.g., large amplitude, chain wagging) lipid motions, from the center of the bilayer to the surface. It is possible that spin diffusion contributes to the effect of protein on lipid T1's although some of the protein-induced T1 change is due to motional effects. The T2 relaxation times are observed to be near 1 ms for the membranes with highest protein concentration and approximately 10 ms for the lipids devoid of protein. This result, combined with the observation that the T2 rates are monophasic, suggests that at least two lipid environments exist in the presence of protein, and that the lipids are exchanging between these environments at a rate greater than 1/T2 or 10(3) s-1. The choline resonance yields single exponential T1 rho relaxation in the presence and absence of protein, whereas the other resonances measured exhibit biexponential relaxation. Protein significantly increases the single T1 rho relaxation

  5. Arginine activity in the proton-motive photocycle of bacteriorhodopsin: solid-state NMR studies of the wild-type and D85N proteins.

    PubMed

    Petkova, A T; Hu, J G; Bizounok, M; Simpson, M; Griffin, R G; Herzfeld, J

    1999-02-02

    15N solid-state NMR (SSNMR) spectra of guanidyl-15N-labeled bacteriorhodopsin (bR) show perturbation of an arginine residue upon deprotonation of the retinal Schiff base during the photocycle. At the epsilon position, an upfield shift of 4 ppm is observed while the eta nitrogens develop a pair of 'wing' peaks separated by 24 ppm. Proton-driven spin diffusion between the two 'wing' peaks indicates that they arise from a single Arg residue. An unusually asymmetric environment for this residue is indicated by comparison with guanidyl-15N chemical shifts in a series of arginine model compounds. The 'wing' peaks are tentatively assigned to Arg-82 on the basis of the SSNMR investigations of the alkaline and neutral dark-adapted forms of the D85N bacteriorhodopsin mutant. Another, less asymmetric pair of eta signals, that is not affected by Schiff base deprotonation or D85 mutation, is tentatively assigned to Arg-134. The results are discussed in relation to existing models of bR structure and function.

  6. Thin-film solid-state proton NMR measurements using a synthetic mica substrate: Polymer blends

    NASA Astrophysics Data System (ADS)

    VanderHart, David L.; Prabhu, Vivek M.; Lavery, Kristopher A.; Dennis, Cindi L.; Rao, Ashwin B.; Lin, Eric K.

    2009-11-01

    Solid-state proton nuclear magnetic resonance (NMR) measurements are performed successfully on polymer blend thin films through the use of synthetic mica as a substrate. When used as a substrate, synthetic fluorophlogopite mica with its proton-free, diamagnetic character, allows for adequate measurement sensitivity while minimally perturbing the proton thin-film spectra, especially relative to more commonly available natural micas. Specifically, we use multiple-pulse techniques in the presence of magic-angle spinning to measure the degree of mixing in two different polymer blend thin films, polystyrene/poly(xylylene ether) and poly(1-methyladamantyl methacrylate) (PMAdMA)/triphenylsulfonium perfluorobutanesulfonate (TPS-PFBS), spin-coated onto mica substrates. Our earlier studies had focused on bulk systems where NMR signals are stronger, but may not be representative of thin films of the same systems that are relevant to many applications such as photoresist formulations in the electronics industry. The superiority of synthetic over natural paramagnetic mica is demonstrated by the maintenance of resolution and spinning sideband intensities (relative to bulk samples) for the synthetic mica samples. In contrast, degraded resolution and large spinning sidebands are shown to typify spectra of the natural mica samples. This approach can be applied to many other proton measurements of solid thin films, thereby greatly extending the types of systems to be investigated. Magnetic susceptibility measurements are also reported for all micas used.

  7. Thin-film solid-state proton NMR measurements using a synthetic mica substrate: polymer blends.

    PubMed

    VanderHart, David L; Prabhu, Vivek M; Lavery, Kristopher A; Dennis, Cindi L; Rao, Ashwin B; Lin, Eric K

    2009-11-01

    Solid-state proton nuclear magnetic resonance (NMR) measurements are performed successfully on polymer blend thin films through the use of synthetic mica as a substrate. When used as a substrate, synthetic fluorophlogopite mica with its proton-free, diamagnetic character, allows for adequate measurement sensitivity while minimally perturbing the proton thin-film spectra, especially relative to more commonly available natural micas. Specifically, we use multiple-pulse techniques in the presence of magic-angle spinning to measure the degree of mixing in two different polymer blend thin films, polystyrene/poly(xylylene ether) and poly(1-methyladamantyl methacrylate) (PMAdMA)/triphenylsulfonium perfluorobutanesulfonate (TPS-PFBS), spin-coated onto mica substrates. Our earlier studies had focused on bulk systems where NMR signals are stronger, but may not be representative of thin films of the same systems that are relevant to many applications such as photoresist formulations in the electronics industry. The superiority of synthetic over natural paramagnetic mica is demonstrated by the maintenance of resolution and spinning sideband intensities (relative to bulk samples) for the synthetic mica samples. In contrast, degraded resolution and large spinning sidebands are shown to typify spectra of the natural mica samples. This approach can be applied to many other proton measurements of solid thin films, thereby greatly extending the types of systems to be investigated. Magnetic susceptibility measurements are also reported for all micas used.

  8. Diffusion of small molecules in a chitosan/water gel determined by proton localized NMR spectroscopy.

    PubMed

    García-Aparicio, Carlos; Quijada-Garrido, Isabel; Garrido, Leoncio

    2012-02-15

    Proton localized NMR spectroscopy (MRS) has been applied to study the diffusion of three small molecules, caffeine, theophylline and caprolactam, in chitosan gels with different concentration of water. This technique allows the non-destructive monitorization of diffusant concentration as a function of time and location. Concentration profiles were compared with theoretical curves based on solutions of Fick's diffusion equation for the best fitting, with the appropriate boundary conditions. The measured concentration profiles show a good agreement with the Fickian law. Values of the diffusion coefficients D ranging from 6.1×10(-6) to 3.4×10(-6)cm(2)s(-1) depending on chitosan concentration and type of diffusant molecule were determined. In addition, measurements of diffusion coefficients at equilibrium conditions with proton pulsed field gradient NMR methods supported the observed Fickian behavior and showed values of D in excellent agreement with those determined by proton MRS. All these facts demonstrate that proton MRS is an appropriate method for investigating diffusion process in complex systems, such as polymer gels.

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

    SciTech Connect

    Zilm, K.W.

    1992-05-27

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

  10. NMR Spectroscopic Assignment of Backbone and Side-Chain Protons in Fully Protonated Proteins: Microcrystals, Sedimented Assemblies, and Amyloid Fibrils.

    PubMed

    Stanek, Jan; Andreas, Loren B; Jaudzems, Kristaps; Cala, Diane; Lalli, Daniela; Bertarello, Andrea; Schubeis, Tobias; Akopjana, Inara; Kotelovica, Svetlana; Tars, Kaspars; Pica, Andrea; Leone, Serena; Picone, Delia; Xu, Zhi-Qiang; Dixon, Nicholas E; Martinez, Denis; Berbon, Mélanie; El Mammeri, Nadia; Noubhani, Abdelmajid; Saupe, Sven; Habenstein, Birgit; Loquet, Antoine; Pintacuda, Guido

    2016-12-12

    We demonstrate sensitive detection of alpha protons of fully protonated proteins by solid-state NMR spectroscopy with 100-111 kHz magic-angle spinning (MAS). The excellent resolution in the Cα-Hα plane is demonstrated for 5 proteins, including microcrystals, a sedimented complex, a capsid and amyloid fibrils. A set of 3D spectra based on a Cα-Hα detection block was developed and applied for the sequence-specific backbone and aliphatic side-chain resonance assignment using only 500 μg of sample. These developments accelerate structural studies of biomolecular assemblies available in submilligram quantities without the need of protein deuteration.

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

    PubMed

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

    2016-02-05

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

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

    PubMed Central

    2016-01-01

    The revision of the structure of the sesquiterpene aquatolide from a bicyclo[2.2.0]hexane to a bicyclo[2.1.1]hexane structure using compelling NMR data, X-ray crystallography, and the recent confirmation via full synthesis exemplify that the achievement of “structural correctness” depends on the completeness of the experimental evidence. Archived FIDs and newly acquired aquatolide spectra demonstrate that archiving and rigorous interpretation of 1D 1H NMR data may enhance the reproducibility of (bio)chemical research and curb the growing trend of structural misassignments. Despite being the most accessible NMR experiment, 1D 1H spectra encode a wealth of information about bonds and molecular geometry that may be fully mined by 1H iterative full spin analysis (HiFSA). Fully characterized 1D 1H spectra are unideterminant for a given structure. The corresponding FIDs may be readily submitted with publications and collected in databases. Proton NMR spectra are indispensable for structural characterization even in conjunction with 2D data. Quantum interaction and linkage tables (QuILTs) are introduced for a more intuitive visualization of 1D J-coupling relationships, NOESY correlations, and heteronuclear experiments. Overall, this study represents a significant contribution to best practices in NMR-based structural analysis and dereplication. PMID:26812443

  13. Water Proton NMR for In Situ Detection of Insulin Aggregates.

    PubMed

    Taraban, Marc B; Truong, Huy C; Feng, Yue; Jouravleva, Elena V; Anisimov, Mikhail A; Yu, Yihua Bruce

    2015-12-01

    The need for quality control during the manufacturing and distribution of biopharmaceuticals is becoming increasingly necessary. At present, detecting drug degradation through the monitoring of active factor aggregation is accomplished through "invasive" techniques, such as size-exclusion chromatography (SEC), analytical ultracentrifugation (AUC), and so on. Unfortunately, these analytical methods require sampling the drug by opening the drug container that renders the remaining drug unusable regardless of the outcome of the test. Visual inspection, the current non-invasive quality control method is qualitative and can only detect visible particulates. Thus, it will miss sub-visible protein aggregates. In this paper, human insulin preparations were used to demonstrate that the transverse relaxation rate of water protons R2 ((1) H2 O) can serve as a sensitive and reliable indicator to detect and quantify both visible and sub-visible protein aggregates. R2 ((1) H2 O) is measured using a wide-bore low-field bench-top NMR instrument with permanent magnets. Such analysis could be carried out without opening the drug container, thus saving a drug for further use. The results suggest a novel, economical, non-destructive in situ analytical technique that allows for on-the-site quantification of protein aggregation in biopharmaceutical products. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  14. Temperature dependence of proton NMR relaxation times at earth's magnetic field

    NASA Astrophysics Data System (ADS)

    Niedbalski, Peter; Kiswandhi, Andhika; Parish, Christopher; Ferguson, Sarah; Cervantes, Eduardo; Oomen, Anisha; Krishnan, Anagha; Goyal, Aayush; Lumata, Lloyd

    The theoretical description of relaxation processes for protons, well established and experimentally verified at conventional nuclear magnetic resonance (NMR) fields, has remained untested at low fields despite significant advances in low field NMR technology. In this study, proton spin-lattice relaxation (T1) times in pure water and water doped with varying concentrations of the paramagnetic agent copper chloride have been measured from 6 to 92oC at earth's magnetic field (1700 Hz). Results show a linear increase of T1 with temperature for each of the samples studied. Increasing the concentration of the copper chloride greatly reduced T1 and reduced dependence on temperature. The consistency of the results with theory is an important confirmation of past results, while the ability of an ultra-low field NMR system to do contrast-enhanced magnetic resonance imaging (MRI) is promising for future applicability to low-cost medical imaging and chemical identification. This work is supported by US Dept of Defense Award No. W81XWH-14-1-0048 and the Robert A. Welch Foundation Grant No. AT-1877.

  15. Low resolution 1H NMR assignment of proton populations in pound cake and its polymeric ingredients.

    PubMed

    Luyts, A; Wilderjans, E; Waterschoot, J; Van Haesendonck, I; Brijs, K; Courtin, C M; Hills, B; Delcour, J A

    2013-08-15

    Based on a model system approach, five different proton populations were distinguished in pound cake crumb using one dimensional low resolution (1)H NMR spectroscopy. In free induction decay (FID) measurements, proton populations were assigned to (i) non-exchanging CH protons of crystalline starch, proteins and crystalline fat and (ii) non-exchanging CH protons of amorphous starch and gluten, which are in little contact with water. In Carr-Purcell-Meiboom-Gill (CPMG) measurements, three proton populations were distinguished. The CPMG population with the lowest mobility and the FID population with the highest mobility represent the same proton population. The two CPMG proton populations with the highest mobility were assigned to exchanging protons (i.e., protons of water, starch, gluten, egg proteins and sugar) and protons of lipids (i.e., protons of egg yolk lipids and amorphous lipid fraction of margarine) respectively. Based on their spin-lattice relaxation times (T1), two dimensional (1)H NMR spectroscopy further resolved the two proton populations with the highest mobility into three and two proton populations, respectively.

  16. Proton 2D NMR and distance geometry study of the folding of Ecballium elaterium trypsin inhibitor, a member of the squash inhibitors family

    SciTech Connect

    Heitz, A.; Chiche, L.; Le-Nguyen, D.; Castro, B. )

    1989-03-21

    The solution conformation of synthetic Ecballium elaterium trypsin inhibitor II, a 28-residue peptide with 3 disulfide bridges, has been studied by {sup 1}H 2D NMR measurements. Secondary structure elements were determined: a miniantiparallel {beta}-sheet Met 7-Cys 9 and Gly 25-Cys 27, a {beta}-hairpin 20-28 with {beta}-turn 22-25, and two tight turns Asp 12-Cys 15 and Leu 16-Cys 19. A set of interproton distance restraints deduced from two-dimensional nuclear Overhauser enhancement spectra and 13 {phi} backbone torsion angles restraints were used as the basis of three-dimensional structure computations including disulfide bridges arrangement by using distance geometry calculations. Computations for the 15 possible S-S linkage combinations lead to the proposal of the array 2-19, 9-21, 15-27 as the most probably structure for EETI II.

  17. High-resolution proton and carbon-13 NMR of membranes: why sonicate

    SciTech Connect

    Oldfield, E.; Bowers, J.L.; Forbes, J.

    1987-11-03

    The authors have obtained high-field (11.7-T) proton and carbon-13 Fourier transform (FT) nuclear magnetic resonance (NMR) spectra of egg lecithin and egg lecithin-chloresterol (1:1) multibilayers, using magic-angle sample spinning (MASS) techniques, and sonicated egg lecithin and egg lecithin-cholesterol (1:1) vesicles, using conventional FT NMR methods. Resolution of the proton and carbon-13 MASS NMR spectra of the pure egg lecithin samples is essentially identical with that of sonicated samples, but spectra of the unsonicated lipid, using MASS, can be obtained very much faster than with the more dilute, sonicated systems. With the 1:1 lecithin-cholesterol system, proton MASS NMR spectra are virtually identical with conventional FT spectra of sonicated samples, while the /sup 13/C NMR, the authors demonstrate that most /sup 13/C nuclei in the cholesterol moiety can be monitored, even though these same nuclei are essentially invisible, i.e., are severely broadened, in the corresponding sonicated systems. In addition, /sup 13/C MASS NMR spectra can again be recorded much faster than with sonicated samples, due to concentration effects. Taken together, these results strongly suggest there will seldom be need in the future to resort to ultransonic disruption of lipid bilayer membranes in order to obtain high-resolution proton or carbon-13 NMR spectra.

  18. Analysis of Proton NMR in Hydrogen Bonds in Terms of Lone-Pair and Bond Orbital Contributions.

    PubMed

    Sutter, Kiplangat; Aucar, Gustavo A; Autschbach, Jochen

    2015-12-07

    NMR spectroscopic parameters of the proton involved in hydrogen bonding are studied theoretically. The set of molecules includes systems with internal resonance-assisted hydrogen bonds, internal hydrogen bonds but no resonance stabilization, the acetic acid dimer (AAD), a DNA base pair, and the hydrogen succinate anion (HSA). Ethanol and guanine represent reference molecules without hydrogen bonding. The calculations are based on zero-point vibrationally averaged molecular structures in order to include anharmonicity effects in the NMR parameters. An analysis of the calculated NMR shielding and J-coupling is performed in terms of "chemist's orbitals", that is, localized molecular orbitals (LMOs) representing lone-pairs, atomic cores, and bonds. The LMO analysis associates some of the strong de-shielding of the protons in resonance-assisted hydrogen bonds with delocalization involving the π-backbone. Resonance is also shown to be an important factor causing de-shielding of the OH protons for AAD and HSA, but not for the DNA base pair. Nitromalonamide (NMA) and HSA have particularly strong hydrogen bonds exhibiting signs of covalency in the associated J-couplings. The analysis results show how NMR spectroscopic parameters that are characteristic for hydrogen bonded protons are influenced by the geometry and degree of covalency of the hydrogen bond as well as intra- and intermolecular resonance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Critical hydrogen bonds and protonation states of pyridoxal 5'-phosphate revealed by NMR.

    PubMed

    Limbach, Hans-Heinrich; Chan-Huot, Monique; Sharif, Shasad; Tolstoy, Peter M; Shenderovich, Ilya G; Denisov, Gleb S; Toney, Michael D

    2011-11-01

    In this contribution we review recent NMR studies of protonation and hydrogen bond states of pyridoxal 5'-phosphate (PLP) and PLP model Schiff bases in different environments, starting from aqueous solution, the organic solid state to polar organic solution and finally to enzyme environments. We have established hydrogen bond correlations that allow one to estimate hydrogen bond geometries from (15)N chemical shifts. It is shown that protonation of the pyridine ring of PLP in aspartate aminotransferase (AspAT) is achieved by (i) an intermolecular OHN hydrogen bond with an aspartate residue, assisted by the imidazole group of a histidine side chain and (ii) a local polarity as found for related model systems in a polar organic solvent exhibiting a dielectric constant of about 30. Model studies indicate that protonation of the pyridine ring of PLP leads to a dominance of the ketoenamine form, where the intramolecular OHN hydrogen bond of PLP exhibits a zwitterionic state. Thus, the PLP moiety in AspAT carries a net positive charge considered as a pre-requisite to initiate the enzyme reaction. However, it is shown that the ketoenamine form dominates in the absence of ring protonation when PLP is solvated by polar groups such as water. Finally, the differences between acid-base interactions in aqueous solution and in the interior of proteins are discussed. This article is part of a special issue entitled: Pyridoxal Phosphate Enzymology. Copyright © 2011. Published by Elsevier B.V.

  20. Proton NMR measurements of bacteriophage T4 lysozyme aided by 15N isotopic labeling: structural and dynamic studies of larger proteins

    SciTech Connect

    McIntosh, L.P.; Griffey, R.H.; Muchmore, D.C.; Nielson, C.P.; Redfield, A.G.; Dahlquist, F.W.

    1987-03-01

    A strategy for resolution and assignment of single proton resonances in proteins of molecular mass up to at least 40 kDa is presented. This approach is based on /sup 15/N (or /sup 13/C) labeling of selected residues in a protein. The resonances from protons directly bonded to labeled atoms are detected in a two-dimensional 1H-/sup 15/N (or /sup 13/C) spectrum. The nuclear Overhauser effects from isotopically tagged protons are selectively observed in one-dimensional isotope-directed measurements. Using this approach, we have observed approximately 160 resonances from /sup 15/N-bonded protons in the backbone and sidechains of uniformly /sup 15/N-labeled T4 lysozyme (molecular mass = 18.7 kDa). Partial proton-deuterium exchange can be used to simplify the 1H-/sup 15/N spectrum of this protein. These resonances are identified by amino acid class using selective incorporation of /sup 15/N-labeled amino acids and are assigned to specific residues by mutational substitution, multiple /sup 15/N and /sup 13/C labeling, and isotope-directed nuclear Overhauser effect measurements. For example, using a phenyl(/sup 15/N)alanine-labeled lysozyme variant containing two consecutive phenylalanine residues in an alpha-helical region, we observe an isotope-directed nuclear Overhauser effect from the amide proton of Phe-66 to that of Phe-67.

  1. Proton NMR studies of Cucurbita maxima trypsin inhibitors: Evidence for pH-dependent conformational change and his25 - try27 interaction

    SciTech Connect

    Krishnamoorthi, R.; Chanlan Sun Lin; Yuxi Gong ); VanderVelde, D. ); Hahn, K. )

    1992-01-28

    A pH-dependent His25-Tyr27 interaction was demonstrated in the case of Cucurbita maxima trypsin inhibitors (CMTI-I and CMTI-III) by means of nuclear magnetic resonance (NMR) spectroscopy. pH titration, line widths, peak shapes, deuterium exchange kinetics, and two-dimensional nuclear Overhauser effect spectroscopy (NOESY) were employed to characterize a conformational change involving Tyr27, which was shown to be triggered by deprotonation of His25 around pH 6. A hydrogen bond is proposed to be formed between N{sub {epsilon}} of His25 and OH of Tyr27, as a distance between the atoms, His25 N{epsilon} and Tyr25 OH, of 3.02 {angstrom} is consistent with a model built with NOE-derived distance constraints. The presently characterized relative orientations of His25 and Tyr27 are of functional significance, as these residues make contact with the enzyme in the enzyme-inhibitor complex. Furthermore, trypsin assay and inhibitor-binding studies showed that conformations of trypsin and the squash inhibitor complex. Furthermore, trypsin assay and inhibitor-binding studies showed that conformations of trypsin and the squash inhibitor were functionally relevant only in the pH range 6-8. The pK{sub a} of His25 was determined and found to be influenced by Glu9/Lys substitution and by the hydrolysis of the reactive-site peptide bond between Arg5 and Ile6. As these sites are located far (>10 {angstrom}) from His25, the results point out conformational changes that are propagated to a distant site in the protein molecule.

  2. NMR structural studies of intramolecular (Y+) sub n ter dot (R+) sub n (Y minus ) sub n DNA triplexes in solution: Imino and amino proton and nitrogen markers of Gter dot TA base triple formation

    SciTech Connect

    Radhakrishnan, I.; de los Santos, C.; Patel, D.J. ); Gao, Xiaolian ); Live, D. )

    1991-09-17

    The authors reported previously on NMR studies of (Y+){sub n}{center dot}(R+){sub n}(Y{minus}){sub n}DNA triple helices containing one oligopurine strand (R){sub n} and two oligopyrimidine strands (Y){sub n} stabilized by T{center dot}AT and C{sup +}{center dot}GC base triples. Recently, it has been established that guanosine can recognize a thymidine{center dot}adenosine base pair to form a G{center dot}TA triple in an otherwise (Y+){sub n}{center dot}(R+){sub n}(Y{minus}){sub n} triple-helix motif. The present study extends the NMR research to the characterization of structural features of a 31-mer deoxyoligonucleotide that folds intramolecularly into a 7-mer (Y+){sub n}{center dot}(R+){sub n}(Y{minus}){sub n} triplex with the strands linked through two T{sub 5} loops and that contains a central G{center dot}TA triple flanked by T{center dot}AT triples. The NMR data are consistent with the proposed pairing alignment for the G{center dot}TA triple where the guanosine in an anti orientation pairs through a single hydrogen bond from one of its 2-amino protons to the 4-carbonyl group of thymidine in the Watson-Crick TA pair. They detect a set of NOEs between adjacent triples that establishes that the G{center dot}TA triple stacks between flanking T{center dot}AT triples in the G{center dot}TA triplex. These results demonstrate the capabilities of the NMR approach in monitoring individual base triples and their pairing alignments, as well as establishing that the G{center dot}TA triple can be readily accommodated in an otherwise intramolecular (Y+){sub n}{center dot}(R+){sub n}(Y{minus}){sub n} triple helix in solution.

  3. Proton NMR Spectra: Deceptively Simple and Deceptively Complex Examples.

    ERIC Educational Resources Information Center

    Gurst, J. E.; And Others

    1985-01-01

    Describes relatively simple nuclear magnetic resonance (NMR) experiments that demonstrate unexpected results of the deceptively simple and deceptively complex types. Background information, experimental procedures, and typical results obtained are included. (JN)

  4. Proton NMR Spectra: Deceptively Simple and Deceptively Complex Examples.

    ERIC Educational Resources Information Center

    Gurst, J. E.; And Others

    1985-01-01

    Describes relatively simple nuclear magnetic resonance (NMR) experiments that demonstrate unexpected results of the deceptively simple and deceptively complex types. Background information, experimental procedures, and typical results obtained are included. (JN)

  5. 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

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

    NASA Astrophysics Data System (ADS)

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

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

  7. Optimum levels of exchangeable protons in perdeuterated proteins for proton detection in MAS solid-state NMR spectroscopy.

    PubMed

    Akbey, Umit; Lange, Sascha; Trent Franks, W; Linser, Rasmus; Rehbein, Kristina; Diehl, Anne; van Rossum, Barth-Jan; Reif, Bernd; Oschkinat, Hartmut

    2010-01-01

    We present a systematic study of the effect of the level of exchangeable protons on the observed amide proton linewidth obtained in perdeuterated proteins. Decreasing the amount of D(2)O employed in the crystallization buffer from 90 to 0%, we observe a fourfold increase in linewidth for both (1)H and (15)N resonances. At the same time, we find a gradual increase in the signal-to-noise ratio (SNR) for (1)H-(15)N correlations in dipolar coupling based experiments for H(2)O concentrations of up to 40%. Beyond 40%, a significant reduction in SNR is observed. Scalar-coupling based (1)H-(15)N correlation experiments yield a nearly constant SNR for samples prepared with < or =30% H(2)O. Samples in which more H(2)O is employed for crystallization show a significantly reduced NMR intensity. Calculation of the SNR by taking into account the reduction in (1)H T (1) in samples containing more protons (SNR per unit time), yields a maximum SNR for samples crystallized using 30 and 40% H(2)O for scalar and dipolar coupling based experiments, respectively. A sensitivity gain of 3.8 is obtained by increasing the H(2)O concentration from 10 to 40% in the CP based experiment, whereas the linewidth only becomes 1.5 times broader. In general, we find that CP is more favorable compared to INEPT based transfer when the number of possible (1)H,(1)H interactions increases. At low levels of deuteration (> or =60% H(2)O in the crystallization buffer), resonances from rigid residues are broadened beyond detection. All experiments are carried out at MAS frequency of 24 kHz employing perdeuterated samples of the chicken alpha-spectrin SH3 domain.

  8. Analysis of 7-Membered Lactones by Computational NMR Methods. Proton NMR Chemical Shift Data are More Discriminating than Carbon

    PubMed Central

    Marell, Daniel J.; Emond, Susanna J.; Kulshrestha, Aman; Hoye, Thomas R.

    2014-01-01

    We report an NMR chemical shift study of conformationally challenging seven-membered lactones (1–11); computed and experimental data sets are compared. The computations involved full conformational analysis of each lactone, Boltzmann-weighted averaging of the chemical shifts across all conformers, and linear correction of the computed chemical shifts. DFT geometry optimizations [M06-2X/6-31+G(d,p)] and GIAO NMR chemical shift calculations [B3LYP/6-311+G(2d,p)] provide the computed chemical shifts. The corrected-mean absolute error (CMAE), the average of the differences between the computed and experimental chemical shifts for each of the eleven lactones, is encouragingly small (0.02–0.08 ppm for 1H or 0.8–2.2 ppm for 13C). Three pairs of cis vs. trans diastereomeric lactones were used to assess the ability of the method to distinguish between stereoisomers. The experimental shifts were compared with the computed shifts for each of the two possible isomers. We introduce the use of a “match ratio”—the ratio of the larger (worse fit) to the smaller (better fit) CMAE. A greater match ratio value indicates better distinguishing ability. The match ratios are larger for proton data [2.4–4.0 (ave = 3.2)] than for carbon [1.1–2.3 (ave = 1.6)], indicating that the former provide a better basis for discriminating these diastereomers. PMID:24354614

  9. Progresses in proton radioactivity studies

    SciTech Connect

    Ferreira, L. S.; Maglione, E.

    2016-07-07

    In the present talk, we will discuss recent progresses in the theoretical study of proton radioactivity and their impact on the present understanding of nuclear structure at the extremes of proton stability.

  10. Surface NMR measurement of proton relaxation times in medium to coarse-grained sand aquifer.

    PubMed

    Shushakov, O A

    1996-01-01

    A surface NMR investigation of groundwater in the geomagnetic field is under study. To detect the surface NMR a wire loop with a diameter of about 100 m, being an antenna for both an exciting field source and the NMR signal receiver, is laid out on the ground. A sinusoidal current pulse with a rectangular envelope is passed through the loop to excite the NMR signal. The carrier frequency of the oscillating current in this pulse is equal to the Larmor frequency of protons in the Earth's magnetic field. The current amplitude is changed up to 200 amps and the pulse duration is fixed and is equal to 40 ms. The exciting pulse is followed by an induction emf signal caused by the Larmor nuclear precession in geomagnetic field. The relaxation times T1, T2, and T2* were measured by the surface NMR for both groundwater in medium to coarse-grained sand at borehole and for bulk water under the ice surface of frozen lake. To determine T1, a longitudinal interference in experiments with repeated pulses was measured. A sequence with equal period between equal excitation pulses was used. The relaxation times T1, T2, measured for bulk water under the ice of the Ob reservoir were 1.0 s and 0.7 s, respectively. To estimate an influence of dissolved oxygen T1 of the same water at the same temperature was measured by lab NMR with and without pumping of oxygen. The relaxation time T1 measured for water in the medium to coarse-grained sand is 0.65 s. The relaxation time T2 estimated by spin echo sequence is found to be equal to 0.15 s. The relaxation time T2* is found to be about 80 ms. This result contradicts published earlier phenomenological correlation between relaxation time T2* and grain size of water-bearing rock. This could be as a result of unsound approach based on grain size or influence of paramagnetic impurities.

  11. 1H NMR Studies of MgH2

    NASA Astrophysics Data System (ADS)

    Itoh, Yutaka; Kado, Ryoichi

    We report on 1H NMR studies of commercially available powder MgH2 exposed to air and maybe humidity, which has been believed to be a promising material for hydrogen storage. The Fourier transform of the free-induction decay of the protons indicatesd superposition of broad and narrow components in the NMR spectrum, while the Fourier transform of the 1H nuclear spin-echo reproduced the narrow component. With cooling down below room temperature, the ratio of the narrow peak to the broad spectrum decreased. The broad spectrum is associated with direct dipolar coupled protons on an inhomogeneous rigid lattice. The narrow peak is associated with interstitial protons with more inhomogeneous surroundings.

  12. NMR spectra and translational diffusion of protons in crystals with hydrogen bonds

    NASA Astrophysics Data System (ADS)

    Timokhin, V. M.; Garmash, V. M.; Tarasov, V. P.

    2015-07-01

    Investigation of proton transport in hydrogen-bond crystals at low temperatures is currently one of important problems in the semiconductor physics. With the use of the NMR spectra of wide-band-gap hydrogen-bond crystals grown in H2O and D2O solutions, we have succeeded in finding a direct proof of the presence of protons in the mobile phase, determined their activation energy in good agreement with the spectra of thermally stimulated depolarization currents and with the infrared spectra, and, as a result, clarified the mechanism of proton transport and tunneling.

  13. Channel orientation anisotropy in perfluorosulfonic acid/SiO 2 composite proton exchange membranes: Water self-diffusion study using NMR

    NASA Astrophysics Data System (ADS)

    Filipoi, Carmen; Demco, Dan E.; Zhu, Xiaomin; Vinokur, Rostislav; Conradi, Oliver; Fechete, Radu; Möller, Martin

    2011-09-01

    A diffusion-exchange model with the assumption of two water pools was applied to describe the water transport in perfluorinated sulfonic acid (PFSA)/SiO 2 nanocomposites. The water diffusivity in-plane and through-plane in solution cast films was measured by NMR revealing higher in-plane mobility. Both diffusion coefficients reached maxima at ˜3%-wt. concentration in SiO 2. The anisotropy of the PFSA channels orientation reflected in the diffusivity anisotropy decreased with the increase in the nanofiller content. Water exchange rates reached a maximum at low concentration of silica. Gaussian displacement distribution for water diffusion was detected in PFSA membrane at 40 °C independent of the direction of gradient for small concentration in silica.

  14. Proton NMR characterization of intact primary and metastatic melanoma cells in 2D & 3D cultures.

    PubMed

    Ramachandran, Gokula Krishnan; Yeow, Chen Hua

    2017-03-16

    To characterize the differences between the primary and metastatic melanoma cell lines grown in 2D cultures and 3D cultures. Primary melanoma cells (WM115) and metastatic melanoma cells (WM266) extracted from a single donor was cultured in 2D as well as 3D cultures. These cells were characterized using proton NMR spectrometry, and the qualitative chemical shifts markers were identified and discussed. In monolayer culture (2D), we observed one qualitative chemical shift marker for primary melanoma cells. In spheroid cultures (3D), we observed nine significant chemical shifts, of which eight markers were specific for primary melanoma spheroids, whereas the other one marker was specific to metastatic melanoma spheroids. This study suggests that the glucose accumulation and phospholipid composition vary significantly between the primary and metastatic cells lines that are obtained from a single donor and also with the cell culturing methods. 14 qualitative chemical shift markers were obtained in the comparison between monolayer culture and spheroids cultures irrespective of the differences in the cell lines. Among which 4 were unique to monolayer cultures whereas 10 chemical shifts were unique to the spheroid cultures. This study also shows that the method of cell culture would drastically affect the phospholipid composition of the cells and also depicts that the cells in spheroid culture closely resembles the cells in vivo. This study shows the high specificity of proton NMR spectrometry in characterizing cancer cell lines and also shows the variations in the glucose accumulation and phospholipid composition between the primary and metastatic melanoma cell lines from the same donor. Differences in the cell culture method does plays an important role in phospholipid composition of the cells.

  15. Empirical NMR Chemical Shift Correlations for Methyl and Methylene Protons.

    ERIC Educational Resources Information Center

    Friedrich, Edwin C.; Runkle, Katherine Gates

    1984-01-01

    Presents an internally consistent set of 63 substituent constants developed for use with the Schoolery Relationship to predict the chemical shifts of methylene protons of acyclic compounds. Chemical shift data used in deriving the constants were taken mainly from primary sources of HNMR (nuclear magnetic resonance) spectra. (JN)

  16. Proton NMR investigation into the basis for the relatively high redox potential of lignin peroxidase

    SciTech Connect

    Banci, L.; Bertini, I.; Turano, P. ); Ming Tien ); Kirk, T.K. )

    1991-08-15

    Lignin peroxidase shares several structural features with the well-studied horseradish peroxidase and cytochrome c peroxidase but carries a higher redox potential. Here the heme domain of lignin peroxidase and the lignin peroxidase cyanide adduct was examined by {sup 1}H NMR spectroscopy, including nuclear Overhauser effect and two-dimensional measurements, and the findings were compared with those for horseradish peroxidase and cytochrome c peroxidase. Structural information was obtained on the orientation of the heme vinyl and propionate groups and the proximal and distal histidines. The shifts of the {var epsilon}1 proton of the proximal histidine were found to be empirically related to the Fe{sup 3+}/Fe{sup 2+} redox potentials.

  17. Line-narrowing in proton-detected nitrogen-14 NMR

    NASA Astrophysics Data System (ADS)

    Cavadini, Simone; Vitzthum, Veronika; Ulzega, Simone; Abraham, Anuji; Bodenhausen, Geoffrey

    2010-01-01

    In solids spinning at the magic angle, the indirect detection of single-quantum (SQ) and double-quantum (DQ) 14N spectra ( I = 1) via spy nuclei S = 1/2 such as protons can be achieved in the manner of heteronuclear single- or multiple-quantum correlation (HSQC or HMQC) spectroscopy. The HMQC method relies on the excitation of two-spin coherences of the type T11IT11S and T21IT11S at the beginning of the evolution interval t1. The spectra obtained by Fourier transformation from t1 to ω1 may be broadened by the homogenous decay of the transverse terms of the spy nuclei S. This broadening is mostly due to homonuclear dipolar S- S' interactions between the proton spy nuclei. In this work we have investigated the possibility of inserting rotor-synchronized symmetry-based C or R sequences and decoupling schemes such as Phase-Modulated Lee-Goldburg (PMLG) sequences in the evolution period. These schemes reduce the homonuclear proton-proton interactions and lead to an enhancement of the resolution of both SQ and DQ proton-detected 14N HMQC spectra. In addition, we have investigated the combination of HSQC with symmetry-based sequences and PMLG and shown that the highest resolution in the 14N dimension is achieved by using HSQC in combination with symmetry-based sequences of the R-type. We show improvements in resolution in samples of L-alanine and the tripeptide ala-ala-gly (AAG). In particular, for L-alanine the width of the 14N SQ peak is reduced from 2 to 1.2 kHz, in agreement with simulations. We report accurate measurements of quadrupolar coupling constants and asymmetry parameters for amide 14N in AAG peptide bonds.

  18. Line-narrowing in proton-detected nitrogen-14 NMR.

    PubMed

    Cavadini, Simone; Vitzthum, Veronika; Ulzega, Simone; Abraham, Anuji; Bodenhausen, Geoffrey

    2010-01-01

    In solids spinning at the magic angle, the indirect detection of single-quantum (SQ) and double-quantum (DQ) (14)N spectra (I=1) via spy nuclei S=1/2 such as protons can be achieved in the manner of heteronuclear single- or multiple-quantum correlation (HSQC or HMQC) spectroscopy. The HMQC method relies on the excitation of two-spin coherences of the type T(11)(I)T(11)(S) and T(21)(I)T(11)(S) at the beginning of the evolution interval t(1). The spectra obtained by Fourier transformation from t(1) to omega(1) may be broadened by the homogenous decay of the transverse terms of the spy nuclei S. This broadening is mostly due to homonuclear dipolar S-S' interactions between the proton spy nuclei. In this work we have investigated the possibility of inserting rotor-synchronized symmetry-based C or R sequences and decoupling schemes such as Phase-Modulated Lee-Goldburg (PMLG) sequences in the evolution period. These schemes reduce the homonuclear proton-proton interactions and lead to an enhancement of the resolution of both SQ and DQ proton-detected (14)N HMQC spectra. In addition, we have investigated the combination of HSQC with symmetry-based sequences and PMLG and shown that the highest resolution in the (14)N dimension is achieved by using HSQC in combination with symmetry-based sequences of the R-type. We show improvements in resolution in samples of l-alanine and the tripeptide ala-ala-gly (AAG). In particular, for l-alanine the width of the (14)N SQ peak is reduced from 2 to 1.2 kHz, in agreement with simulations. We report accurate measurements of quadrupolar coupling constants and asymmetry parameters for amide (14)N in AAG peptide bonds.

  19. Protein-Inhibitor Interaction Studies Using NMR

    PubMed Central

    Ishima, Rieko

    2015-01-01

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

  20. Study of proton radioactivities

    SciTech Connect

    Davids, C.N.; Back, B.B.; Henderson, D.J.

    1995-08-01

    About a dozen nuclei are currently known to accomplish their radioactive decay by emitting a proton. These nuclei are situated far from the valley of stability, and mark the very limits of existence for proton-rich nuclei: the proton drip line. A new 39-ms proton radioactivity was observed following the bombardment of a {sup 96}Ru target by a beam of 420-MeV {sup 78}Kr. Using the double-sided Si strip detector implantation system at the FMA, a proton group having an energy of 1.05 MeV was observed, correlated with the implantation of ions having mass 167. The subsequent daughter decay was identified as {sup 166}Os by its characteristic alpha decay, and therefore the proton emitter is assigned to the {sup 167}Ir nucleus. Further analysis showed that a second weak proton group from the same nucleus is present, indicating an isomeric state. Two other proton emitters were discovered recently at the FMA: {sup 171}Au and {sup 185}Bi, which is the heaviest known proton radioactivity. The measured decay energies and half-lives will enable the angular momentum of the emitted protons to be determined, thus providing spectroscopic information on nuclei that are beyond the proton drip line. In addition, the decay energy yields the mass of the nucleus, providing a sensitive test of mass models in this extremely proton-rich region of the chart of the nuclides. Additional searches for proton emitters will be conducted in the future, in order to extend our knowledge of the location of the proton drip line.

  1. 31P nuclear magnetic resonance study of the proton-irradiated KTiOPO4

    NASA Astrophysics Data System (ADS)

    Kim, Se-Hun; Lee, Cheol Eui

    2013-08-01

    31P nuclear magnetic resonance (NMR) was employed to study the effects of proton irradiation on KTiOPO4 (KTP) in view of the previously studied paramagnetic impurity doping effects. High-resolution 31P NMR measurements showed significant increase in the isotropic chemical shifts of the two inequivalent phosphorus sites in the proton-irradiated KTP system, indicating decrease in the electron density around the phosphorous nuclei. The 31P NMR linewidths of the KTP system manifested anomalies associated with the superionic transition and with the polaron formation, which became much weaker after proton irradiation. Besides, the activation energy of the charge carriers increased significantly after proton irradiation.

  2. TU-EF-BRA-01: NMR and Proton Density MRI of the 1D Patient

    SciTech Connect

    Wolbarst, A.

    2015-06-15

    applications of MRI exploit its capability to detect and image distinct movements of fluids: MR angiography (MRA), which rivals CT angiography but often requires no contrast medium, monitors the bulk flow of blood; functional MRI ( f MRI), distinguishes the perfusion of oxygenated blood from that of de-oxygenated, and lights up parts of the brain that are activated by a stimulus, rather like PET; and diffusion tensor imaging (DTI) indicates the diffusion of free water along tracts of axons, thereby bringing nerve trunks into view. There are variants on all of these themes, and on others as well. Magnetic Resonance Spectroscopy (MRS), for example, can perform non-invasive ‘virtual biopsies’ that allow identification of certain cancers and other lesions. And an MRI-guided needle biopsy can sample brain tissue from a region only millimeters in dimensions. MRI, however, involves deeper and more complex aspects of physics, technology, and biology than do most other imaging modalities, and it is widely considered to be correspondingly more difficult to learn. We could probably cover all of this rather comprehensively if we had 50 hours available rather than 2 ̶ but, to paraphrase a former Secretary of Defense, you tell your story in the time you have allotted. The four presenters and another physicist, Kevin King from GE, have combined their efforts to co-author a single slide show that describes essentials of MRI as simply as possible. It is obviously far from thorough, but hopefully it will succeed in explaining some of the basics in a simplified but still valid fashion; in providing a taste of the numerous capabilities and complexities of the modality; and in whetting your appetite to learn more. Part I. NMR, and Proton Density MRI of the 1D Patient (Wolbarst), begins with an introductory case study that illustrates a half dozen ways in which MRI provides valuable clinical information. It then explores the nuclear magnetic resonance (NMR) phenomenon, which underlies MRI. NMR

  3. Proton detection of MAS solid-state NMR spectra of half-integer quadrupolar nuclei.

    PubMed

    Venkatesh, Amrit; Hanrahan, Michael P; Rossini, Aaron J

    Fast magic angle spinning (MAS) and proton detection has found widespread application to enhance the sensitivity of solid-state NMR experiments with spin-1/2 nuclei such as (13)C, (15)N and (29)Si, however, this approach is not yet routinely applied to half-integer quadrupolar nuclei. Here we have investigated the feasibility of using fast MAS and proton detection to enhance the sensitivity of solid-state NMR experiments with half-integer quadrupolar nuclei. The previously described dipolar hetero-nuclear multiple quantum correlation (D-HMQC) and dipolar refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT) pulse sequences were used for proton detection of half-integer quadrupolar nuclei. Quantitative comparisons of signal-to-noise ratios and the sensitivity of proton detected D-HMQC and D-RINEPT and direct detection spin echo and quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) solid-state NMR spectra, demonstrate that one dimensional proton detected experiments can provide sensitivity similar to or exceeding that obtainable with direct detection QCPMG experiments. 2D D-HMQC and D-RINEPT experiments provide less sensitivity than QCPMG experiments but proton detected 2D hetero-nuclear correlation solid-state NMR spectra of half-integer nuclei can still be acquired in about the same time as a 1D spin echo spectrum. Notably, the rarely used D-RINEPT pulse sequence is found to provide similar, or better sensitivity than D-HMQC in some cases. Proton detected D-RINEPT benefits from the short longitudinal relaxation times (T1) normally associated with half-integer quadrupolar nuclei, it can be combined with existing signal enhancement methods for quadrupolar nuclei, and t1-noise in the indirect dimension can easily be removed by pre-saturation of the (1)H nuclei. The rapid acquisition of proton detected 2D HETCOR solid-state NMR spectra of a range of half-integer quadrupolar nuclei such as (17)O, (27)Al, (35)Cl and (71)Ga is demonstrated. Copyright

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

    SciTech Connect

    Zilm, K.W.

    1988-01-01

    This report covers the progress made on the title project during the current reporting period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines we are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. This quarter we have focused on variable temperature spin lattice relaxation measurements for several of the Argonne coals. 5 figs.

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

    SciTech Connect

    Zilm, K.W.

    1988-01-01

    This report covers the progress made on the title project during the current reporting period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines we are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. This quarter we have focussed on spin lattice relaxation measurements for several of the Argonne coals. 2 figs., 1 tab.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  7. Anatomising proton NMR spectra with pure shift 2D J-spectroscopy: A cautionary tale

    NASA Astrophysics Data System (ADS)

    Kiraly, Peter; Foroozandeh, Mohammadali; Nilsson, Mathias; Morris, Gareth A.

    2017-09-01

    Analysis of proton NMR spectra has been a key tool in structure determination for over 60 years. A classic tool is 2D J-spectroscopy, but common problems are the difficulty of obtaining the absorption mode lineshapes needed for accurate results, and the need for a 45° shear of the final 2D spectrum. A novel 2D NMR method is reported here that allows straightforward determination of homonuclear couplings, using a modified version of the PSYCHE method to suppress couplings in the direct dimension. The method illustrates the need for care when combining pure shift data acquisition with multiple pulse methods.

  8. Detection and follow-up, after partial liver resection, of the urinary paracetamol metabolites by proton NMR spectroscopy.

    PubMed

    Galinski, Michel; Racine, Stephane-Xavier; Bossard, Anne-Elisabeth; Fleyfel, Maher; Hamza, Lilia; Bouchemal, Nadia; Adnet, Frédéric; Le Moyec, Laurence

    2014-01-01

    Combination drug therapy is often used to achieve optimal analgesia in surgery. Paracetamol can be used as one component of an analgesic regime following hepatic resection. This study was designed to investigate paracetamol and its metabolites by proton NMR spectroscopy in patient urine and to assess whether N-acetyl-p-benzoquinone imine (NAPQI, a hepatotoxic metabolite) formation is increased after liver resection. We studied the excretion of acetaminophen and its metabolites by 5 patients who were operated on for partial liver resection by proton NMR spectroscopy. As an intravenous infusion 1 g of paracetamol was given over 15 min every 6 h during 48 h. The first injection was given in the operating theatre after liver resection was completed. Urine samples were collected before injection (T1) and 24 and 48 h after the first injection (T2 and T3); the samples were frozen and kept at -20°C up to the analysis by NMR spectroscopy. Metabolites of the paracetamol were detected for all patients. Among the discerned metabolites, 4 were identified as metabolites of paracetamol: paracetamol glucuronide, paracetamol sulfate, N-acetyl-L-cysteinyl paracetamol (metabolite of NAPQI) and paracetamol. Their ratios, respectively, were: 46-82.9, 12.6-30.0, 0.5-5.5 and 1.43-3.54%. This study showed that there was no increase in the formation of toxic metabolite (NAPQI) after treatment with paracetamol in these few cases of liver resections. A larger study is necessary to confirm these results.

  9. Analysis of human muscle extracts by proton NMR

    SciTech Connect

    Venkatasubramanian, P.N.; Barany, M.; Arus, C.

    1986-03-01

    Perchloric acid extracts were prepared from pooled human muscle biopsies from patients diagnosed with scoliosis (SCOL) and cerebral palsy (CP). After neutralization with KOH and removal of perchlorate, the extracts were concentrated by freeze drying and dissolved in /sup 2/H/sub 2/O to contain 120 O.D. units at 280 nm per 0.5 ml. /sup 1/H NMR spectroscopy was performed with the 5 mm probe of a Varian XL300 instrument. Creatine, lactate, carnosine, and choline were the major resonances in the one-dimensional spectra of both extracts. With creatine as reference, 2.5-fold more lactate was found in SCOL than in CP, and a much smaller difference was also found in their carnosine content. Two-dimensional COSY comparison revealed several differences between the two extracts. Taurine, N-acetyl glutamate, glycerophosphoryl choline (or phosphoryl choline) and an unidentified spot were present only in the extract from SCOL but not in that from CP. On the other hand, aspartate, hydroxy-proline, carnitine and glycerophosphoryl ethanolamine were only present in CP but absent in SCOL. Alanine, cysteine, lysine and arginine appeared in both extracts without an apparent intensity difference.

  10. Diffusion dependence of proton NMR relaxation rates in the presence of ferritin

    NASA Astrophysics Data System (ADS)

    Boss, Michael; Hammel, P. Chris

    2009-03-01

    Ferritin is the predominant iron-storage protein in living organisms. It may serve as an indicator of neurodegenerative diseases such as Alzheimer's. Measuring brain ferritin concentration non-invasively via MRI could enable better diagnoses and treatments of such diseases. Quantitative MRI determination of the ferritin concentration requires an understanding of the NMR relaxation mechanisms of hydrogen protons in the presence of ferritin. In aqueous solutions, ferritin enhances the transverse relaxation rate (R2) of the protons. This is thought to occur due to a diffusive mechanism, where protons diffusing near ferritin pass through a region of elevated magnetic field, and a chemical exchange mechanism, where protons bind to the protein for a period of time, experiencing an even higher magnetic field. These two mechanisms exhibit different dependencies on the self-diffusion coefficient of the protons. By adding glycerol to aqueous solutions, we control the self-diffusion of protons. We measure the R2 of protons in ferritin-containing binary mixtures of water and glycerol using CPMG sequences, and compare the experimental results to theoretical predictions of diffusion dependence in order to distinguish the relative importance of the mechanisms.

  11. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  12. Selective excitation enables assignment of proton resonances and {sup 1}H-{sup 1}H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of {sup 1}H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as {sup 13}C or {sup 15}N. In this method, after the initial preparation of proton magnetization and cross-polarization to {sup 13}C nuclei, transverse magnetization of desired {sup 13}C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific {sup 13}C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of {sup 1}H-{sup 1}H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  13. Selective excitation enables assignment of proton resonances and 1H-1H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-01

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of 1H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as 13C or 15N. In this method, after the initial preparation of proton magnetization and cross-polarization to 13C nuclei, transverse magnetization of desired 13C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific 13C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of 1H-1H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

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

    SciTech Connect

    Zilm, K.W.

    1990-01-01

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

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

    SciTech Connect

    Zilm, K.W.

    1989-01-01

    This report covers the progress made on the title project and summarizes the accomplishments for the project period. Four major areas of inquiry have been pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concern how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines we are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. The effects of very high MAS rates (>10 kHz) on cross polarization dynamics are also being investigated for similar reasons. During the last quarter the authors have concentrated on improvements in cross polarization (CP) sequences with a goal of making the CP process insensitive to experimental conditions such as the magic angle spinning (MAS) rate. In order to be able to use fields the order of 7.0 T or higher, CP efficiency must be maintained at MAS rates of over 10 kHz. The standard sequences have severe limitations at these rates which lead to intensity distortions in {sup 13}C CPMAS spectra. Thus in order to be able to take advantage of the increases in sensitivity and resolution that accompany high field operation, improvements in the NMR methods are required. The new sequences the authors are developing will be especially important for quantitative analysis of coal structure by {sup 13}C solid state NMR at high field strengths. 13 refs., 7 figs., 2 tabs.

  16. Detection and characterization of serine and threonine hydroxyl protons in Bacillus circulans xylanase by NMR spectroscopy.

    PubMed

    Brockerman, Jacob A; Okon, Mark; McIntosh, Lawrence P

    2014-01-01

    Hydroxyl protons on serine and threonine residues are not well characterized in protein structures determined by both NMR spectroscopy and X-ray crystallography. In the case of NMR spectroscopy, this is in large part because hydroxyl proton signals are usually hidden under crowded regions of (1)H-NMR spectra and remain undetected by conventional heteronuclear correlation approaches that rely on strong one-bond (1)H-(15)N or (1)H-(13)C couplings. However, by filtering against protons directly bonded to (13)C or (15)N nuclei, signals from slowly-exchanging hydroxyls can be observed in the (1)H-NMR spectrum of a uniformly (13)C/(15)N-labeled protein. Here we demonstrate the use of a simple selective labeling scheme in combination with long-range heteronuclear scalar correlation experiments as an easy and relatively inexpensive way to detect and assign these hydroxyl proton signals. Using auxtrophic Escherichia coli strains, we produced Bacillus circulans xylanase (BcX) labeled with (13)C/(15)N-serine or (13)C/(15)N-threonine. Signals from two serine and three threonine hydroxyls in these protein samples were readily observed via (3)JC-OH couplings in long-range (13)C-HSQC spectra. These scalar couplings (~5-7 Hz) were measured in a sample of uniformly (13)C/(15)N-labeled BcX using a quantitative (13)C/(15)N-filtered spin-echo difference experiment. In a similar approach, the threonine and serine hydroxyl hydrogen exchange kinetics were measured using a (13)C/(15)N-filtered CLEANEX-PM pulse sequence. Collectively, these experiments provide insights into the structural and dynamic properties of several serine and threonine hydroxyls within this model protein.

  17. NMR resonance splitting of urea in stretched hydrogels: proton exchange and (1)H/(2)H isotopologues.

    PubMed

    Kuchel, Philip W; Naumann, Christoph; Chapman, Bogdan E; Shishmarev, Dmitry; Håkansson, Pär; Bacskay, George; Hush, Noel S

    2014-10-01

    Urea at ∼12 M in concentrated gelatin gel, that was stretched, gave (1)H and (2)H NMR spectral splitting patterns that varied in a predictable way with changes in the relative proportions of (1)H2O and (2)H2O in the medium. This required consideration of the combinatorics of the two amide groups in urea that have a total of four protonation/deuteration sites giving rise to 16 different isotopologues, if all the atoms were separately identifiable. The rate constant that characterized the exchange of the protons with water was estimated by back-transformation analysis of 2D-EXSY spectra. There was no (1)H NMR spectral evidence that the chiral gelatin medium had caused in-equivalence in the protons bonded to each amide nitrogen atom. The spectral splitting patterns in (1)H and (2)H NMR spectra were accounted for by intra-molecular scalar and dipolar interactions, and quadrupolar interactions with the electric field gradients of the gelatin matrix, respectively.

  18. Differential protonation and dynamic structure of doxylamine succinate in solution using 1H and 13C NMR.

    PubMed

    Somashekar, B S; Nagana Gowda, G A; Ramesha, A R; Khetrapal, C L

    2004-07-01

    A protonation and dynamic structural study of doxylamine succinate, a 1:1 salt of succinic acid with dimethyl-[2-(1-phenyl-1-pyridin-2-yl-ethoxy)ethyl]amine, in solution using one- and two-dimensional 1H and 13C NMR experiments at variable temperature and concentration is presented. The two acidic protons of the salt doxylamine succinate are in 'intermediate' exchange at room temperature, as evidenced by the appearance of a broad signal. This signal evolves into two distinct signals below about -30 degrees C. A two-dimensional 1H-1H double quantum filtered correlation experiment carried out at -55 degrees C shows protonation of one of the acidic protons to the dimethylamine nitrogen. A two-dimensional rotating frame 1H-1H NOE experiment at the same temperature reveals that the other proton remains with the succinate moiety. Comparison of the 1H and 13C chemical shifts and the 13C T1 relaxation times of the salt with those of the free base further substantiate the findings.

  19. Intermolecular triple proton and deuteron transfer in crystalline 3,5-dimethylpyrazole studied by NMR, NQR, and x-ray methods

    SciTech Connect

    Wehrle, B.; Aguilar-Parrilla, F.; Limbach, H.H. ); de la Concepcion Foces-Foces, M.; Cano, F.H. ); Elguero, J. ); Baldy, A.; Pierrot, M. ); Khurshid, M.M.T.; Larcombe-McDouall, J.B.; Smith, J.A.S. )

    1989-09-13

    A combination of {sup 13}C, {sup 15}N magnetic resonance, {sup 14}N quadrupole double resonance, and x-ray studies of solid 3,5-dimethylpyrazole between 270 and 350 K has shown that the NH...N hydrogen bond units present in the crystal are dynamically disordered, so that each nitrogen atom is on average attached to half a hydrogen atom. The molecules form discrete hydrogen-bonded cyclic trimers, in which the hydrogen atoms move in a double minimum potential energy surface which is symmetrical, to within experimental error. The experimental evidence in this temperature range is consistent with disorder by means of correlated triple hydrogen jumps with an activation energy of 45 kJ mol{sup {minus}1}. There is a large kinetic hydrogen (HHH)/deuterium (DDD) isotope effort of >20 at 299 K and equal to 8 at 347 K.

  20. High resolution NMR study of T1 magnetic relaxation dispersion. III. Influence of spin 1/2 hetero-nuclei on spin relaxation and polarization transfer among strongly coupled protons.

    PubMed

    Korchak, Sergey E; Ivanov, Konstantin L; Pravdivtsev, Andrey N; Yurkovskaya, Alexandra V; Kaptein, Robert; Vieth, Hans-Martin

    2012-09-07

    Effects of spin-spin interactions on the nuclear magnetic relaxation dispersion (NMRD) of protons were studied in a situation where spin ½ hetero-nuclei are present in the molecule. As in earlier works [K. L. Ivanov, A. V. Yurkovskaya, and H.-M. Vieth, J. Chem. Phys. 129, 234513 (2008); S. E. Korchak, K. L. Ivanov, A. V. Yurkovskaya, and H.-M. Vieth, ibid. 133, 194502 (2010)], spin-spin interactions have a pronounced effect on the relaxivity tending to equalize the longitudinal relaxation times once the spins become strongly coupled at a sufficiently low magnetic field. In addition, we have found influence of (19)F nuclei on the proton NMRD, although in the whole field range, studied protons and fluorine spins were only weakly coupled. In particular, pronounced features in the proton NMRD were found; but each feature was predominantly observed only for particular spin states of the hetero-nuclei. The features are explained theoretically; it is shown that hetero-nuclei can affect the proton NMRD even in the limit of weak coupling when (i) protons are coupled strongly and (ii) have spin-spin interactions of different strengths with the hetero-nuclei. We also show that by choosing the proper magnetic field strength, one can selectively transfer proton spin magnetization between spectral components of choice.

  1. Proton and fluorine NMR imaging for the assessment of myocardial perfusion

    SciTech Connect

    Horner, B.S.D.

    1985-01-01

    A high field, small bore NMR spectrometer was converted to an imaging system for the detection of fluorine and protons in phantoms and small biological samples. The modified spectrometer system was used to image various phantoms for the assessment of imaging performance. After assessment of the imaging system performance, a water soluble fluorinated compound of relatively low toxicity was investigated for use as an imaging agent for the detection of myocardial perfusion. New Zealand white rabbits were used as the model. Hearts were rapidly extracted and hung via the aorta to a perfusion apparatus which was capable of prolonging heart function throughout the course of the experiment. Perfusion with a standard nutrient solution was followed either by perfusion with a solution to which the fluorinated compound had been added or by ligation of the left coronary artery with subsequent perfusion with the fluorinated compound in perfusate solution. The hearts were then sectioned and imaged. The ligation of the left coronary artery produced a region of impaired perfusion in the left ventricular wall and parts of the septum. The regions of reduced perfusion appeared in the F-19 NMR images as areas of reduced intensity. Proton images of the tissue sections were also obtained for comparison. It was found that infarcted regions may be best visualized by combining the fluorine and proton images. Infarct damage was verified by Gentian violet stain. Relaxation times of fluorine and protons were measured both in perfused tissue and in various concentration solutions.

  2. Proton-bound dimers of 1-methylcytosine and its derivatives: vibrational and NMR spectroscopy.

    PubMed

    Ung, Hou U; Moehlig, Aaron R; Kudla, Ryan A; Mueller, Leonard J; Oomens, Jos; Berden, Giel; Morton, Thomas Hellman

    2013-11-21

    Vibrational spectroscopy and NMR demonstrate that the proton-bound dimer of 1-methylcytosine, 1, has an unsymmetrical structure at room temperature. In the gas phase, investigation of isolated homodimer 1 reveals five fundamental NH vibrations by IR Multiple Photon Dissociation (IRMPD) action spectroscopy. The NH···N stretching vibration between the two ring nitrogens exhibits a frequency of 1570 cm(-1), as confirmed by examination of the proton-bound homodimers of 5-fluoro-1-methycytosine, 2, and of 1,5-dimethylcytosine, 3, which display absorptions in the same region that disappear upon deuterium substitution. (13)C, and (15)N NMR of the solid iodide salt of 1 confirm the nonequivalence of the two rings in the anhydrous proton-bound homodimer at room temperature. IRMPD spectra of the three possible heterodimers also show NH···N stretches in the same domain, and at least one of the heterodimers, the proton-bound dimer of 1,5-dimethylcytosine with 1-methylcytosine, exhibits two bands suggestive of the presence of two tautomers close in energy.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

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

    SciTech Connect

    Zilm, K.W.

    1989-01-01

    This report covers the progress made on the title project and summarizes the accomplishments for the project period. Four major areas of inquiry have been pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coal models. Along the same lines the author are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. The effects of very high MAS rates (>10 kHz) on cross polarization dynamics are also being investigated for similar reasons. During the last quarter the authors has concentrated on improvements in cross polarization (CP) sequences with a goal of making the CP process insensitive to experimental conditions such as the Hartmann-Hahn mismatch. It has been found that the usual theories of CP are incorrect, and that the CP process is very heterogeneous in nature. This has significant implications on methods typically used in quantifying {sup 13}C CPMAS spectra of coals. 19 refs., 11 figs.

  6. Characterization of the protonic distribution and environment in amorphous silicon-hydrogen alloys using proton NMR and ESR

    SciTech Connect

    Jeffrey, F.R.; Lowry, M.E.; Garcia, M.L.S.; Barnes, R.G.; Torgeson, D.E.

    1981-06-01

    We present magnetic resonance data from a series of a-Si(H) samples deposited under varied hydrogen partial pressures. This parameter has been shown to be directly related to the sample-wide average proton density. The other sputtering parameters were maintained such that no dihydride bonding (as determined by the 890 cm/sup -1/ir bending mode) is present. Measurements presented are the NMR absorption spectrum (from the Fourier transform of the free induction decay), relaxation time T/sub 1/, and ESR absorption. The NMR absorption spectrum identifies two distinct forms of H incorporation. One is a tightly clustered form, such as H bonded on the inner surface of a microvoid of maximum dimension 5A, while the other is a randomly distributed phase with local H density of 3.5 x 10/sup 21/ cm/sup -3/. The distributed phase H density is independent of the sample-wide average, indicating a fixed composition phase which occupies a larger percentage of the sample as H pressure is increased during deposition. This phase appears to extend to a maximum of 88% of the sample. The protonic spin-lattice relaxation time (T/sub 1/) measures the coupling of the spin system to its enviroment, ''the lattice''. For the series of samples, we find that T/sub 1/ first increases from 2.8 s to 44.8 s with increasing H content and then decreases to 8.1 s as H density is further increased. In an effort to understand this unusual relaxation behavior, we have made temperature dependant T/sub 1/ and ESR measurements. Utilizing these results, the protonic relaxation mechanism is discussed in terms ''disorder mode'' and electronic state models.

  7. Ab initio study of {sup 13}C NMR chemical shifts for the chromophores of rhodopsin and bacteriorhodopsin. 2. Comprehensive analysis of the {sup 13}C chemical shifts of protonated all-trans-retinylidene Schiff base

    SciTech Connect

    Sakurai, Minoru; Wada, Mitsuhito; Inoue, Yoshio; Tamura, Yusuke; Watanabe, Yoichi

    1996-02-01

    Theoretical analysis was performed for the {sup 13}C chemical shifts of the retinal chromophore in bacteriorhodopsin (bR) by means of ab initio NMR shielding calculation, based on the localized orbital/ local origin method. In order to comprehensively investigate the correlation between the {sup 13}C chemical shieldings of the unsaturated carbons and physicochemical perturbations relating to the spectral tuning of bacteriorhodopsin, the following three factors are taken into account in the present calculation: (1) change in strength of the hydrogen bonding between protonated retinylidene Schiff base and its counterion, (2) conformational changes about single bonds of the conjugated chain, and (3) electrostatic interactions between the Schiff base and electric dipoles. On the basis of these calculations, we successfully find a molecular model for which the shielding calculation almost completely reproduces the observed chemical shift data for the chromophore of bR. 47 refs., 13 figs.

  8. Quantification of Water-Soluble Metabolites in Medicinal Mushrooms Using Proton NMR Spectroscopy.

    PubMed

    Lo, Yu-Chang; Chien, Shih-Chang; Mishchuk, Darya O; Slupsky, Carolyn M; Mau, Jeng-Leun

    2016-01-01

    The water-soluble metabolites in 5 mushrooms were identified and quantified using proton nuclear magnetic resonance (NMR) spectroscopy and software for targeted metabolite detection and quantification. In total, 35 compounds were found in Agaricus brasiliensis, 25 in Taiwanofungus camphoratus, 23 in Ganoderma lucidum (Taiwan) and Lentinus edodes, and 16 in G. lucidum (China). Total amounts of all identified metabolites in A. brasiliensis, T. camphoratus, G. lucidum, G. lucidum (China), and L. edodes were 149,950.51, 12,834.18, 9,549.09, 2,788.41, and 111,726.51 mg/kg dry weight, respectively. These metabolites were categorized into 4 groups: free amino acids and derivatives, carbohydrates, carboxylic acids, and nucleosides. Carbohydrates were the most abundant metabolites among all 4 groups, with mannitol having the highest concentration among all analyzed metabolites (848-94,104 mg/kg dry weight). Principal components analysis (PCA) showed obvious distinction among the metabolites of the 5 different kinds of mushrooms analyzed in this study. Thus PCA could provide an optional analytical way of identifying and recognizing the compositions of flavor products. Furthermore, the results of this study demonstrate that NMRbased metabolomics is a powerful tool for differentiating between various medicinal mushrooms.

  9. Probing microstructure evolution during the hardening of gypsum by proton NMR relaxometry.

    PubMed

    Jaffel, Hamouda; Korb, Jean-Pierre; Ndobo-Epoy, Jean-Philippe; Morin, Vincent; Guicquero, Jean-Pierre

    2006-04-13

    We report a comprehensive proton NMR relaxation study of the water confined in the evolving porous structure of hardened gypsum prepared with different water-to-plaster ratios (w/p) and increasing additions of crushed gypsum. This study gives some new information on the microstructure, the water distribution, and the hydration kinetics without any drying or perturbing preparation. The bi-exponential transverse magnetization decay reveals the existence of two water populations in slow exchange. However, the different behaviors of these populations during saturation and desaturation experiments show evidence of a fast exchange of each population with the surface. Two modes of organization of the microstructure of this material are identified through an original model of exchange as a function of the water-to-plaster ratio (0.4 < or = w/p < or = 0.6 and 0.7 < or = w/p < or = 1). A clear gap is shown in the exchange rate value above w/p = 0.6 that could be representative of a percolation threshold. Both the method and the theory presented can be applied more widely to other porous media with reactive surface areas.

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

    PubMed

    Chaudhari, Sachin Rama; Suryaprakash, N

    2015-04-07

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

  11. NMR studies of exocyclic 1,N sup 2 -propanodeoxyguanosine adducts (X) opposite purines in DNA duplexes: Protonated X(syn)ter dot A(anti) pairing (acidic pH) and X(syn)ter dot G(anti) pairing (neutral pH) at the lesion site

    SciTech Connect

    Kouchakdjian, M.; Gao, X.; Patel, D. ); Marinelli, E.; Johnson, F.; Grollman, A. )

    1989-06-27

    Proton and phosphorus two-dimensional NMR studies are reported for the complementary d(C1-A2-T3-G4-X5-G6-T7-A8-C9){center dot}d(G10-T11-A12-C13-A14-C15-A16-T17-G18) nonanucleotide duplex (designated X{center dot}A 9-mer) that contains a 1,N{sup 2}-propanodeoxyguanosine exocyclic adduct, X5, opposite deoxyadenosine A14 in the center of the helix. The NMR studies detect a pH-dependent conformational transition; this paper focuses on the structure present at pH 5.8. The two-dimensional NOESY studies of the X{center dot}A 9-mer duplex in H{sub 2}O and D{sub 2}O solution establish that X5 adopts a syn orientation while A14 adopts an anti orientation about the glycosidic bond at the lesion site. At pH 5.8, the observed NOE between the H8 proton of X5 and the H2 proton of A14 in the X{center dot}A 9-mer duplex demonstrates unequivocally the formation of the protonated X5(syn){center dot}A14(anti) pair. A perturbation in the phosphodiester backbone is detected at the C13-A14 phosphorus located at the lesion site by {sup 31}P NMR spectroscopy. The two-dimensional NMR studies have been extended to the related complementary X{center dot}G 9-mer duplex that contains a central X5{center dot}G14 lesion in a sequence that is otherwise identical with the X{center dot}A 9-mer duplex. The NMR experimental parameters are consistent with formation of a pH-independent X5(syn){center dot}G14(anti) pair stabilized by two hydrogen bonds with the 1,N{sup 2}-propano exocyclic adduct of X5(syn) located in the major groove.

  12. Natural-abundance 15N NMR studies of Turkey ovomucoid third domain. Assignment of peptide 15N resonances to the residues at the reactive site region via proton-detected multiple-quantum coherence

    NASA Astrophysics Data System (ADS)

    Ortiz-Polo, Gilberto; Krishnamoorthi, R.; Markley, John L.; Live, David H.; Davis, Donald G.; Cowburn, David

    Heteronuclear two-dimensional 1H{ 15N} multiple-quantum (MQ) spectroscopy has been applied to a protein sample at natural abundance: ovomucoid third domain from turkey ( Meleagris gallopavo), a serine proteinase inhibitor of 56 amino acid residues. Peptide amide 1H NMR assignments obtained by two-dimensional 1H{ 1H} NMR methods (R. Krishnamoorthi and J. L. Markley, unpublished data) led to identification of the corresponding 1H{ 15N} MQ coherence cross peaks. From these, 15N NMR chemical shifts were determined for several specific backbone amide groups of amino acid residues located around the reactive site region of the inhibitor. The results suggest that amide 15N chemical shifts, which are readily obtained in this way, may serve as sensitive probes for conformational studies of proteins.

  13. Beta-alanine-oxalic acid (1:1) hemihydrate crystal: structure, 13C NMR and vibrational properties, protonation character.

    PubMed

    Godzisz, D; Ilczyszyn, M; Ilczyszyn, M M

    2003-03-01

    The crystal structure of beta-alanine-oxalic acid (1:1) hemihydrate complex has been reinvestigated by X-ray diffraction method at 293 K. Formation of monoclinic crystal system belonging to C2/c space group and consisting of semi-oxalate chains, diprotonated beta-alanine dimers and water molecules bonded to both these units is confirmed. New results are obtained for distances in the carboxylic groups and hydrogen bonds. These structural observations are used for protonation degree monitoring on the carboxylic oxygen atoms. They are in accordance with our vibrational study. The 13C NMR spectra provide insights into the solid structure of this complex, character of its hydrogen bonds and the beta-alanine protonation.

  14. Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy

    SciTech Connect

    Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy

    2015-10-14

    Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110–120 kHz), {sup 1}H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong {sup 1}H–{sup 1}H homonuclear dipolar couplings and narrow {sup 1}H chemical shift (CS) ranges, which render it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) {sup 1}H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about {sup 1}H–{sup 1}H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic

  15. Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Mroue, Kamal H; Ramamoorthy, Ayyalusamy

    2015-10-14

    Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110-120 kHz), (1)H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong (1)H-(1)H homonuclear dipolar couplings and narrow (1)H chemical shift (CS) ranges, which render it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) (1)H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about (1)H-(1)H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic-level structural and dynamical

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

    PubMed

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

    2010-01-01

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

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

    PubMed Central

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

    2009-01-01

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

  18. Fast proton exchange in histidine: measurement of rate constants through indirect detection by NMR spectroscopy.

    PubMed

    Sehgal, Akansha Ashvani; Duma, Luminita; Bodenhausen, Geoffrey; Pelupessy, Philippe

    2014-05-19

    Owing to its imidazole side chain, histidine participates in various processes such as enzyme catalysis, pH regulation, metal binding, and phosphorylation. The determination of exchange rates of labile protons for such a system is important for understanding its functions. However, these rates are too fast to be measured directly in an aqueous solution by using NMR spectroscopy. We have obtained the exchange rates of the NH3(+) amino protons and the labile NH(ε2) and NH(δ1) protons of the imidazole ring by indirect detection through nitrogen-15 as a function of temperature (272 Kprotons H(i) and the three one-bond scalar coupling constants (1)J(N,H(i)) could also be determined accurately.

  19. 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

    2015-04-07

    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.

  20. Relativistic force field: parametric computations of proton-proton coupling constants in (1)H NMR spectra.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2014-09-05

    Spin-spin coupling constants in (1)H NMR carry a wealth of structural information and offer a powerful tool for deciphering molecular structures. However, accurate ab initio or DFT calculations of spin-spin coupling constants have been very challenging and expensive. Scaling of (easy) Fermi contacts, fc, especially in the context of recent findings by Bally and Rablen (Bally, T.; Rablen, P. R. J. Org. Chem. 2011, 76, 4818), offers a framework for achieving practical evaluation of spin-spin coupling constants. We report a faster and more precise parametrization approach utilizing a new basis set for hydrogen atoms optimized in conjunction with (i) inexpensive B3LYP/6-31G(d) molecular geometries, (ii) inexpensive 4-31G basis set for carbon atoms in fc calculations, and (iii) individual parametrization for different atom types/hybridizations, not unlike a force field in molecular mechanics, but designed for the fc's. With the training set of 608 experimental constants we achieved rmsd <0.19 Hz. The methodology performs very well as we illustrate with a set of complex organic natural products, including strychnine (rmsd 0.19 Hz), morphine (rmsd 0.24 Hz), etc. This precision is achieved with much shorter computational times: accurate spin-spin coupling constants for the two conformers of strychnine were computed in parallel on two 16-core nodes of a Linux cluster within 10 min.

  1. Interfaces in polymer nanocomposites - An NMR study

    NASA Astrophysics Data System (ADS)

    Böhme, Ute; Scheler, Ulrich

    2016-03-01

    Nuclear Magnetic Resonance (NMR) is applied for the investigation of polymer nanocomposites. Solid-state NMR is applied to study the modification steps to compatibilize layered double hydroxides with non-polar polymers. 1H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T2 is most suited. In this presentation we report on two applications of T2 measurements under external mechanical stress. In a low-field system relaxation NMR studies are performed in-situ under uniaxial stress. High-temperature experiments in a Couette cell permit the investigation of the polymer dynamics in the melt under shear flow.

  2. NMR Methods to Study Dynamic Allostery.

    PubMed

    Grutsch, Sarina; Brüschweiler, Sven; Tollinger, Martin

    2016-03-01

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

  3. NMR Methods to Study Dynamic Allostery

    PubMed Central

    Grutsch, Sarina; Brüschweiler, Sven; Tollinger, Martin

    2016-01-01

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

  4. Rapid acquisition of wideline MAS solid-state NMR spectra with fast MAS, proton detection, and dipolar HMQC pulse sequences.

    PubMed

    Rossini, Aaron J; Hanrahan, Michael P; Thuo, Martin

    2016-09-14

    The solid-state NMR spectra of many NMR active elements are often extremely broad due to the presence of chemical shift anisotropy (CSA) and/or the quadrupolar interaction (for nuclei with spin I > 1/2). These NMR interactions often give rise to wideline solid-state NMR spectra which can span hundreds of kHz or several MHz. Here we demonstrate that by using fast MAS, proton detection and dipolar hetero-nuclear multiple-quantum (D-HMQC) pulse sequences, it is possible to rapidly acquire 2D spectra which correlate (1)H chemical shifts to the indirectly detected wideline MAS powder patterns of dipolar coupled hetero-nuclei. The D-HMQC pulse sequence enables broadband excitation of the wideline hetero-nuclear NMR spectrum and provides higher sensitivity by detecting the narrower and more sensitive (1)H NMR signal. This approach is demonstrated for the rapid acquisition of 2D (1)H detected (195)Pt solid-state NMR spectra of cisplatin and transplatin and the (71)Ga solid-state NMR spectrum of a self-assembled Ga coordination polymer of unconfirmed structure. This approach should be broadly applicable for the rapid acquisition of wideline MAS solid-state NMR spectra of moderately abundant NMR nuclei.

  5. Multinuclear NMR studies of gaseous and liquid sevoflurane

    NASA Astrophysics Data System (ADS)

    Macięga, E.; Makulski, W.; Jackowski, K.; Blicharska, B.

    2006-03-01

    For the first time, a small amount of sevoflurane ((CF 3) 2CHOCH 2F) in carbon dioxide and xenon as the gaseous solvents has been studied using 19F and 1H NMR spectra. Density-dependent 19F and 1H nuclear magnetic shielding was observed when the pressure of each solvent was increased. After extrapolation of the results to the zero-density limit it was possible to determine the appropriate shielding constants free from intermolecular interactions, σ0(F) and σ0(H). Similar procedure has also been applied for the investigation of fluorine-proton spin-spin couplings and the 2J 0(FH) and 3J 0(FH) constants of an isolated (CF 3) 2CHOCH 2F molecule were also obtained. Additionally, high-resolution 1H, 13C, 17O and 19F NMR spectra of pure liquid sevoflurane were also recorded and all the 1H- 13C, 1H- 19F and 19F- 13C spin-spin coupling constants and NMR chemical shifts were measured. It is shown that the experimental NMR parameters are suitable for comparison with the results of recent quantum-chemical calculations.

  6. Orientation-dependent proton double-quantum NMR build-up function for soft materials with anisotropic mobility.

    PubMed

    Naumova, Anna; Tschierske, Carsten; Saalwächter, Kay

    In recent years, the analysis of proton double-quantum NMR build-up curves has become an important tool to quantify anisotropic mobility in different kinds of soft materials such as polymer networks or liquid crystals. In the former case, such data provides a measure of orientation-dependent residual (time-averaged) dipolar couplings arising from anisotropic segmental motions, informing about the length and the state of local stretching of the network chains. Previous studies of macroscopically ordered, i.e. stretched, networks were subject to the limitation that a detailed build-up curve analysis on the basis of a universal "Abragam-like" (A-l) build-up function valid for a proton multi-spin system was only possible for an isotropic orientation-averaged response. This situation is here remedied by introducing a generic orientation-dependent build-up function for an anisotropically mobile protonated molecular segment. We discuss an application to the modeling of data for a stretched network measured at different orientations with respect to the magnetic field, and present a validation by fitting data of different liquid-crystal molecules oriented in the magnetic field.

  7. Charge transport studies of proton and ion conducting materials

    NASA Astrophysics Data System (ADS)

    Versek, Craig Wm

    The development of a high-throughput impedance spectroscopy instrumentation platform for conductivity characterization of ion transport materials is outlined. Collaborative studies using this system are summarized. Charge conduction mechanisms and conductivity data for small molecule proton conducting liquids, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, and select mixtures of these compounds are documented. Furthermore, proton diffusivity measurements using a Pulse Field Gradient Nuclear Magnetic Resonance (PFG NMR) technique for imidazole and 1,2,3-triazole binary mixtures are compared. Studies of azole functionalized discotic and linear mesogens with conductivity, structural, and thermal characterizations are detailed.

  8. NMR studies on an oligodeoxynucleotide containing 2-aminopurine opposite adenine

    SciTech Connect

    Fazakerley, G.V.; Sowers, L.C.; Eritja, R.; Kaplan, B.E.; Goodman, M.F.

    1987-09-08

    A heteroduplex containing the mismatch 2-aminopurine (AP)-adenine has been synthesized and studied by proton NMR. The mismatch was incorporated into the sequence d(CGG(AP)GGC) x d-(GCCACCG). One-dimensional nuclear Overhauser effect measurements in H/sub 2/O and two-dimensional nuclear Overhauser effect spectra in D/sub 2/O show AP x A base pairs in a wobble structure in which both bases are in the anti conformation. The adenine is stacked well in the helix, but the helix twist between the adenine and neighboring cytosine in the 3' direction is unusually small. As a result, the aminopurine on the opposite strand is somewhat pushed out of the helix. From the measurements of the imino proton line widths, the two adjacent G x C base pairs are not found to be significantly destabilized by the presence of the purine-purine wobble pair.

  9. 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.

  10. NMR structural studies on antifreeze proteins.

    PubMed

    Sönnichsen, F D; Davies, P L; Sykes, B D

    1998-01-01

    Antifreeze proteins (AFPs) are a structurally diverse class of proteins that bind to ice and inhibit its growth in a noncolligative manner. This adsorption-inhibition mechanism operating at the ice surface results in a lowering of the (nonequilibrium) freezing point below the melting point. A lowering of approximately 1 degree C, which is sufficient to prevent fish from freezing in ice-laden seawater, requires millimolar AFP levels in the blood. The solubility of AFPs at these millimolar concentrations and the small size of the AFPs (typically 3-15 kDa) make them ideal subjects for NMR analysis. Although fish AFPs are naturally abundant, seasonal expression, restricted access to polar fishes, and difficulties in separating numerous similar isoforms have made protein expression the method of choice for producing AFPs for structural studies. Expression of recombinant AFPs has also facilitated NMR analysis by permitting isotopic labeling with 15N and 13C and has permitted mutations to be made to help with the interpretation of NMR data. NMR analysis has recently solved two AFP structures and provided valuable information about the disposition of ice-binding side chains in a third. The potential exists to solve other AFP structures, including the newly described insect AFPs, and to use solid-state NMR techniques to address fundamental questions about the nature of the interaction between AFPs and ice.

  11. New insight into hydration and aging mechanisms of paper by the line shape analysis of proton NMR spectra

    NASA Astrophysics Data System (ADS)

    Mallamace, D.; Vasi, S.; Missori, M.; Corsaro, C.

    2016-05-01

    The action of water within biological systems is strictly linked either with their physical chemical properties and with their functions. Cellulose is one of the most studied biopolymers due to its biological importance and its wide use in manufactured products. Among them, paper is mainly constituted by an almost equimolar ratio of cellulose and water. Therefore the study of the behavior of water within pristine and aged paper samples can help to shed light on the degradation mechanisms that irremediably act over time and spoil paper. In this work we present Nuclear Magnetic Resonance (NMR) experiments on modern paper samples made of pure cellulose not aged and artificially aged as well as on ancient paper samples made in 1413 in Perpignan (France). The line shape parameters of the proton NMR spectra were studied as a function of the hydration content. Results indicate that water in aged samples is progressively involved in the hydration of the byproducts of cellulose degradation. This enhances the degradation process itself through the progressive consumption of the cellulose amorphous regions.

  12. Sequence dependence of base-pair stacking in right-handed DNA in solution: proton nuclear Overhauser effect NMR measurements.

    PubMed Central

    Patel, D J; Kozlowski, S A; Bhatt, R

    1983-01-01

    Single-crystal x-ray studies of d(C-G-C-G-A-A-T-T-C-G-C-G) exhibit base-pair propeller twisting [Dickerson, R. E. & Drew, H. R. (1981) J. Mol. Biol. 149, 761-786] that results in close contacts between adjacent purines in the minor groove in pyrimidine (3'-5')-purine steps and in the major groove in purine (3'-5')-pyrimidine steps [Calladine, C. R. (1982) J. Mol. Biol. 161, 343-362]. These observations require an approximately 3.4 A separation between the minor groove edges of adenosines on adjacent base pairs for the dA-dA step but predict a smaller separation for the dT-dA step and a larger separation for the dA-dT step in a D(A-T-T-A).d(T-A-A-T) fragment. We have confirmed these predictions from steady-state nuclear Overhauser effect measurements between assigned minor groove adenosine H-2 protons on adjacent base pairs in the proton NMR spectrum of the d(C1-G2-A3-T4-T5-A6-T6-A5-A4-T3-C2-G1) self-complementary dodecanucleotide duplex (henceforth called the Pribnow 12-mer) in solution. The measured cross-relaxation rates (product of steady-state nuclear Overhauser effect and selective spin- lattice relaxation rates) translate to interproton separations between adjacent adenosine H-2 protons of 4.22 A in the (dA3-dT4).(dA4-dT3) step, of 3.56 A in the (dT4-dT5).dA5-dA4) step, and of 3.17 A in the (dT5-dA6).(dT6-dA5) step for the Pribnow 12-mer duplex with an isotropic rotational correlation time of 9 ns at 5 degrees C. These proton NMR results show that the sequence-dependent base-pair stacking resulting from base-pair propeller twisting of defined handedness for right-handed DNA in the solid state is maintained in aqueous solution. PMID:6575384

  13. The Structural Response of Polyelectrolyte Dendrimer toward the Molecular Protonation: The Inconsistence Revealed by SANS and NMR

    SciTech Connect

    Chen, Wei-Ren; Herwig, Kenneth W; Hong, Kunlun; Li, Xin; Liu, Emily; Liu, Yun; Porcar, L.; Shew, Chwen-Yang; Smith, Gregory Scott; Wu, Bin; Liu, Dazhi; Gao, Carrie Y

    2012-01-01

    Polyamidoamine (PAMAM) dendrimers and their charged state in deuterium oxide have been investigated with diffusion NMR and small angle neutron scattering (SANS) techniques. NMR measurement suggests that, upon increasing the molecular protonation by progressive acidification of solutions, significant variation of hydrodynamic radius, calculated by the Stokes-Einstein relation with given surface condition, is observed upon increasing the molecular protonation. However, comparative SANS experiment indicates little dependence of dendrimer global size, in terms of radius of gyration, on molecular protonation. This observed inconsistence indicates the necessity of incorporating the effect of molecular interface modification by dressed counterion, when dynamical measurements are used for determination the structural characteristics of ionic soft colloids even in a dilute enough suspension.

  14. 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.

  15. 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.

  16. 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.

  17. ADVANCED SOLIDS NMR STUDIES OF COAL STRUCTURE AND CHEMISTRY

    SciTech Connect

    1997-03-01

    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. 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 methane groups, identification of carbons adjacent to nitrogen and sites with exchangeable protons, and methods to more finely characterize the distribution of hydrogen in coals. The motivation for investigating these specific structural features of coals arises from their relevance to the chemical reactivity of coals, and their suitability for possible correlations with the oil sourcing potential 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. In this report period we have focused our work on 1 segment of the program. Our last report outlined progress in using our NMR editing methods with higher field operation where higher magic angle spinning rates are required. Significant difficulties were identified, and these have been the main subject of study during the most recent granting period.

  18. Proton NMR of isomorphous paramagnetic and diamagnetic monohydrates MeSO4.1 H2O Me = Mn2+, Fe2+, Ni2+ AND Mg2+

    NASA Astrophysics Data System (ADS)

    Murín, J.; Olčák, D.; Oravcová, J.; Rákoš, M.; Jelšovská, K.

    1981-03-01

    Nuclear magnetic resonance of protons of crystallization water in isomorphous paramagnetic and diamagnetic monohydrates MeSO4. 1 H2O with Me = Mn2+, Fe2+, Ni2+ and Mg2+ is studied in the present paper. Proton NMR spectra in paramagnetic hydrates are asymmetric and their second moments, M2, depend linearly on the square of the induction of the external magnetic field B0. NMR spectrum of diamagnetic hydrate MgSO4. 1 H2O is symmetric and its shape and the second moment do not change with B0. The parameters M20 and K which characterize nuclear dipole-dipole interaction of protons and interaction of protons and paramagnetic ions, respectively, are derived from experimentally obtained dependences M2 vs B{0/2} and on the other hand, they are calculated by means of crystallographic data for substances studied. Calculations were realized in approximation where two nearest neighbour ions Me2+ to each water molecule are considered. The influence of the demagnetizing magnetic field of the sample was neglected.

  19. Proton decay studies at HRIBF

    SciTech Connect

    Batchelder, J. C.; Bingham, C. R.; Rykaczewski, K.; Toth, K. S.; Mas, J. F.; McConnell, J. W.; Yu, C.-H.; Davinson, T.; Slinger, R. C.; Woods, P. J.; Ginter, T. N.; Gross, C. J.; Grzywacz, R.; Kim, S. H.; Weintraub, W.; Janas, Z.; Karny, M.; MacDonald, B. D.; Piechaczek, A.; Zganjar, E. F.

    1998-12-21

    A double-sided Si-strip detector system has been installed and commissioned at the focal plane of the Recoil Mass Spectrometer at the Holifield Radioactive Ion Beam Facility. The system can be used for heavy charged particle emission studies with half-lives as low as a few {mu}sec. In this paper we present identification and study of the decay properties of the five new proton emitters: {sup 140}Ho, {sup 141m}Ho, {sup 145}Tm, {sup 150m}Lu and {sup 151m}Lu.

  20. Proton decay studies at HRIBF

    SciTech Connect

    Batchelder, J.C.; Bingham, C.R.; Rykaczewski, K.; Toth, K.S.; Mas, J.F.; McConnell, J.W.; Yu, C.; Bingham, C.R.; Grzywacz, R.; Kim, S.H.; Weintraub, W.; Rykaczewski, K.; Janas, Z.; Karny, M.; Davinson, T.; Slinger, R.C.; Woods, P.J.; Ginter, T.N.; Gross, C.J.; MacDonald, B.D.; Piechaczek, A.; Zganjar, E.F.; Ressler, J.J.; Walters, W.B.; Szerypo, J.

    1998-12-01

    A double-sided Si-strip detector system has been installed and commissioned at the focal plane of the Recoil Mass Spectrometer at the Holifield Radioactive Ion Beam Facility. The system can be used for heavy charged particle emission studies with half-lives as low as a few {mu}sec. In this paper we present identification and study of the decay properties of the five new proton emitters: {sup 140}Ho, {sup 141m}Ho, {sup 145}Tm, {sup 150m}Lu and {sup 151m}Lu. {copyright} {ital 1998 American Institute of Physics.}

  1. Solid state NMR studies of materials for energy technology

    NASA Astrophysics Data System (ADS)

    Nambukara Kodiweera Arachchilage, Chandana K.

    Presented in this dissertation are NMR investigations of the dynamical and structural properties of materials for energy conversion and storage devices. 1H and 2H NMR was used to study water and methanol transportation in sulfonated poly(arylene ether ketone) based membranes for direct methanol fuel cells (DMFC). These results are presented in chapter 3. The amount of liquid in the membrane and ion exchange capacity (IEC) are two main factors that govern the dynamics in these membranes. Water and methanol diffusion coefficients also are comparable. Chapters 4 and 5 are concerned with 31P and 1H NMR in phosphoric acid doped PBI membranes (para-PBI and 2OH-PBI) as well as PBI membranes containing ionic liquids (H3PO4/PMIH2PO4/PBI). These membranes are designed for higher-temperature fuel cell operation. In general, stronger short and long range interactions were observed in the 2OH-PBI matrix, yielding reduced proton transport compared to that of para-PBI. In the case of H3PO4/PMIH2PO 4/PBI, both conductivity and diffusion are higher for the sample with molar ratio 2/4/1. Finally, chapter 6 is devoted to the 31P NMR MAS study of phosphorus-containing structural groups on the surfaces of micro/mesoporous activated carbons. Two spectral features were observed and the narrow feature identifies surface phosphates while the broad component identifies heterogeneous subsurface phosphorus environments including phosphate and more complex structure multiple P-C, P-N and P=N bonds.

  2. Symmetrization of cationic hydrogen bridges of protonated sponges induced by solvent and counteranion interactions as revealed by NMR spectroscopy.

    PubMed

    Pietrzak, Mariusz; Wehling, Jens P; Kong, Shushu; Tolstoy, Peter M; Shenderovich, Ilya G; López, Concepción; Claramunt, Rosa María; Elguero, José; Denisov, Gleb S; Limbach, Hans-Heinrich

    2010-02-01

    The properties of the intramolecular hydrogen bonds of doubly (15)N-labeled protonated sponges of the 1,8-bis(dimethylamino)naphthalene (DMANH(+)) type have been studied as a function of the solvent, counteranion, and temperature using low-temperature NMR spectroscopy. Information about the hydrogen-bond symmetries was obtained by the analysis of the chemical shifts delta(H) and delta(N) and the scalar coupling constants J(N,N), J(N,H), J(H,N) of the (15)NH(15)N hydrogen bonds. Whereas the individual couplings J(N,H) and J(H,N) were averaged by a fast intramolecular proton tautomerism between two forms, it is shown that the sum |J(N,H)+J(H,N)| generally represents a measure of the hydrogen-bond strength in a similar way to delta(H) and J(N,N). The NMR spectroscopic parameters of DMANH(+) and of 4-nitro-DMANH(+) are independent of the anion in the case of CD(3)CN, which indicates ion-pair dissociation in this solvent. By contrast, studies using CD(2)Cl(2), [D(8)]toluene as well as the freon mixture CDF(3)/CDF(2)Cl, which is liquid down to 100 K, revealed an influence of temperature and of the counteranions. Whereas a small counteranion such as trifluoroacetate perturbed the hydrogen bond, the large noncoordinating anion tetrakis[3,5-bis(trifluoromethyl)phenyl]borate B[{C(6)H(3)(CF(3))(2)}(4)](-) (BARF(-)), which exhibits a delocalized charge, made the hydrogen bond more symmetric. Lowering the temperature led to a similar symmetrization, an effect that is discussed in terms of solvent ordering at low temperature and differential solvent order/disorder at high temperatures. By contrast, toluene molecules that are ordered around the cation led to typical high-field shifts of the hydrogen-bonded proton as well as of those bound to carbon, an effect that is absent in the case of neutral NHN chelates.

  3. Mechanism of adenylate kinase. Demonstration of a functional relationship between aspartate 93 and Mg2+ by site-directed mutagenesis and proton, phosphorus-31, and magnesium-25 NMR.

    PubMed

    Yan, H G; Tsai, M D

    1991-06-04

    Earlier magnetic resonance studies suggested no direct interaction between Mg2+ ions and adenylate kinase (AK) in the AK.MgATP (adenosine 5'-triphosphate) complex. However, recent NMR studies concluded that the carboxylate of aspartate 119 accepts a hydrogen bond from a water ligand of the bound Mg2+ ion in the muscle AK.MgATP complex [Fry, D.C., Kuby, S.A., & Mildvan, A.S. (1985) Biochemistry 24, 4680-4694]. On the other hand, in the 2.6-A crystal structure of the yeast AK.MgAP5A [P1,P5-bis(5'-adenosyl)pentaphosphate] complex, the Mg2+ ion is in proximity to aspartate 93 [Egner, U., Tomasselli, A.G., & Schulz, G.E. (1987) J. Mol. Biol. 195, 649-658]. Substitution of Asp-93 with alanine resulted in no change in dissociation constants, 4-fold increases in Km, and a 650-fold decrease in kcat. Notable changes have been observed in the chemical shifts of the aromatic protons of histidine 36 and a few other aromatic residues. However, the results of detailed analyses of the free enzymes and the AK.MgAP5A complexes by one- and two-dimensional NMR suggested that the changes are due to localized perturbations. Thus it is concluded that Asp-93 stabilizes the transition state by ca. 3.9 kcal/mol. The next question is how. Since proton NMR results indicated that binding of Mg2+ to the AK.AP5A complex induces some changes in the proton NMR signals of WT but not those of D93A, the functional role of Asp-93 should be in binding to Mg2+.(ABSTRACT TRUNCATED AT 250 WORDS)

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

    PubMed

    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.

  5. 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.

  6. Proton-detected solid-state NMR spectroscopy of fully protonated proteins at slow to moderate magic-angle spinning frequencies.

    PubMed

    Mote, Kaustubh R; Madhu, Perunthiruthy K

    2015-12-01

    (1)H-detection offers a substitute to the sensitivity-starved experiments often used to characterize biomolecular samples using magic-angle spinning solid-state NMR spectroscopy (MAS-ssNMR). To mitigate the effects of the strong (1)H-(1)H dipolar coupled network that would otherwise severely broaden resonances, high MAS frequencies (>40kHz) are often employed. Here, we have explored the alternative of stroboscopic (1)H-detection at moderate MAS frequencies of 5-30kHz using windowed version of supercycled-phase-modulated Lee-Goldburg homonuclear decoupling. We show that improved resolution in the (1)H dimension, comparable to that obtainable at high spinning frequencies of 40-60kHz without homonuclear decoupling, can be obtained in these experiments for fully protonated proteins. Along with detailed analysis of the performance of the method on the standard tri-peptide f-MLF, experiments on micro-crystalline GB1 and amyloid-β aggregates are used to demonstrate the applicability of these pulse-sequences to challenging biomolecular systems. With only two parameters to optimize, broadbanded performance of the homonuclear decoupling sequence, linear dependence of the chemical-shift scaling factor on resonance offset and a straightforward implementation under experimental conditions currently used for many biomolecular studies (viz. spinning frequencies and radio-frequency amplitudes), we expect these experiments to complement the current (13)C-detection based methods in assignments and characterization through chemical-shift mapping. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Assignments of proton populations in dough and bread using NMR relaxometry of starch, gluten, and flour model systems.

    PubMed

    Bosmans, Geertrui M; Lagrain, Bert; Deleu, Lomme J; Fierens, Ellen; Hills, Brian P; Delcour, Jan A

    2012-05-30

    Starch-water, gluten-water, and flour-water model systems as well as straight-dough bread were investigated with (1)H NMR relaxometry using free induction decay and Carr-Purcell-Meiboom-Gill pulse sequences. Depending on the degree of interaction between polymers and water, different proton populations could be distinguished. The starch protons in the starch-water model gain mobility owing to amylopectin crystal melting, granule swelling, and amylose leaching, whereas water protons lose mobility due to increased interaction with starch polymers. Heating of the gluten-water sample induces no pronounced changes in proton distributions. Heating changes the proton distributions of the flour-water and starch-water models in a similar way, implying that the changes are primarily attributable to starch gelatinization. Proton distributions of the heated flour-water model system and those of fresh bread crumb are very similar. This allows identifying the different proton populations in bread on the basis of the results from the model systems.

  8. NMR studies of protein structure and dynamics

    NASA Astrophysics Data System (ADS)

    Kay, Lewis E.

    2011-12-01

    Recent advances in solution NMR spectroscopy have significantly extended the spectrum of problems that can now be addressed with this technology. In particular, studies of proteins with molecular weights on the order of 100 kDa are now possible at a level of detail that was previously reserved for much smaller systems. An example of the sort of information that is now accessible is provided in a study of malate synthase G, a 723 residue enzyme that has been a focal point of research efforts in my laboratory. Details of the labeling schemes that have been employed and optimal experiments for extraction of structural and dynamics information on this protein are described. NMR studies of protein dynamics, in principle, give insight into the relation between motion and function. A description of deuterium-based spin relaxation methods for the investigation of side chain dynamics is provided. Examples where millisecond (ms) time scale dynamics play an important role and where relaxation dispersion NMR spectroscopy has been particularly informative, including applications involving the membrane enzyme PagP and mutants of the Fyn SH3 domain that fold on a ms time scale, are presented.

  9. The proton driver design study

    SciTech Connect

    Editors: W. Chou, C.M. Ankenbrandt and E.I. Malamud

    2001-03-08

    In a 1997 summer study, a team led by Steve Holmes formulated a development plan for the Fermilab proton source and described the results in TM-2021. Subsequently, at the end of 1998, a task group was formed to prepare a detailed design of a high intensity facility called the Proton Driver to replace the Fermilab Booster. In the past two years the design effort has attracted more than fifty participants, mostly from the Beams Division. Physicists and engineers from the Technical Division and FESS as well as other institutions, including the Illinois Institute of Technology (IIT), Stanford University, University of Hawaii, CERN in Switzerland, Rutherford Appleton Laboratory in England and the IHEP in Russia also contributed heavily. The results of that effort are summarized in this document describing the design of a 16 GeV synchrotron, two new beam transport lines (a 400 MeV injection line and a 12/16 GeV extraction line), and related improvements to the present negative ion source and the 400 MeV Linac. A construction cost estimate is presented in Appendix A.

  10. NMR spin locking of proton magnetization under a frequency-switched Lee-Goldburg pulse sequence.

    PubMed

    Fu, Riqiang; Tian, Changlin; Cross, Timothy A

    2002-01-01

    The spin dynamics of NMR spin locking of proton magnetization under a frequency-switched Lee-Goldburg (FSLG) pulse sequence is investigated for a better understanding of the line-narrowing mechanism in PISEMA experiments. For the sample of oriented 15N(1,3,5,7)-labeled gramicidin A in hydrated DMPC bilayers, it is found that the spin-lattice relaxation time T(1rho)(H) in the tilted rotating frame is about five times shorter when the 1H magnetization is spin locked at the magic angle by the FSLG sequence compared to the simple Lee-Goldburg sequence. It is believed that the rapid phase alternation of the effective fields during the FSLG cycles results in averaging of the spin lock field so that the spin lock becomes less efficient. A FSLG supercycle has been suggested here to slow the phase alternation. It has been demonstrated experimentally that a modified PISEMA pulse sequence with such supercycles gives rise to about 30% line narrowing in the dipolar dimension in the PISEMA spectra compared to a standard PISEMA pulse sequence.

  11. Site-specific protonation kinetics of acidic side chains in proteins determined by pH-dependent carboxyl (13)C NMR relaxation.

    PubMed

    Wallerstein, Johan; Weininger, Ulrich; Khan, M Ashhar I; Linse, Sara; Akke, Mikael

    2015-03-04

    Proton-transfer dynamics plays a critical role in many biochemical processes, such as proton pumping across membranes and enzyme catalysis. The large majority of enzymes utilize acid-base catalysis and proton-transfer mechanisms, where the rates of proton transfer can be rate limiting for the overall reaction. However, measurement of proton-exchange kinetics for individual side-chain carboxyl groups in proteins has been achieved in only a handful of cases, which typically have involved comparative analysis of mutant proteins in the context of reaction network modeling. Here we describe an approach to determine site-specific protonation and deprotonation rate constants (kon and koff, respectively) of carboxyl side chains, based on (13)C NMR relaxation measurements as a function of pH. We validated the method using an extensively studied model system, the B1 domain of protein G, for which we measured rate constants koff in the range (0.1-3) × 10(6) s(-1) and kon in the range (0.6-300) × 10(9) M(-1) s(-1), which correspond to acid-base equilibrium dissociation constants (Ka) in excellent agreement with previous results determined by chemical shift titrations. Our results further reveal a linear free-energy relationship between log kon and pKa, which provides information on the free-energy landscape of the protonation reaction, showing that the variability among residues in these parameters arises primarily from the extent of charge stabilization of the deprotonated state by the protein environment. We find that side-chain carboxyls with extreme values of koff or kon are involved in hydrogen bonding, thus providing a mechanistic explanation for the observed stabilization of the protonated or deprotonated state.

  12. Proton NMR characterization of isomeric sulfmyoglobins: preparation, interconversion, reactivity patterns, and structural features

    SciTech Connect

    Chatfield, M.J.; La Mar, G.N.; Kauten, R.J.

    1987-11-03

    The preparations of sulfmyoglobin (sulf-Mb) by standard procedures have been found heterogeneous by /sup 1/H NMR spectroscopy. Presented here are the results of a comprehensive study of the factors that influence the selection among the three dominant isomeric forms of sperm whale sulf-Mb and their resulting detailed optical and /sup 1/H NMR properties as related to their detectability and structural properties of the heme pocket. A single isomer is formed initially in the deoxy state; further treatment in any desired oxidation/ligation state can yield two other major isomers. Acid catalysis and chromatography facilitate formation of a second isomer, particularly in the high-spin state. At neutral pH, a third isomer is formed by a first-order process. The processes that alter oxidation/ligation state are found to be reversible and are judged to affect only the metal center, but the three isomeric sulf-Mbs are found to exhibit significantly different ligand affinity and chemical stability. The present results allow, for the first time, a rational approach for preparing a given isomeric sulf-Mb in an optimally pure state for subsequent characterization by other techniques. While optical spectroscopy can distinguish the alkaline forms, only /sup 1/H NMR clearly distinguishes all three ferric isomers. The hyperfine shift patterns in the various oxidation/spin states of sulf-Mbs indicate relatively small structural alteration, and the proximal and distal sides of the heme suggest that peripheral electronic effects are responsible for the differentially reduced ligand affinities for the three isomeric sulf-Mbs. The first /sup 1/H NMR spectra of sulfhemoglobins are presented, which indicate a structure similar to that of the initially formed sulf-Mb isomer but also suggest the presence of a similar molecular heterogeneity as found for sulf-Mb, albiet to a smaller extent.

  13. 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.

  14. Indirect use of deuterium in solution NMR studies of protein structure and hydrogen bonding.

    PubMed

    Tugarinov, Vitali

    2014-02-01

    A description of the utility of deuteration in protein NMR is provided with an emphasis on quantitative evaluation of the effects of deuteration on a number of NMR parameters of proteins: (1) chemical shifts, (2) scalar coupling constants, (3) relaxation properties (R1 and R2 rates) of nuclei directly attached to one or more deuterons as well as protons of methyl groups in a highly deuterated environment, (4) scalar relaxation of 15N and 13C nuclei in 15N-D and 13C-D spin systems as a measure of hydrogen bonding strength, and (5) NOE-based applications of deuteration in NMR studies of protein structure. The discussion is restricted to the 'indirect' use of deuterium in the sense that the description of NMR parameters and properties of the nuclei affected by nearby deuterons (15N, 13C, 1H) is provided rather than those of deuterium itself. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Insights into the distribution of water in a self-humidifying H2/O2 proton-exchange membrane fuel cell using 1H NMR microscopy.

    PubMed

    Feindel, Kirk W; Bergens, Steven H; Wasylishen, Roderick E

    2006-11-01

    Proton ((1)H) NMR microscopy is used to investigate in-situ the distribution of water throughout a self-humidifying proton-exchange membrane fuel cell, PEMFC, operating at ambient temperature and pressure on dry H(2)(g) and O(2)(g). The results provide the first experimental images of the in-plane distribution of water within the PEM of a membrane electrode assembly in an operating fuel cell. The effect of gas flow configuration on the distribution of water in the PEM and cathode flow field is investigated, revealing that the counter-flow configurations yield a more uniform distribution of water throughout the PEM. The maximum power output from the PEMFC, while operating under conditions of constant external load, occurs when H(2)O(l) is first visible in the (1)H NMR image of the cathode flow field, and subsequently declines as this H(2)O(l) continues to accumulate. The (1)H NMR microscopy experiments are in qualitative agreement with predictions from several theoretical modeling studies (e.g., Pasaogullari, U.; Wang, C. Y. J. Electrochem. Soc. 2005, 152, A380-A390), suggesting that combined theoretical and experimental approaches will constitute a powerful tool for PEMFC design, diagnosis, and optimization.

  16. Polymeric proanthocyanidins 13C NMR studies of procyanidins

    Treesearch

    Lawrence J. Porter; Roger H. Newman; Lai Yeap Foo; Herbert Wong; Richard W. Hemingway

    1982-01-01

    Proanthocyanidin polymers have been shown to consist entirely of flavan-3-ol units by a combination of techniques including 13C n.m.r. spectroscopy. The 13C n.m.r. spectra of the polymers and related molecules are now considered in more detail. Prior to this study UC n.m.r. data has been published of procyanidins and...

  17. NMR Relaxation and Diffusion Study of Ultrasound Recycling of Polyurethanes

    NASA Astrophysics Data System (ADS)

    von Meerwall, E.; Ghose, S.; Isayev, A. I.

    2004-04-01

    We have examined the effect of intense ultrasound on unfilled polyurethane foam and rubber using proton NMR transverse relaxation and pulsed-gradient diffusion studies, sol extraction, GPC characterization, and glass transition measurements. Results correlate well with ultrasound amplitude. The proton T2 relaxation at 70.5 deg. C exhibits three discrete components, due to heavily entangled sol and crosslinked network; unentangled polymeric sol plus dangling network chain ends; and oligomer remnants. Devulcanizing produces heavy sol, increases segmental mobility of all species, and generates more dangling chain ends. In foams, but not in rubber, additional light sol is generated at the expense of network. All mobilities are significantly lower than in the other rubbers we have studied, an effect unrelated to the glass transition, nearly constant at -60 deg. C. Diffusion measurements, possible only in foams, show a bimodal spectrum whose fast component slows markedly with ultrasound amplitude, attesting to the production of fragments heavier than the original oligomers, as confirmed by GPC analysis. This work is the first to study ultrasound devulcanization in industrial rubbery foams.

  18. HPLC & NMR-based forced degradation studies of ifosfamide: The potential of NMR in stability studies.

    PubMed

    Salman, D; Peron, J-M R; Goronga, T; Barton, S; Swinden, J; Nabhani-Gebara, S

    2016-03-01

    The aim of this study is to conduct a forced degradation study on ifosfamide under several stress conditions to investigate the robustness of the developed HPLC method. It also aims to provide further insight into the stability of ifosfamide and its degradation profile using both HPLC and NMR. Ifosfamide solutions (20mg/mL; n=15, 20mL) were stressed in triplicate by heating (70°C), under acidic (pH 1 & 4) and alkaline (pH 10 & 12) conditions. Samples were analysed periodically using HPLC and FT-NMR. Ifosfamide was most stable under weakly acidic conditions (pH 4). NMR results suggested that the mechanism of ifosfamide degradation involves the cleavage of the PN bond. For all stress conditions, HPLC was not able to detect ifosfamide degradation products that were detected by NMR. These results suggest that the developed HPLC method for ifosfamide did not detect the degradation products shown by NMR. It is possible that degradation products co-elute with ifosfamide, do not elute altogether or are not amenable to the detection method employed. Therefore, investigation of ifosfamide stability requires additional techniques that do not suffer from the aforementioned shortcomings. Copyright © 2015 Académie Nationale de Pharmacie. Published by Elsevier Masson SAS. All rights reserved.

  19. Flexible and rigid structures in HIV-1 p17 matrix protein monitored by relaxation and amide proton exchange with NMR.

    PubMed

    Ohori, Yuka; Okazaki, Honoka; Watanabe, Satoru; Tochio, Naoya; Arai, Munehito; Kigawa, Takanori; Nishimura, Chiaki

    2014-03-01

    The HIV-1 p17 matrix protein is a multifunctional protein that interacts with other molecules including proteins and membranes. The dynamic structure between its folded and partially unfolded states can be critical for the recognition of interacting molecules. One of the most important roles of the p17 matrix protein is its localization to the plasma membrane with the Gag polyprotein. The myristyl group attached to the N-terminus on the p17 matrix protein functions as an anchor for binding to the plasma membrane. Biochemical studies revealed that two regions are important for its function: D14-L31 and V84-V88. Here, the dynamic structures of the p17 matrix protein were studied using NMR for relaxation and amide proton exchange experiments at the physiological pH of 7.0. The results revealed that the α12-loop, which includes the 14-31 region, was relatively flexible, and that helix 4, including the 84-88 region, was the most protected helix in this protein. However, the residues in the α34-loop near helix 4 had a low order parameter and high exchange rate of amide protons, indicating high flexibility. This region is probably flexible because this loop functions as a hinge for optimizing the interactions between helices 3 and 4. The C-terminal long region of K113-Y132 adopted a disordered structure. Furthermore, the C-terminal helix 5 appeared to be slightly destabilized due to the flexible C-terminal tail based on the order parameters. Thus, the dynamic structure of the p17 matrix protein may be related to its multiple functions.

  20. Entangled Polymer Melt Dynamics Studied By Low-Field NMR

    NASA Astrophysics Data System (ADS)

    Vaca Chavez, Fabian; Huebsch, Patrick; Zirbs, Ronald; Binder, Wolfgang; Saalwaechter, Kay

    2009-03-01

    Proton Multiple-Quantum (MQ) NMR is a powerful technique to investigate polymer dynamics due to its sensitivity to molecular motions on very different timescales. Entangled melts exhibit dynamic processes that cover a wide range of timescales, starting from fast ps-scale segmental reorientation up to diffusive and cooperative motions on the ms-s-scale. In this work, we apply MQ NMR to linear poly(cis-1,4-isoprene) and poly(isobutylene) of different molecular weight above the glass transition over suitable ranges of temperature, in order to establish the dynamic regimes predicted by the tube model, and, for the first time, to extract actual time scale information. This directly complements many neutron scattering studies, which are restricted to the sub-μs-timescale. Measurements on PIB-grafted silica particles with different molecular weights and different chain densities on the surface of the particle are also shown. The data is analyzed by establishing scaling laws which can be directly associated with different dynamic regimes predicted by the tube/reptation model. Full analytical analyses based on a correlation function which explicitly includes segmental, Rouse, and reptation dynamics are discussed.

  1. Quantification of hydrolytic charge loss of DMAEA-Q-based polyelectrolytes by proton NMR spectroscopy and implications for colloid titration.

    PubMed

    Saveyn, Hans; Hendrickx, Pieter M S; Dentel, Steven K; Martins, José C; Van der Meeren, Paul

    2008-05-01

    Copolymers of acrylamide and quaternised dimethylaminoethyl acrylate (DMAEA-Q) constitute an economically important range of cationic polyelectrolytes used in sludge conditioning. The latter treatment involves charge neutralisation and bridging induced by these polymers. Since both of these phenomena rely on charge-driven sorption onto the negatively charged colloidal particles, the accurate assessment of their charge density is of primary importance in polyelectrolyte characterisation. The experimental determination of this characteristic generally relies on colloidal charge titration, in which the cationic polymer is titrated against an anionic polymer. Hereby, one of the requirements to have a stoichiometric reaction between the oppositely charged polymers is a sufficiently low polymer concentration. In this study, it is shown that such a low polymer concentration may entail a pronounced hydrolysis effect for DMAEA-Q-based polymers, which leads to a release of the cationic side groups and hence causes considerable errors on the charge titration results. Proton nuclear magnetic resonance spectroscopy was applied to investigate the fast hydrolysis kinetics of DMAEA-Q polymers together with time-dependent charge titration measurements. Diffusion NMR spectroscopy was used to assist in establishing the nature of the hydrolysis compounds. The results from both techniques indicate that a high degree of hydrolysis is reached within minutes after dilution of a concentrated polymer stock solution into aqueous solutions of slightly acidic to neutral pH values. Therefore, a modification to the classic colloid titration procedure is proposed, using a buffered dilution liquid to avoid polymer hydrolysis. It is shown that a buffer pH value of 4.5 avoids not only polymer hydrolysis effects but also possible protonation of the anionic titrant, thereby avoiding overestimation of the charge density. By means of this procedure, reproducible and time-independent charge titration

  2. Toxicometabolomics approach to urinary biomarkers for mercuric chloride (HgCl{sub 2})-induced nephrotoxicity using proton nuclear magnetic resonance ({sup 1}H NMR) in rats

    SciTech Connect

    Kim, Kyu-Bong; Um, So Young; Chung, Myeon Woo; Jung, Seung Chul; Oh, Ji Seon; Kim, Seon Hwa; Na, Han Sung; Lee, Byung Mu; Choi, Ki Hwan

    2010-12-01

    The primary objective of this study was to determine and characterize surrogate biomarkers that can predict nephrotoxicity induced by mercuric chloride (HgCl{sub 2}) using urinary proton nuclear magnetic resonance ({sup 1}H NMR) spectral data. A procedure for {sup 1}H NMR urinalysis using pattern recognition was proposed to evaluate nephrotoxicity induced by HgCl{sub 2} in Sprague-Dawley rats. HgCl{sub 2} at 0.1 or 0.75 mg/kg was administered intraperitoneally (i.p.), and urine was collected every 24 h for 6 days. Animals (n = 6 per group) were sacrificed 3 or 6 days post-dosing in order to perform clinical blood chemistry tests and histopathologic examinations. Urinary {sup 1}H NMR spectroscopy revealed apparent differential clustering between the control and HgCl{sub 2} treatment groups as evidenced by principal component analysis (PCA) and partial least square (PLS)-discriminant analysis (DA). Time- and dose-dependent separation of HgCl{sub 2}-treated animals from controls was observed by PCA of {sup 1}H NMR spectral data. In HgCl{sub 2}-treated rats, the concentrations of endogenous urinary metabolites of glucose, acetate, alanine, lactate, succinate, and ethanol were significantly increased, whereas the concentrations of 2-oxoglutarate, allantoin, citrate, formate, taurine, and hippurate were significantly decreased. These endogenous metabolites were selected as putative biomarkers for HgCl{sub 2}-induced nephrotoxicity. A dose response was observed in concentrations of lactate, acetate, succinate, and ethanol, where severe disruption of the concentrations of 2-oxoglutarate, citrate, formate, glucose, and taurine was observed at the higher dose (0.75 mg/kg) of HgCl{sub 2}. Correlation of urinary {sup 1}H NMR PLS-DA data with renal histopathologic changes suggests that {sup 1}H NMR urinalysis can be used to predict or screen for HgCl{sub 2}-induced nephrotoxicity{sub .}

  3. 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

  4. Sigmatropic proton shifts: a quantum chemical study.

    PubMed

    Wang, Yi; Yu, Zhi-Xiang

    2017-09-13

    A quantum chemical study of [1,j] sigmatropic proton shifts in polyenyl anions and related conjugated systems has been performed. We found that the Woodward-Hoffmann rules can be applied to understand the stereochemical outcome of these sigmatropic rearrangements, showing that [1,j] sigmatropic proton shift occurs antarafacially when j = 4n + 2, while suprafacial proton shift is symmetry-allowed when j = 4n. The activation barriers for [1,j] proton shifts in polyenyl anions CjHj+3(-) are 48.2 (j = 2), 32.8 (j = 4), 21.0 (j = 6), 40.5 (j = 8), and 49.1 (j = 10) kcal mol(-1), respectively. This trend can be explained by the trade-off between stereoelectronic requirement and ring strain in the proton shift transition structure. Among these reactions, only the [1,6] proton shift with the lowest activation barrier can occur intramolecularly under mild reaction conditions. The others are unlikely to take place in a direct manner. Consequently, proton shuttles are generally required to facilitate these sigmatropic proton shifts through a protonation/deprotonation mechanism.

  5. 1H NMR, 13C NMR and mass spectral studies of some Schiff bases derived from 3-amino-1,2,4-triazole.

    PubMed

    Issa, Y M; Hassib, H B; Abdelaal, H E

    2009-11-01

    Heterocyclic Schiff bases derived from 3-amino-1,2,4-triazole and different substituted aromatic aldehydes are prepared and subjected to (1)H NMR, (13)C NMR and mass spectral analyses. (1)H NMR spectra in DMSO exhibit a sharp singlet within the 9.35-8.90ppm region which corresponds to the azomethine proton. The position of this signal is largely dependent on the nature of the substituents on the benzal moiety. It is observed that the shape, position and the integration value of the signal of the aromatic proton of the triazole ring ((5)C) are clearly affected by the rate of exchange, relaxation time, concentration of solution as well as the solvent used. (13)C NMR is taken as substantial support for the results reached from (1)H NMR studies. The mass spectral results are taken as a tool to confirm the structure of the investigated compounds. The base peak (100%), mostly the M-1 peak, indicates the facile loss of hydrogen radical. The fragmentation pattern of the unsubstituted Schiff base is taken as the general scheme. Differences in the other schemes result from the effect of the electronegativity of the substituents attached to the aromatic ring.

  6. Reaction pathways of proton transfer in hydrogen-bonded phenol-carboxylate complexes explored by combined UV-vis and NMR spectroscopy.

    PubMed

    Koeppe, Benjamin; Tolstoy, Peter M; Limbach, Hans-Heinrich

    2011-05-25

    Combined low-temperature NMR/UV-vis spectroscopy (UVNMR), where optical and NMR spectra are measured in the NMR spectrometer under the same conditions, has been set up and applied to the study of H-bonded anions A··H··X(-) (AH = 1-(13)C-2-chloro-4-nitrophenol, X(-) = 15 carboxylic acid anions, 5 phenolates, Cl(-), Br(-), I(-), and BF(4)(-)). In this series, H is shifted from A to X, modeling the proton-transfer pathway. The (1)H and (13)C chemical shifts and the H/D isotope effects on the latter provide information about averaged H-bond geometries. At the same time, red shifts of the π-π* UV-vis absorption bands are observed which correlate with the averaged H-bond geometries. However, on the UV-vis time scale, different tautomeric states and solvent configurations are in slow exchange. The combined data sets indicate that the proton transfer starts with a H-bond compression and a displacement of the proton toward the H-bond center, involving single-well configurations A-H···X(-). In the strong H-bond regime, coexisting tautomers A··H···X(-) and A(-)···H··X are observed by UV. Their geometries and statistical weights change continuously when the basicity of X(-) is increased. Finally, again a series of single-well structures of the type A(-)···H-X is observed. Interestingly, the UV-vis absorption bands are broadened inhomogeneously because of a distribution of H-bond geometries arising from different solvent configurations.

  7. 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.

  8. 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.

  9. Proton decoupling and recoupling under double-nutation irradiation in solid-state NMR

    NASA Astrophysics Data System (ADS)

    Takeda, Kazuyuki; Wakisaka, Asato; Takegoshi, K.

    2014-12-01

    The effect of 1H decoupling in magic-angle spinning solid-state NMR is studied under radiofrequency irradiation causing simultaneous nutations around a pair of orthogonal axes. Double-nutation with an arbitrary pair of nutation frequencies is implemented through modulation of the amplitude, phase, and frequency of the transmitting pulses. Similarity and difference of double-nutation decoupling and two-pulse phase-modulation decoupling schemes [A. E. Bennett, C. M. Rienstra, M. Auger, K. V. Lakshmi, and R. G. Griffin, J. Chem. Phys. 103, 6951-6958 (1995) and I. Scholz, P. Hodgkinson, B. H. Meier, and M. Ernst, J. Chem. Phys. 130, 114510 (2009)] are discussed. The structure of recoupling bands caused by interference of the 1H spin nutation with sample spinning is studied by both experiments and numerical simulations.

  10. Proton decoupling and recoupling under double-nutation irradiation in solid-state NMR

    SciTech Connect

    Takeda, Kazuyuki Wakisaka, Asato; Takegoshi, K.

    2014-12-14

    The effect of {sup 1}H decoupling in magic-angle spinning solid-state NMR is studied under radiofrequency irradiation causing simultaneous nutations around a pair of orthogonal axes. Double-nutation with an arbitrary pair of nutation frequencies is implemented through modulation of the amplitude, phase, and frequency of the transmitting pulses. Similarity and difference of double-nutation decoupling and two-pulse phase-modulation decoupling schemes [A. E. Bennett, C. M. Rienstra, M. Auger, K. V. Lakshmi, and R. G. Griffin, J. Chem. Phys. 103, 6951–6958 (1995) and I. Scholz, P. Hodgkinson, B. H. Meier, and M. Ernst, J. Chem. Phys. 130, 114510 (2009)] are discussed. The structure of recoupling bands caused by interference of the {sup 1}H spin nutation with sample spinning is studied by both experiments and numerical simulations.

  11. NMR study of n-dodecane adsorbed on graphite.

    PubMed

    Alba, M D; Castro, M A; Clarke, S M; Perdigón, A C

    2003-05-01

    In this brief contribution we demonstrate that 1H and 2H NMR spectroscopy can be an effective method of investigating adsorption from liquids at the solid-liquid interface. The method is illustrated here with the adsorption of a simple alkane adsorbed on graphite, in particular the system n-dodecane and graphite at coverages of 1 and 5 monolayers. Static single-pulse proton nuclear magnetic resonance and static quadrupolar echo deuterium nuclear magnetic resonance spectra were recorded for both coverages. The experimental NMR results presented here show features clearly consistent with earlier calorimetric and neutron scattering work and demonstrate the formation of solid adsorbed layers that coexist with the bulk adsorbate with both isotopes. This ability to probe both deuterated and protonated materials simultaneously illustrates that this experimental approach can be readily extended to investigate the adsorption behaviour of multicomponent mixtures.

  12. Multicomponent analysis of radiolytic products in human body fluids using high field proton nuclear magnetic resonance (NMR) spectroscopy

    NASA Astrophysics Data System (ADS)

    Grootveld, Martin C.; Herz, Herman; Haywood, Rachel; Hawkes, Geoffrey E.; Naughton, Declan; Perera, Anusha; Knappitt, Jacky; Blake, David R.; Claxson, Andrew W. D.

    1994-05-01

    High field proton Hahn spin-echo nuclear magnetic resonance (NMR) spectroscopy has been employed to investigate radiolytic damage to biomolecules present in intact human body fluids. γ-Radiolysis of healthy or rheumatoid human serum (5.00 kGy) in the presence of atmospheric O 2 gave rise to reproducible elevations in the concentration of NMR-detectable acetate which are predominantly ascribable to the prior oxidation of lactate to pyruvate by hydroxyl radical (·OH) followed by oxidative decarboxylation of pyruvate by radiolytically-generated hydrogen peroxide (H 2O 2) and/or further ·OH radical. Increases in the serum levels of non-protein-bound, low-molecular-mass components such as citrate and glutamine were also observed subsequent to γ-radiolysis, an observation which may reflect their mobilisation from protein binding-sites by ·OH radical, superoxide anion and/or H 2O 2. Moreover, substantial radiolytically-mediated elevations in the concentration of serum formate were also detectable. In addition to the above modifications, γ-radiolysis of inflammatory knee-joint synovial fluid (SF) generated a low-molecular-mass oligosaccharide species derived from the radiolytic fragmentation of hyaluronate. The radiolytically-mediated production of acetate in SF samples was markedly greater than that observed in serum samples, a consequence of the much higher levels of ·OH radical-scavenging lactate present. Indeed, increases in SF acetate concentration were detectable at doses as low as 48 Gy. We conclude that high field proton NMR analysis provides much useful information regarding the relative radioprotectant abilities of endogenous components and the nature, status and levels of radiolytic products generated in intact biofluids. We also suggest that NMR-detectable radiolytic products with associated toxicological properties (e.g. formate) may play a role in contributing to the deleterious effects observed following exposure of living organisms to sources of

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

    PubMed

    Kupka, Teobald; Wieczorek, Piotr P

    2016-01-15

    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 (1)H and (13)C 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.

  14. 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.

  15. Two-dimensional NMR studies of the porcine muscle adenylate kinase

    SciTech Connect

    Klaus, W.; Scharf, M.; Zimmermann, S.; Roesch, P.

    1988-07-26

    Porcine adenylate kinase was subjected to one- and two-dimensional proton NMR studies in order to identify amino acid spin systems and obtain sequence-specific resonance assignments. With a combination of results from a map of side-chain distances resulting from the refined X-ray crystallographic data and nuclear Overhauser effect spectroscopy (NOESY), assignments are suggested for all the aromatic spin systems.

  16. ⁵¹V NMR Crystallography of Vanadium Chloroperoxidase and Its Directed Evolution P395D/L241V/T343A Mutant: Protonation Environments of the Active Site.

    PubMed

    Gupta, Rupal; Hou, Guangjin; Renirie, Rokus; Wever, Ron; Polenova, Tatyana

    2015-04-29

    Vanadium-dependent haloperoxidases (VHPOs) perform two-electron oxidation of halides using hydrogen peroxide. Their mechanism, including the factors determining the substrate specificity and the pH-dependence of the catalytic rates, is poorly understood. The vanadate cofactor in the active site of VHPOs contains "spectroscopically silent" V(V), which does not change oxidation state during the reaction. We employed an NMR crystallography approach based on (51)V magic angle spinning NMR spectroscopy and Density Functional Theory, to gain insights into the structure and coordination environment of the cofactor in the resting state of vanadium-dependent chloroperoxidases (VCPO). The cofactor environments in the wild-type VCPO and its P395D/L241V/T343A mutant exhibiting 5-100-fold improved catalytic activity are examined at various pH values. Optimal sensitivity attained due to the fast MAS probe technologies enabled the assignment of the location and number of protons on the vanadate as a function of pH. The vanadate cofactor changes its protonation from quadruply protonated at pH 6.3 to triply protonated at pH 7.3 to doubly protonated at pH 8.3. In contrast, in the mutant, the vanadate protonation is the same at pH 5.0 and 8.3, and the cofactor is doubly protonated. This methodology to identify the distinct protonation environments of the cofactor, which are also pH-dependent, could help explain the different reactivities of the wild-type and mutant VCPO and their pH-dependence. This study demonstrates that (51)V-based NMR crystallography can be used to derive the detailed coordination environments of vanadium centers in large biological molecules.

  17. Microslot NMR probe for metabolomics studies.

    PubMed

    Krojanski, Hans Georg; Lambert, Jörg; Gerikalan, Yilmaz; Suter, Dieter; Hergenröder, Roland

    2008-11-15

    A NMR microprobe based on microstrip technology suitable for investigations of volume-limited samples in the low nanoliter range was designed. NMR spectra of sample quantities in the 100 pmol range can be obtained with this probe in a few seconds. The planar geometry of the probe is easily adaptable to the size and geometry requirements of the samples.

  18. Detection of Phosphomonoester Signals in Proton-Decoupled 31P NMR Spectra of the Myocardium of Patients with Myocardial Hypertrophy

    NASA Astrophysics Data System (ADS)

    Jung, Wulf-Ingo; Sieverding, Ludger; Breuer, Johannes; Schmidt, Oliver; Widmaier, Stefan; Bunse, Michael; van Erckelens, Franz; Apitz, Jürgen; Dietze, Guenther J.; Lutz, Otto

    1998-07-01

    Proton-decoupled31P NMR spectroscopy at 1.5 T of the anterior left ventricular myocardium was used to monitor myocardial phosphate metabolism in asymptomatic patients with hypertrophic cardiomyopathy (HCM,n= 14) and aortic stenosis (AS,n= 12). In addition to the well-known phosphorus signals a phosphomonoester (PME) signal was detected at about 6.9 ppm in 7 HCM and 2 AS patients. This signal was not observed in the spectra of normal controls (n= 11). We suggest that in spectra of patients with myocardial hypertrophy the presence of a PME signal reflects alterations in myocardial glucose metabolism.

  19. Rapid proton-detected NMR assignment for proteins with fast magic angle spinning.

    PubMed

    Barbet-Massin, Emeline; Pell, Andrew J; Retel, Joren S; Andreas, Loren B; Jaudzems, Kristaps; Franks, W Trent; Nieuwkoop, Andrew J; Hiller, Matthias; Higman, Victoria; Guerry, Paul; Bertarello, Andrea; Knight, Michael J; Felletti, Michele; Le Marchand, Tanguy; Kotelovica, Svetlana; Akopjana, Inara; Tars, Kaspars; Stoppini, Monica; Bellotti, Vittorio; Bolognesi, Martino; Ricagno, Stefano; Chou, James J; Griffin, Robert G; Oschkinat, Hartmut; Lesage, Anne; Emsley, Lyndon; Herrmann, Torsten; Pintacuda, Guido

    2014-09-03

    Using a set of six (1)H-detected triple-resonance NMR experiments, we establish a method for sequence-specific backbone resonance assignment of magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of 5-30 kDa proteins. The approach relies on perdeuteration, amide (2)H/(1)H exchange, high magnetic fields, and high-spinning frequencies (ωr/2π ≥ 60 kHz) and yields high-quality NMR data, enabling the use of automated analysis. The method is validated with five examples of proteins in different condensed states, including two microcrystalline proteins, a sedimented virus capsid, and two membrane-embedded systems. In comparison to contemporary (13)C/(15)N-based methods, this approach facilitates and accelerates the MAS NMR assignment process, shortening the spectral acquisition times and enabling the use of unsupervised state-of-the-art computational data analysis protocols originally developed for solution NMR.

  20. Rapid Proton-Detected NMR Assignment for Proteins with Fast Magic Angle Spinning

    PubMed Central

    2015-01-01

    Using a set of six 1H-detected triple-resonance NMR experiments, we establish a method for sequence-specific backbone resonance assignment of magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of 5–30 kDa proteins. The approach relies on perdeuteration, amide 2H/1H exchange, high magnetic fields, and high-spinning frequencies (ωr/2π ≥ 60 kHz) and yields high-quality NMR data, enabling the use of automated analysis. The method is validated with five examples of proteins in different condensed states, including two microcrystalline proteins, a sedimented virus capsid, and two membrane-embedded systems. In comparison to contemporary 13C/15N-based methods, this approach facilitates and accelerates the MAS NMR assignment process, shortening the spectral acquisition times and enabling the use of unsupervised state-of-the-art computational data analysis protocols originally developed for solution NMR. PMID:25102442

  1. Phase Separation in Polyurethanes - A Deuterium NMR Study.

    DTIC Science & Technology

    1985-02-18

    from the diphenylmethane diisocyanate (MDI) or the soft segment polyol residues. The deuteriunm NMR spectra’ 9 for these four samples are shown in...other decays more slowly and is assigned to the polyester soft segments. With proton spin diffusion as an experimental probe, Assink and Wilkes3 4 35...evaluated phase mixing in a series of MDI- polyester polyurethanes. Their data require the presence of both short and long range degrees of mixing

  2. Beta-alanine-hydrochloride (2:1) crystal: structure, 13C NMR and vibrational properties, protonation character.

    PubMed

    Godzisz, D; Ilczyszyn, M; Ciunik, Z

    2003-01-15

    The crystal structure of beta-alanine-hydrochloride (2:1) complex (2A-HCl) has been determined by X-ray diffraction method at 298 and 100 K as monoclinic, space group C2/c, Z=4. The crystal comprises chloride anions and protonated beta-alanine dimers: two beta-alanine zwitterions are joined by strong, symmetric (Ci) hydrogen bond with the O...O distance of 2.473 A at room temperature. Powder FT-IR and FT-Raman as well as solid state 13C NMR spectra provide insights into the solid structure of this complex, character of its hydrogen bonds and the beta-alanine protonation.

  3. Biochemical and proton NMR characterization of the isolated functional beta-subunit of coupling factor one from spinach chloroplasts

    SciTech Connect

    Roux-Fromy, M.; Neumann, J.M.; Andre, F.; Berger, G.; Girault, G.; Galmiche, J.M.; Remy, R.

    1987-04-29

    Beta subunits have been dissociated from CF1 of spinach chloroplasts, purified by HPLC and characterized by two-dimensional electrophoresis and fluorescence emission. The solutions of isolated beta subunits are able to hydrolyze MgATP; this ATPase activity is an intrinsic property of the beta molecule. From proton NMR at 300 and 500 MHz, it is shown that the preparations are fully reproducible and that beta subunits remain monomeric with 75% aliphatic protons associated with rigid parts of the molecule. The other 25% give rise to separate resonances and belong to mobile side-chains and/or to flexible regions. The measurement of the transverse relaxation times T2 has permitted a detailed characterization of the molecular dynamics of the isolated beta subunits.

  4. N-H...F hydrogen bonds in fluorinated benzanilides: NMR and DFT study.

    PubMed

    Manjunatha Reddy, G N; Vasantha Kumar, M V; Guru Row, T N; Suryaprakash, N

    2010-10-28

    Using (19)F and (1)H-NMR (with (14)N decoupling) spectroscopic techniques together with density functional theoretical (DFT) calculations, we have investigated weak molecular interactions in isomeric fluorinated benzanilides. Simultaneous presence of through space nuclear spin-spin couplings ((1h)J(N-HF)) of diverse strengths and feeble structural fluctuations are detected as a function of site specific substitution of fluorine atoms within the basic identical molecular framework. The transfer of hydrogen bonding interaction energies through space is established by perturbing their strengths and monitoring the effect on NMR parameters. Multiple quantum (MQ) excitation, up to the highest possible MQ orders of coupled protons, is utilized as a tool for accurate (1)H assignments. Results of NMR studies and DFT calculations are compared with the relevant structural parameters taken from single crystal X-ray diffraction studies.

  5. Proton NMR assignments and secondary structure of the snake venom protein echistatin

    SciTech Connect

    Yuan Chen; Baum, J. ); Pitzenberger, S.M.; Garsky, V.M.; Lumma, P.K.; Sanyal, G. )

    1991-12-17

    The snake venom protein echistatin is a potent inhibitor of platelet aggregation. The inhibitory properties of echistatin have been attributed to the Arg-Gly-Asp sequence at residues 24-26. In this paper, sequence-specific nuclear magnetic resonance assignments are presented for the proton resonances of echistatin in water. The single-chain protein contains 49 amino acids and 4 cystine bridges. All of the backbone amide, C{sub alpha}H, and side-chain resonances, except for the {eta}-NH of the arginines, have been assigned. The secondary structure of the protein was characterized from the pattern of nuclear Overhauser enhancements, from the identification of slowly exchanging amide protons, from {sup 3}J{sub c{alpha}H-NH} coupling constants, and from circular dichroism studies. The data suggest that the secondary structure consists of a type I {beta}-turn, a short {beta}-hairpin, and a short-, irregular, antiparallel {beta}-sheet and that the Arg-Gly-Asp sequence is in a flexible loop connecting two strands of the distorted antiparallel {beta}-sheet.

  6. Identification of endogenous metabolites in human sperm cells using proton nuclear magnetic resonance ((1) H-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).

    PubMed

    Paiva, C; Amaral, A; Rodriguez, M; Canyellas, N; Correig, X; Ballescà, J L; Ramalho-Santos, J; Oliva, R

    2015-05-01

    The objective of this study was to contribute to the first comprehensive metabolomic characterization of the human sperm cell through the application of two untargeted platforms based on proton nuclear magnetic resonance ((1) H-NMR) spectroscopy and gas chromatography coupled to mass spectrometry (GC-MS). Using these two complementary strategies, we were able to identify a total of 69 metabolites, of which 42 were identified using NMR, 27 using GC-MS and 4 by both techniques. The identity of some of these metabolites was further confirmed by two-dimensional (1) H-(1) H homonuclear correlation spectroscopy (COSY) and (1) H-(13) C heteronuclear single-quantum correlation (HSQC) spectroscopy. Most of the metabolites identified are reported here for the first time in mature human spermatozoa. The relationship between the metabolites identified and the previously reported sperm proteome was also explored. Interestingly, overrepresented pathways included not only the metabolism of carbohydrates, but also of lipids and lipoproteins. Of note, a large number of the metabolites identified belonged to the amino acids, peptides and analogues super class. The identification of this initial set of metabolites represents an important first step to further study their function in male gamete physiology and to explore potential reasons for dysfunction in future studies. We also demonstrate that the application of NMR and MS provides complementary results, thus constituting a promising strategy towards the completion of the human sperm cell metabolome.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    USDA-ARS?s Scientific Manuscript database

    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. 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.

  11. Proton nuclear magnetic resonance studies of boronated nucleosides

    SciTech Connect

    Banks, B.N.

    1992-01-01

    Modified nucleosides are an emerging class of potentially therapeutic agents. Recently, a number of 2[prime]-deoxynucleosides with boronated bases have been synthesized in this laboratory, including: 2[prime]-deoxy-N7-cyanoborano guanosine (bGua), 2[prime]-deoxy-N3-cyanoborano cytidine (bCyt), and 2[prime]-deoxy-N1-cyanoborano adenosine (bAde). The author has utilized proton NMR spectroscopy to determine the molecular recognition of these boronated nucleosides with their complementary base pairing partners. The self-association as well as heteroassociation were studied by varying the temperature, concentration, and mole fraction of each component. Proton NMR techniques include normal proton studies to measure the chemical shifts and homonuclear 1-D NOE difference to measure through space interactions, all of which help to determine the exact pairing behaviour of these nucleosides. Similar studies have been performed on unboronated nucleosides in order to determine if the boronated nucleosides can form stable Watson-Crick type base pairs; similar to unboronated nucleosides. From the results, the author concludes that bGua forms a stable Watson-Crick type base pair with Cyt. Both bGua and Cyt are able to self associate although the homodimers are less stable than the bGua:Cyt heterodimers. The other two boronated nucleosides because the cyanoborane group blocks the normal base pairing sites. The results are consistent with Hoogsteen pairing. Continuous variation studies suggest the existence of trimers of bCyt with Gua[sub 2] as well as other possible pairing schemes. The ability of bGua to complex with Cyt in a Watson-Crick type base pair suggests that it might be able to be incorporated like normal Gua into DNA.

  12. Antimalarial drugs and heme in detergent micelles: An NMR study.

    PubMed

    Casabianca, Leah B; Kallgren, Joye B; Natarajan, Jayakumar K; Alumasa, John N; Roepe, Paul D; Wolf, Christian; de Dios, Angel C

    2009-05-01

    Proton nuclear magnetic resonance relaxation times were measured for the protons of micelles formed by the detergents sodium dodecyl sulfate, dodecyltrimethyl ammonium bromide, and polyethylene glycol sorbitan monolaureate in the presence of ferriprotoporphyrin IX and the antimalarial drugs chloroquine, 7-chloro-4-quinolyl 4-N,N-diethylaminobutyl sulfide, and primaquine. Diffusion coefficients were extracted from pulsed gradient NMR experiments to evaluate the degree of association of these drugs with the detergent micelles. Results indicate that at low or neutral pH when the quinolyl N is protonated, chloroquine does not associate with neutral or cationic detergent micelles. For this reason, chloroquine's interaction with heme perturbs the partitioning of heme between the aqueous medium and detergent micelles.

  13. The Synthesis and Proton NMR Spectrum of Methyl 7-Cycloheptatrienylacetate: An Advanced Undergraduate Laboratory Experiment.

    ERIC Educational Resources Information Center

    Jurch, G. R., Jr.; And Others

    1980-01-01

    Describes an advanced undergraduate laboratory experiment designed to give the senior chemistry student an opportunity to apply several synthetic and purification techniques as well as possibilities for the application of NMR spectroscopy. (CS)

  14. 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.

  15. Access to aliphatic protons as reporters in non-deuterated proteins by solid-state NMR.

    PubMed

    Vasa, Suresh Kumar; Rovó, Petra; Giller, Karin; Becker, Stefan; Linser, Rasmus

    2016-03-28

    Interactions within proteins, with their surrounding, and with other molecules are mediated mostly by hydrogen atoms. In fully protonated, inhomogeneous, or larger proteins, however, aliphatic proton shifts tend to show little dispersion despite fast Magic-Angle Spinning. 3D correlations dispersing aliphatic proton shifts by their better resolved amide N/H shifts can alleviate this problem. Using inverse second-order cross-polarization (iSOCP), we here introduce dedicated and improved means to sensitively link site-specific chemical shift information from aliphatic protons with a backbone amide resolution. Thus, even in cases where protein deuteration is impossible, this approach may enable access to various aspects of protein functions that are reported on by protons.

  16. 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.

  17. 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.

  18. Hepatitis B virus direct repeat sequence: imino proton exchange rates and distance and torsion angle restraints from NMR.

    PubMed

    Bishop, K D; Blocker, F J; Egan, W; James, T L

    1994-01-18

    Structural features of a trisdecamer duplex, [d(GGCAGAGGTGAAA).d(TTTCACCTCTGCC)], in solution are being investigated by proton one-dimensional (1D) and two-dimensional (2D) NMR spectroscopy. This DNA sequence is comprised of the 11-base-pair direct repeat sequence found in the hepatitis B viral genome with an additional base pair from the genome included on each end to minimize end effects on the 11-bp sequence of interest. The direct repeat sequence occurs twice in the viral genome; both are essential for initiation of DNA synthesis. The critical nature of this sequence suggests it may be a target to control replication of the virus. Elucidation of the structure of the direct repeat sequence could prove to be beneficial in targeting efforts. Structural determination via restrained molecular dynamics requires experimentally derived distance restraints. The ability to determine solution structures of biomolecules by NMR spectroscopy is limited by the quality and quantity of distance and torsion angle restraints that can be extracted from the NMR data. Techniques used to establish these restraints are constantly evolving and improving. Modifications in procedure are applied to the trisdecamer duplex to yield improvements in the determination of sugar conformations from COSY data and a substantial increase in the number of distance restraints typically garnered from 2D NOE intensity data. This increase in the number of distance restraints normally obtained from 2D NOE intensities was accomplished by utilizing a new version of the iterative complete relaxation matrix program MARDIGRAS with intensities extracted from a 2D NOE data set acquired in 90% H2O. The exchange rate of the imino and amino protons with the solvent water protons can now be included in the relaxation matrix calculations, thereby providing more accurate distances when utilizing the 2D NOE cross-peaks involving at least one exchangeable proton. In this lab, analysis of two-quantum-filtered correlation

  19. Proton–proton Overhauser NMR spectroscopy with polypeptide chains in large structures

    PubMed Central

    Horst, Reto; Wider, Gerhard; Fiaux, Jocelyne; Bertelsen, Eric B.; Horwich, Arthur L.; Wüthrich, Kurt

    2006-01-01

    The use of 1H–1H nuclear Overhauser effects (NOE) for structural studies of uniformly deuterated polypeptide chains in large structures is investigated by model calculations and NMR experiments. Detailed analysis of the evolution of the magnetization during 1H–1H NOE experiments under slow-motion conditions shows that the maximal 1H–1H NOE transfer is independent of the overall rotational correlation time, even in the presence of chemical exchange with the bulk water, provided that the mixing time is adjusted for the size of the structure studied. 1H–1H NOE buildup measurements were performed for the 472-kDa complex of the 72-kDa cochaperonin GroES with a 400-kDa single-ring variant of the chaperonin GroEL (SR1). These experiments demonstrate that multidimensional NOESY experiments with cross-correlated relaxation-enhanced polarization transfer and transverse relaxation-optimized spectroscopy elements can be applied to structures of molecular masses up to several hundred kilodaltabs, which opens new possibilities for studying functional interactions in large maromolecular assemblies in solution. PMID:17032756

  20. 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.

  1. Prospects for future proton studies at HRIBF

    NASA Astrophysics Data System (ADS)

    Bingham, C. R.; Batchelder, J. C.; Ginter, T. N.; Gross, C. J.; Grzywacz, R.; Janas, Z.; Karny, M.; McConnell, J. W.; Rykaczewski, K.; Toth, K. S.; Zganjar, E. F.

    2000-05-01

    Great progress has been made in the last 20 years in the study of proton emission from unstable nuclei, but the prospects for additional strides in the next several years are bright. The present main limitations on the study of proton radioactivity are related to the inability to produce copious quantities of nuclides beyond the proton drip line, and the difficulty of measuring proton radioactivity of a mass-separated nucleus in the first few microseconds of its existence. At the Holifield Facility we will attack the second of these limitations by using new signal processing CAMAC modules DGF-4C. Digitizing of the preamplifier signals should enable the analysis of a proton decay occurring at times even less than 1 microsecond after an implant in a strip detector. In the same process, the threshold energy at which we can make measurements will be lowered. These two things will hopefully enable the measurement of lower-energy, but faster decays of isotopes in the 100Sn region and below. For the latter region, the proton decays crucial for a rp-process scenario are of particular interest (e.g. 69Br decay). Secondly, for very short-lived species, we plan to make measurements (without residue separation) at points much closer to the target, thus reducing the flight time between the target and detector. As more intense radioactive beams become available, eg. 56Ni, we will utilize these to produce more neutron-deficient nuclides by use of colder reactions than is possible with stable beams. In some cases where delayed proton emitters are present in the same isobaric chain, the use of the cold reactions with radioactive beams can provide purer samples of the isotope of interest, with a reduction in background from the delayed proton emitters in the same mass chain.

  2. Two dimensional NMR and NMR relaxation studies of coal structure. Progress report, September 13, 1991--December 31, 1991

    SciTech Connect

    Zilm, K.W.

    1992-05-27

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

  3. 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.

  4. 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.

  5. 500-MHz proton NMR evidence for two solution structures of the common arm base-paired segment of wheat germ 5S ribosomal RNA

    SciTech Connect

    Wu, Jiejun; Marshall, A.G. )

    1990-02-20

    The base-pair protons of the common arm duplex fragment of wheat germ (Triticum aestivum) ribosomal 5S RNA have been identified and assigned by means of 500-MHz proton NMR spectroscopy. The two previously reported extra base pairs within the fragment are now explained by the presence of two distinct solution structures of the common arm fragment (and its corresponding base-paired segment in intact 5S rRNA). The present conclusions are supported by one- and two-dimensional proton homonuclear Overhauser enhancements in H{sub 2}O and by temperature variation and Mg{sup 2+} titration of the downfield {sup 1}H NMR spectrum. The difference between the two conformers is most likely due to difference in helical tightness. Some additional amino proton resonances have also been assigned.

  6. Contemporary NMR Studies of Protein Electrostatics.

    PubMed

    Hass, Mathias A S; Mulder, Frans A A

    2015-01-01

    Electrostatics play an important role in many aspects of protein chemistry. However, the accurate determination of side chain proton affinity in proteins by experiment and theory remains challenging. In recent years the field of nuclear magnetic resonance spectroscopy has advanced the way that protonation states are measured, allowing researchers to examine electrostatic interactions at an unprecedented level of detail and accuracy. Experiments are now in place that follow pH-dependent (13)C and (15)N chemical shifts as spatially close as possible to the sites of protonation, allowing all titratable amino acid side chains to be probed sequence specifically. The strong and telling response of carefully selected reporter nuclei allows individual titration events to be monitored. At the same time, improved frameworks allow researchers to model multiple coupled protonation equilibria and to identify the underlying pH-dependent contributions to the chemical shifts.

  7. NMR studies of the conformational interconversion of butaclamol in solution.

    PubMed

    Casarotto, M G; Craik, D J; Lloyd, E J

    1991-07-01

    1H NMR experiments at 300 MHz have been carried out to determine the identity and study the interconversion of two conformations of butaclamol in solution. The hydrochloride salt in DMSO exists as an equilibrium mixture of two conformations, which differ in their stereochemistry about the ring junction that contains the single nitrogen atom in butaclamol. The trans form has a relative population of 80% and the cis I form 20%. In CDCl3 only the trans form is observed, while in CDCl3-DMSO mixtures, both forms are detected in a ratio (trans:cis I) that decreases as the percentage of CDCl3 decreases. For the free base in either CD2Cl2 or DMSO, only a single set of resonances is observed at room temperature, but as temperature is lowered, peaks from methine protons H4a and H13b near the ring junction broaden and (for samples in CD2Cl2) eventually split into two resonances corresponding to the cis and trans forms. It is suggested that nitrogen inversion is the dynamic process responsible for the interconversion of the two forms. Line shape analysis as a function of temperature yielded an energy barrier of 9.6 +/- 0.5 kcal/mol for the interconversion, in good agreement with values obtained from saturation transfer experiments. In the hydrochloride salt, the barrier in DMSO was somewhat higher, i.e., 17.3 +/- 0.9 kcal/mol, as determined by saturation transfer and variable-temperature measurements.

  8. Dynamics of Antibody Domains Studied by Solution NMR

    PubMed Central

    Vu, Bang K.; Walsh, Joseph D.; Dimitrov, Dimiter S.; Ishima, Rieko

    2012-01-01

    Information on local dynamics of antibodies is important to evaluate stability, to rationally design variants, and to clarify conformational disorders at the epitope binding sites. Such information may also be useful for improved understanding of antigen recognition. NMR can be used for characterization of local protein dynamics at the atomic level through relaxation measurements. Due to the complexity of the NMR spectra, an extensive use of this method is limited to small protein molecules, for example, antibody domains and some scFv. Here, we describe a protocol that was used to study the dynamics of an antibody domain in solution using NMR. We describe protein preparation for NMR studies, NMR sample optimization, signal assignments, and dynamics experiments. PMID:19252840

  9. High-resolution, high-pressure NMR studies of proteins.

    PubMed Central

    Jonas, J; Ballard, L; Nash, D

    1998-01-01

    Advanced high-resolution NMR spectroscopy, including two-dimensional NMR techniques, combined with high pressure capability, represents a powerful new tool in the study of proteins. This contribution is organized in the following way. First, the specialized instrumentation needed for high-pressure NMR experiments is discussed, with specific emphasis on the design features and performance characteristics of a high-sensitivity, high-resolution, variable-temperature NMR probe operating at 500 MHz and at pressures of up to 500 MPa. An overview of several recent studies using 1D and 2D high-resolution, high-pressure NMR spectroscopy to investigate the pressure-induced reversible unfolding and pressure-assisted cold denaturation of lysozyme, ribonuclease A, and ubiquitin is presented. Specifically, the relationship between the residual secondary structure of pressure-assisted, cold-denatured states and the structure of early folding intermediates is discussed. PMID:9649405

  10. NMR studies of molecules in liquid crystals and graphite

    SciTech Connect

    Rosen, Mark Edward

    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.

  11. High-resolution NMR study of a synthetic DNA-RNA hybrid dodecamer containing the consensus Pribnow promoter sequence

    SciTech Connect

    Chou, S.H.; Flynn, P.; Reid, B. )

    1989-03-21

    The nonsymmetrical double-helical hybrid dodecamer d(CGTTATAATGCG){center dot}r(CGCAUUAUAACG) was synthesized with solid-phase phosphoramidite methods and studied by high-resolution 2D-NMR. The imino protons were assigned by one-dimensional nuclear Overhauser methods. All the base protons and H1', H2', H2'', H3', and H4' sugar protons of the DNA strand and the base protons, H1', H2', and most of the H3'-H4' protons of the RNA strand were assigned by 2D NMR techniques. The well-resolved spectra allowed a qualitative analysis of relative proton-proton distances in both strands of the dodecamer. The chemical shifts of the hybrid duplex were compared to those of the pure DNA double helix with the same sequence. The intrastrand and cross-strand NOEs from adenine H2 to H1' resonances of neighboring base pairs exhibited characteristic patterns that were very useful for checking the spectral assignments, and their highly nonsymmetric nature reveals that the conformations of the two strands are quite different. Detailed analysis of the NOESY and COSY spectra, as well as the chemical shift data, indicate that the RNA strand assumes a normal A-type conformation (C3'-endo) whereas the DNA strand is in the general S domain but not exactly in the normal C2'-endo conformation.

  12. Studies of organic paint binders by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Spyros, A.; Anglos, D.

    2006-06-01

    Nuclear magnetic resonance spectroscopy is applied to the study of aged binding media used in paintings, namely linseed oil, egg tempera and an acrylic medium. High resolution 1D and 2D NMR experiments establish the state of hydrolysis and oxidation of the linseed and egg tempera binders after five years of aging, by determining several markers sensitive to the hydrolytic and oxidative processes of the binder lipid fraction. The composition of the acrylic binder co-polymer is determined by 2D NMR spectroscopy, while the identification of a surfactant, poly(ethylene glycol), found in greater amounts in aged acrylic medium, is reported. The non-destructive nature of the proposed analytical NMR methodology, and minimization of the amount of binder material needed through the use of sophisticated cryoprobes and hyphenated LC-NMR techniques, make NMR attractive for the arts analyst, in view of its rapid nature and experimental simplicity.

  13. Analysis of ethanol-soluble extractives in southern pine wood by low-field proton NMR

    Treesearch

    Thomas L. Eberhardt; Thomas Elder; Nicole Labbe

    2007-01-01

    Low-field portion NMR was evaluated as a nondestructive and rapid technique for measuring ethanol-soluble extractives in southern pine wood. Matchstick-sized wood specimens were steeped in extractive-containing solutions to generate extractive-enriched samples for analysis. decay curves obtained by the Carr-Purcell-Meiboom-gill (CPMG) pulse sequence were analyzed with...

  14. The effects of bone on proton NMR relaxation times of surrounding liquids

    NASA Technical Reports Server (NTRS)

    Davis, C. A.; Genant, H. K.; Dunham, J. S.

    1986-01-01

    Preliminary attempts by our group at UCSF to assess fat content of vertebral marrow in the lumbar spine using relaxation time information demonstrated that the presence of trabecular bone affects relaxation times. The objective of this work was a thorough study of the effects of bone on NMR relaxation characteristics of surrounding liquids. Trabecular bone from autopsy specimens was ground up and sifted into a series of powders with graded densities ranging from 0.3 gm/cc to 0.8 gm/cc. Each powder was placed first in n-saline and then in cottonseed oil. With spectroscopy, spin-lattice relaxation times (T1) and effective spin-spin relaxation times (T2*) were measured for each liquid in each bone powder. As bone density and surface to volume ratio increased, T1 decreased faster for saline than for oil. T2* decreased significantly for both water and oil as the surface to volume ratio increased. It was concluded that effects of water on T1 could be explained by a surface interaction at the bone/liquid interface, which restricted rotational and translational motion of nearby molecules. The T1s of oil were not affected since oil molecules are nonpolar, do not participate in significant intermolecular hydrogen bonding, and therefore would not be expected to interact strongly with the bone surface. Effects on T2* could be explained by local magnetic field inhomogeneities created by discontinuous magnetic susceptibility near the bone surface. These preliminary results suggest that water in contact with trabecular bone in vivo will exhibit shortened relaxation times.

  15. Long-lived states to monitor protein unfolding by proton NMR.

    PubMed

    Bornet, Aurélien; Ahuja, Puneet; Sarkar, Riddhiman; Fernandes, Laetitia; Hadji, Sonia; Lee, Shirley Y; Haririnia, Aydin; Fushman, David; Bodenhausen, Geoffrey; Vasos, Paul R

    2011-10-24

    The relaxation of long-lived states (LLS) corresponds to the slow return to statistical thermal equilibrium between symmetric and antisymmetric proton spin states. This process is remarkably sensitive to the presence of external spins and can be used to obtain information about partial unfolding of proteins. We detected the appearance of a destabilized conformer of ubiquitin when urea is added to the protein in its native state. This conformer shows increased mobility in the C-terminus, which significantly extends the lifetimes of proton LLS magnetisation in Ser-65. These changes could not be detected by conventional measurements of T(1) and T(2) relaxation times of protons, and would hardly be sensed by carbon-13 or nitrogen-15 relaxation measurements. Conformers with similar dynamic and structural features, as revealed by LLS relaxation times, could be observed, in the absence of urea, in two ubiquitin mutants, L67S and L69S.

  16. The role of diffusion in NMR proton relaxation enhancement by ferritin

    NASA Astrophysics Data System (ADS)

    Boss, Michael A.

    By using binary solutions of water and glycerol, we controlled diffusion so as to better understand its role in the relaxation rate enhancement of protons in the vicinity of ferritin at 7 tesla. The slower diffusion rates and higher external magnetic field used in these experiments are more consistent with the conditions expected in MRI experiments. New data was obtained on the diffusion coefficients of water and glycerol in binary solutions with relatively dilute amounts of glycerol. The effects of chemical exchange in such systems was also quantified. Two main relaxation mechanisms have been proposed for protons in the vicinity of ferritin: an outer-sphere mechanism (OS) in which spins diffuse past ferritin and experience a changing Larmor frequency by moving through the ferritin's magnetic field, and a proton exchange dephasing mechanism (PE), where protons temporarily reside on the surface of the ferritin core and sample a single, enhanced, Larmor frequency. At high-field, the OS mechanism becomes increasingly important because of a quadratic dependence on field strength, versus linear for the competing mechanism involving proton exchange. It was found that the relaxation enhancement of protons of both water and glycerol in the presence of ferritin was inversely proportional to their diffusion coefficients, in agreement with the OS model of relaxation enhancement. The strength of the relaxation enhancement on inverse diffusion coefficient was weaker for slow-diffusing glycerol than for water: glycerol molecules spent more time in a weaker magnetic field, indicating that glycerol did not approach the ferritin core as closely as water, potentially answering questions about molecular intake into the ferritin structure. The results of these experiments have important implications for the quantification of brain iron in vivo.

  17. Solid-state proton NMR of paramagnetic metal complexes: DANTE spin echoes for selective excitation in inhomogeneously broadened lines

    NASA Astrophysics Data System (ADS)

    Carnevale, Diego; Perez Linde, A. J.; Bauer, Gerald; Bodenhausen, Geoffrey

    2013-08-01

    The paramagnetic complex bis(oxazolinylphenyl)amine-Fe(III)Cl2 is investigated by means of solid-state proton NMR at 18.8 T (800 MHz) using magic-angle spinning at 65 kHz. Spin echoes that are excited and refocused by combs of rotor-synchronized pulses in the manner of 'Delays Alternating with Nutation for Tailored Excitation' (DANTE) allow one to characterize different chemical environments that severely overlap in conventional MAS spectra. Such sequences combine two apparently contradictory features: an overall bandwidth exceeding several MHz, and very selective irradiation of a few kHz within inhomogeneously broadened sidebands. The experimental hyperfine interactions correlate well with DFT calculations.

  18. 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

  19. 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.

  20. Simulation study of proton transport in ionomers

    NASA Astrophysics Data System (ADS)

    Taylor, Philip; Allahyarov, Elshad

    2008-03-01

    Coarse-grained molecular-dynamics simulations were used to study the morphological changes induced in a Nafion-like ionomer by the imposition of a strong electric field. We observe that proton transport through this polymer electrolyte membrane is accompanied by morphological changes that include the formation of structures aligned along the direction of the applied field. The polar head groups of the ionomer side chains assemble into clusters, which then form rod-like formations, and these cylindrical structures then assemble into a hexagonally ordered array aligned with the direction of current flow. For dry ionomers, at current densities in excess of 1 A/cm^2 these rod-like clusters undergo an inner micro-phase separation, in which distinct wire-like lines of sulfonate head groups are accompanied by similar wire-like alignments of bound protons. The clusters appear to be of two types. If there are two, four, or five lines of sulfonates then there is an equal number of lines of protons, but if there are three lines of sulfonates then they are accompanied by four lines of protons. Occasionally these lines of sulfonates and protons form a helical structure. Upon removal of the electric field, the hexagonal array of rod-like structures remains, but the microphase separation disappears below the threshold current of 1 A/cm^2.

  1. Proton irradiation study of GFR candidate ceramics

    NASA Astrophysics Data System (ADS)

    Gan, Jian; Yang, Yong; Dickson, Clayton; Allen, Todd

    2009-06-01

    This work investigated the microstructural response of SiC, ZrC and ZrN irradiated with 2.6 MeV protons at 800 °C to a fluence of 2.75 × 10 19 protons/cm 2, corresponding to 0.71-1.8 displacement per atom (dpa), depending on the material. The change of lattice constant evaluated using HOLZ patterns is not observed. In comparison to Kr ion irradiation at 800 °C to 10 dpa from the previous studies, the proton irradiated ZrC and ZrN at 1.8 dpa show less irradiation damage to the lattice structure. The proton irradiated ZrC exhibits faulted loops which are not observed in the Kr ion irradiated sample. ZrN shows the least microstructural change from proton irradiation. The microstructure of 6H-SiC irradiated to 0.71 dpa consists of black dot defects at high density.

  2. A LEAN approach toward automated analysis and data processing of polymers using proton NMR spectroscopy.

    PubMed

    de Brouwer, Hans; Stegeman, Gerrit

    2011-02-01

    To maximize utilization of expensive laboratory instruments and to make most effective use of skilled human resources, the entire chain of data processing, calculation, and reporting that is needed to transform raw NMR data into meaningful results was automated. The LEAN process improvement tools were used to identify non-value-added steps in the existing process. These steps were eliminated using an in-house developed software package, which allowed us to meet the key requirement of improving quality and reliability compared with the existing process while freeing up valuable human resources and increasing productivity. Reliability and quality were improved by the consistent data treatment as performed by the software and the uniform administration of results. Automating a single NMR spectrophotometer led to a reduction in operator time of 35%, doubling of the annual sample throughput from 1400 to 2800, and reducing the turn around time from 6 days to less than 2.

  3. High-resolution proton-detected NMR of proteins at very fast MAS

    NASA Astrophysics Data System (ADS)

    Andreas, Loren B.; Le Marchand, Tanguy; Jaudzems, Kristaps; Pintacuda, Guido

    2015-04-01

    When combined with high-frequency (currently ∼60 kHz) magic-angle spinning (MAS), proton detection boosts sensitivity and increases coherence lifetimes, resulting in narrow 1H lines. Herein, we review methods for efficient proton detected techniques and applications in highly deuterated proteins, with an emphasis on 100% selected 1H site concentration for the purpose of sensitivity. We discuss the factors affecting resolution and sensitivity that have resulted in higher and higher frequency MAS. Next we describe the various methods that have been used for backbone and side-chain assignment with proton detection, highlighting the efficient use of scalar-based 13C-13C transfers. Additionally, we show new spectra making use of these schemes for side-chain assignment of methyl 13C-1H resonances. The rapid acquisition of resolved 2D spectra with proton detection allows efficient measurement of relaxation parameters used as a measure of dynamic processes. Under rapid MAS, relaxation times can be measured in a site-specific manner in medium-sized proteins, enabling the investigation of molecular motions at high resolution. Additionally, we discuss methods for measurement of structural parameters, including measurement of internuclear 1H-1H contacts and the use of paramagnetic effects in the determination of global structure.

  4. High-resolution proton-detected NMR of proteins at very fast MAS.

    PubMed

    Andreas, Loren B; Le Marchand, Tanguy; Jaudzems, Kristaps; Pintacuda, Guido

    2015-04-01

    When combined with high-frequency (currently ∼60 kHz) magic-angle spinning (MAS), proton detection boosts sensitivity and increases coherence lifetimes, resulting in narrow ((1))H lines. Herein, we review methods for efficient proton detected techniques and applications in highly deuterated proteins, with an emphasis on 100% selected ((1))H site concentration for the purpose of sensitivity. We discuss the factors affecting resolution and sensitivity that have resulted in higher and higher frequency MAS. Next we describe the various methods that have been used for backbone and side-chain assignment with proton detection, highlighting the efficient use of scalar-based ((13))C-((13))C transfers. Additionally, we show new spectra making use of these schemes for side-chain assignment of methyl ((13))C-((1))H resonances. The rapid acquisition of resolved 2D spectra with proton detection allows efficient measurement of relaxation parameters used as a measure of dynamic processes. Under rapid MAS, relaxation times can be measured in a site-specific manner in medium-sized proteins, enabling the investigation of molecular motions at high resolution. Additionally, we discuss methods for measurement of structural parameters, including measurement of internuclear ((1))H-((1))H contacts and the use of paramagnetic effects in the determination of global structure.

  5. NMR studies of nucleic acid dynamics

    NASA Astrophysics Data System (ADS)

    Al-Hashimi, Hashim M.

    2013-12-01

    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.

  6. 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.

  7. Improving resolution in proton solid-state NMR by removing nitrogen-14 residual dipolar broadening

    NASA Astrophysics Data System (ADS)

    Stein, Robin S.; Elena, Bénédicte; Emsley, Lyndon

    2008-06-01

    Residual dipolar coupling between quadrupolar and other nuclei under MAS has not usually been thought to be important in high field NMR spectroscopy. We show that coupling to 14N broadens 1H lineshapes significantly even at 11.7 T, and that we can decouple 14N from 1H during 1H homonuclear decoupling to successfully improve 1H resolution. The method used for decoupling is the application of evenly spaced pulses to the quadrupolar nucleus.

  8. Sensitivity of proton NMR relaxation times in a HTPB based polyurethane elastomer to thermo-oxidative aging.

    SciTech Connect

    Assink, Roger Alan; Mowery, Daniel Michael; Celina, Mathias Christopher

    2004-09-01

    Solid-state {sup 1}H NMR relaxometry studies were conducted on a hydroxy-terminated polybutadiene (HTPB) based polyurethane elastomer thermo-oxidatively aged at 80 C. The {sup 1}H T{sub 1}, T{sub 2}, and T{sub 1{rho}} relaxation times of samples thermally aged for various periods of time were determined as a function of NMR measurement temperature. The response of each measurement was calculated from a best-fit linear function of the relaxation time vs. aging time. It was found that the T{sub 2,H} and T{sub 1{rho},H} relaxation times exhibited the largest response to thermal degradation, whereas T{sub 1,H} showed minimal change. All of the NMR relaxation measurements on solid samples showed significantly less sensitivity to thermal aging than the T{sub 2,H} relaxation times of solvent-swollen samples.

  9. Spectroscopic studies near the proton drip line

    SciTech Connect

    Toth, K.S. ); Moltz, D.M.; Nitschke, J.M.; Wilmarth, P.A. ); Robertson, J.D. )

    1990-01-01

    We have investigated nuclei close to the proton drip line by using heavy-ion fusion reactions to produce extremely neutron-deficient nuclides. Their nuclear decay properties were studied by using on-line isotope separators at Oak Ridge (UNISOR) and Berkeley (OASIS), the Oak Ridge National Laboratory velocity filter, and a fast helium-gas-jet transport system at Lawrence Berkeley Laboratory 88-Inch Cyclotron. Many isotopes, isomers, and {beta}-delayed-proton and {alpha}-particle emitters were discovered. This contribution summarizes three topics that are part of our overall program: decay rates of even-even {alpha}-particle emitters, mass excesses of {sup 181}Pb, {sup 182}Pb, and {sup 183}Pb, and {beta}-delayed proton emitters near N = 82. 14 refs., 6 figs.

  10. Investigating the Dissolution Performance of Amorphous Solid Dispersions Using Magnetic Resonance Imaging and Proton NMR.

    PubMed

    Tres, Francesco; Coombes, Steven R; Phillips, Andrew R; Hughes, Leslie P; Wren, Stephen A C; Aylott, Jonathan W; Burley, Jonathan C

    2015-09-10

    We have investigated the dissolution performance of amorphous solid dispersions of poorly water-soluble bicalutamide in a Kollidon VA64 polymeric matrix as a function of the drug loading (5% vs. 30% bicalutamide). A combined suite of state-of-the-art analytical techniques were employed to obtain a clear picture of the drug release, including an integrated magnetic resonance imaging UV-Vis flow cell system and 1H-NMR. Off-line 1H-NMR was used for the first time to simultaneously measure the dissolution profiles and rates of both the drug and the polymer from a solid dispersion. MRI and 1H-NMR data showed that the 5% drug loading compact erodes linearly, and that bicalutamide and Kollidon VA64 are released at approximately the same rate from the molecular dispersion. For the 30% extrudate, data indicated a slower water ingress into the compact which corresponds to a slower dissolution rate of both bicalutamide and Kollidon VA64.

  11. 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

  12. 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.

  13. NMR and computational studies of chiral discrimination by amylose tris(3,5-dimethylphenylcarbamate).

    PubMed

    Ye, Yun K; Bai, Shi; Vyas, Shyam; Wirth, Mary J

    2007-02-08

    Proton NMR and simulations were combined to study the origin of chiral selectivity by a polysaccharide used in a commercial chromatographic stationary phase: amylose tris(3,5-dimethylphenylcarbamate). This material has unusually high enantioselectivity for p-O-tert-butyltyrosine allyl ester, which is activated by the presence of an acid. Proton NMR spectra agreed with the HPLC in showing that the l-enantiomer interacts much more strongly with the polysaccharide and that acidity switches on the selectivity. 2D NOESY spectra revealed which protons of each enantiomer and the polysaccharide were in proximity, and these spectra revealed folding of the l-enantiomer. Computations generated energy-minimized structures for the polysaccharide-enantiomer complexes, independently predicting folding of the l-enantiomer. Molecular dynamics simulations 2 ns in duration, repeated for three different energy-minimized structures, generated pair distribution functions that are in excellent agreement with the 2D NOESY spectra. The modeling studies revealed why acidity switches on chiral selectivity and minimally affects the chromatographic retention time of the unfavored d-enantiomer. The results comprise the first case of a chiral separation by a commercial polysaccharide stationary phase being explained using a combination of 2D NOESY and simulations, providing excellent agreement between experiment and computation and lending detailed molecular insight into enantioselectivity for this system.

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

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  15. In vivo high-resolution magic angle spinning proton NMR spectroscopy of Drosophila melanogaster flies as a model system to investigate mitochondrial dysfunction in Drosophila GST2 mutants.

    PubMed

    Righi, Valeria; Apidianakis, Yiorgos; Psychogios, Nikolaos; Rahme, Laurence G; Tompkins, Ronald G; Tzika, A Aria

    2014-07-01

    In vivo nuclear magnetic resonance spectroscopy (NMR), a non-destructive biochemical tool used for investigating live organisms, has recently been performed in studies of the fruit fly Drosophila melanogaster, a useful model organism for investigating genetics and physiology. We used a novel high-resolution magic angle-spinning (HRMAS) NMR method to investigate live Drosophila GST2 mutants using a conventional 14.1-T NMR spectrometer equipped with an HRMAS probe. The results showed that, compared to wild-type (wt) controls, the GST2 mutants had a 48% greater (CH(2))n lipid signal at 1.33 ppm, which is an insulin resistance biomarker in Drosophila skeletal muscle (P=0.0444). The mutants also had a 57% greater CH(2)C= lipid signal at 2.02 ppm (P=0.0276) and a 100% greater -CH=CH- signal at 5.33 ppm (P=0.0251). Since the -CH=CH- signal encompasses protons from ceramide, this latter difference is consistent with the hypothesis that the GST2 mutation is associated with insulin resistance and apoptosis. The findings of this study corroborate our previous results, support the hypothesis that the GST2 mutation is associated with insulin signaling and suggest that the IMCL level may be a biomarker of insulin resistance. Furthermore, direct links between GST2 mutation (the Drosophila ortholog of the GSTA4 gene in mammals) and insulin resistance, as suggested in this study, have not been made previously. These findings may thus be directly relevant to a wide range of metabolically disruptive conditions, such as trauma, aging and immune system deficiencies, that lead to increased susceptibility to infection.

  16. Characterizing source fingerprints and ageing processes in laboratory-generated secondary organic aerosols using proton-nuclear magnetic resonance (1H-NMR) analysis and HPLC HULIS determination

    NASA Astrophysics Data System (ADS)

    Zanca, Nicola; Lambe, Andrew T.; Massoli, Paola; Paglione, Marco; Croasdale, David R.; Parmar, Yatish; Tagliavini, Emilio; Gilardoni, Stefania; Decesari, Stefano

    2017-09-01

    The study of secondary organic aerosol (SOA) in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM) oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescales that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization - proton nuclear magnetic resonance (1H-NMR) spectroscopy and HPLC determination of humic-like substances (HULIS). Results were compared with previous Aerodyne aerosol mass spectrometer (AMS) measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1 × 1012 molec OH cm-3 × s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC), providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.

  17. 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.

  18. Interfaces in polymer nanocomposites – An NMR study

    SciTech Connect

    Böhme, Ute; Scheler, Ulrich

    2016-03-09

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

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

    PubMed

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

    1991-04-01

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

  20. Diamond Deposition and Defect Chemistry Studied via Solid State NMR

    DTIC Science & Technology

    1994-06-30

    same integrated NMR signal, regardless of its chemical environment, provided complete spin-lattice relaxation occurs between averages 3 . Gem -quality...occurs between averages, and broadening from years, a large research effort has been devoted to the study paramagnetic centers is insignificant. Gem ...information on the distribution and motion mond’s durability very attractive. However, while gem - of hydrogen can be obtained from the solid-state NMR

  1. 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

  2. Expanding the horizons for structural analysis of fully protonated protein assemblies by NMR spectroscopy at MAS frequencies above 100 kHz.

    PubMed

    Struppe, Jochem; Quinn, Caitlin M; Lu, Manman; Wang, Mingzhang; Hou, Guangjin; Lu, Xingyu; Kraus, Jodi; Andreas, Loren B; Stanek, Jan; Lalli, Daniela; Lesage, Anne; Pintacuda, Guido; Maas, Werner; Gronenborn, Angela M; Polenova, Tatyana

    2017-07-03

    The recent breakthroughs in NMR probe technologies resulted in the development of MAS NMR probes with rotation frequencies exceeding 100 kHz. Herein, we explore dramatic increases in sensitivity and resolution observed at MAS frequencies of 110-111 kHz in a novel 0.7 mm HCND probe that enable structural analysis of fully protonated biological systems. Proton- detected 2D and 3D correlation spectroscopy under such conditions requires only 0.1-0.5 mg of sample and a fraction of time compared to conventional (13)C-detected experiments. We discuss the performance of several proton- and heteronuclear- ((13)C-,(15)N-) based correlation experiments in terms of sensitivity and resolution, using a model microcrystalline fMLF tripeptide. We demonstrate the applications of ultrafast MAS to a large, fully protonated protein assembly of the 231-residue HIV-1 CA capsid protein. Resonance assignments of protons and heteronuclei, as well as (1)H-(15)N dipolar and (1)H(N) CSA tensors are readily obtained from the high sensitivity and resolution proton-detected 3D experiments. The approach demonstrated here is expected to enable the determination of atomic-resolution structures of large protein assemblies, inaccessible by current methodologies. Copyright © 2017. Published by Elsevier Inc.

  3. Proton Dynamics in the Anti-ferroelectric CsH3(SeO3)2 by using 1H NMR Measurements

    NASA Astrophysics Data System (ADS)

    Lee, Moohee; Ndiaye, B.; Kang, K.; Kim, H.; Sim, J.; Lim, Ae Ran

    2014-03-01

    1H NMR techniques have been employed on the anti-ferroelectric CsH3(SeO3)2 to measure spectrum, shift, T1 and T2 from 300 K down to 80 K at 4.85 T. The 1H NMR spectrum at 300 K shows a composite structure; one dominant broad peak and two small narrow peaks. From the temperature dependences of both intensity and T1 for each peak, we identify that the narrow peaks come from rapidly moving protons whereas the broad peaks originate from rigid protons. The spectra below 200 K show several peaks associated with six nonequivalent proton sites and also the T1 decays show a non-exponential curve coming from many proton sites. T1 is very long even at 300 K and becomes even longer at low temperature. By analyzing T1 decays with T1S and T1L, we confirm that 1/T1(T) show an activated behavior; the short component originates from proton dynamics with activation energy of ~ 140 K and the long component is associated with that of ~ 100 K. Further analysis suggests that some protons show an abrupt change in both shift and T1L across Tc and may be responsible for the phase transition.

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

    NASA Astrophysics Data System (ADS)

    Tang, J. H.

    1981-11-01

    The theoretical background of spin Hamiltonians, the density matrix formalism of multiple quantum NMR are discussed as well as creation and detection of multiple quantum coherence by multiple pulse sequence. Prototype multiple quantum spectra of oriented benzene are presented. Redfield relaxation theory and the application of multiple quantum NMR to the study of correlations in fluctuations are considered. An oriented methyl group relaxed by paramagnetic impurities is examined and possible correlated motion between two coupled methyl groups is investigated by multiple quantum NMR. For a six spin system it is shown that the four quantum spectrum is sensitive to two body correlations, and serves a ready test of correlated motion. The spin lattice dynamics of orienting or tunneling methyl groups (CH3 and CD3) at low temperatures and the anisotropic spin lattice relaxation of deuterated hexamethylbenzene, caused by the sixfold reorientation of the molecules are described as well as NMR spectrometers.

  5. Proton nuclear magnetic resonance studies on brain edema

    SciTech Connect

    Naruse, S.; Horikawa, Y.; Tanaka, C.; Hirakawa, K.; Nishikawa, H.; Yoshizaki, K.

    1982-06-01

    The water in normal and edematous brain tissues of rats was studied by the pulse nuclear magnetic resonance (NMR) technique, measuring the longitudinal relaxation time (T1) and the transverse relaxation time (T2). In the normal brain, T1 and T2 were single components, both shorter than in pure water. Prolongation and separation of T2 into two components, one fast and one slow, were the characteristic findings in brain edema induced by both cold injury and triethyl tin (TET), although some differences between the two types of edema existed in the content of the lesion and in the degree of changes in T1 and T2 values. Quantitative analysis of T1 and T2 values in their time course relating to water content demonstrated that prolongation of T1 referred to the volume of increased water in tissues examined, and that two phases of T2 reflected the distribution and the content of the edema fluid. From the analysis of the slow component of T2 versus water content during edema formation, it was demonstrated that the increase in edema fluid was steady, and its content was constant during formation of TET-induced edema. On the contrary, during the formation of cold-injury edema, water-rich edema fluid increased during the initial few hours, and protein-rich edema fluid increased thereafter. It was concluded that proton NMR relaxation time measurements may provide new understanding in the field of brain edema research.

  6. /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.

  7. 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

  8. 1H and 19 F NMR Study of Cation and Anion Motions in Guanidinium Hexafluorozirconate

    NASA Astrophysics Data System (ADS)

    Grottel, M.; Kozak, A.; Pająk, Z.

    1996-09-01

    Proton and fluorine NMR second moments and spin-lattice relaxation times of polycrystalline guanidinium hexafluorozirconate and its deuterated analogue were studied in laboratory (60 MHz) and rotating (H1 = 20 G) frames over a wide range of temperature. An analysis of the experimental results enabled us to reveal a dynamical inequivalence of two crystallographically independent cations and an unexpected high mobility of nonspherical anion dimers. A comparison of the ions dynamics in 2:1 complex studied with the guanidinium 1:1 and 3:1 complexes has shown a significant contribution of the hydrogen bonds to the potential barriers hindering the anion reorientations. At low temperatures a proton motion in the hydrogen bond and at 400 K a solid-solid phase transition have been discerned.

  9. The potential utility of predicted one bond carbon-proton coupling constants in the structure elucidation of small organic molecules by NMR spectroscopy.

    PubMed

    Venkata, Chandrasekhar; Forster, Mark J; Howe, Peter W A; Steinbeck, Christoph

    2014-01-01

    NMR spectroscopy is the most popular technique used for structure elucidation of small organic molecules in solution, but incorrect structures are regularly reported. One-bond proton-carbon J-couplings provide additional information about chemical structure because they are determined by different features of molecular structure than are proton and carbon chemical shifts. However, these couplings are not routinely used to validate proposed structures because few software tools exist to predict them. This study assesses the accuracy of Density Functional Theory for predicting them using 396 published experimental observations from a diverse range of small organic molecules. With the B3LYP functional and the TZVP basis set, Density Functional Theory calculations using the open-source software package NWChem can predict one-bond CH J-couplings with good accuracy for most classes of small organic molecule. The root-mean-square deviation after correction is 1.5 Hz for most sp3 CH pairs and 1.9 Hz for sp2 pairs; larger errors are observed for sp3 pairs with multiple electronegative substituents and for sp pairs. These results suggest that prediction of one-bond CH J-couplings by Density Functional Theory is sufficiently accurate for structure validation. This will be of particular use in strained ring systems and heterocycles which have characteristic couplings and which pose challenges for structure elucidation.

  10. The Potential Utility of Predicted One Bond Carbon-Proton Coupling Constants in the Structure Elucidation of Small Organic Molecules by NMR Spectroscopy

    PubMed Central

    Venkata, Chandrasekhar; Forster, Mark J.; Howe, Peter W. A.; Steinbeck, Christoph

    2014-01-01

    NMR spectroscopy is the most popular technique used for structure elucidation of small organic molecules in solution, but incorrect structures are regularly reported. One-bond proton-carbon J-couplings provide additional information about chemical structure because they are determined by different features of molecular structure than are proton and carbon chemical shifts. However, these couplings are not routinely used to validate proposed structures because few software tools exist to predict them. This study assesses the accuracy of Density Functional Theory for predicting them using 396 published experimental observations from a diverse range of small organic molecules. With the B3LYP functional and the TZVP basis set, Density Functional Theory calculations using the open-source software package NWChem can predict one-bond CH J-couplings with good accuracy for most classes of small organic molecule. The root-mean-square deviation after correction is 1.5 Hz for most sp3 CH pairs and 1.9 Hz for sp2 pairs; larger errors are observed for sp3 pairs with multiple electronegative substituents and for sp pairs. These results suggest that prediction of one-bond CH J-couplings by Density Functional Theory is sufficiently accurate for structure validation. This will be of particular use in strained ring systems and heterocycles which have characteristic couplings and which pose challenges for structure elucidation. PMID:25365289

  11. NMR relaxation of protein and water protons in diamagnetic hemoglobin solutions.

    PubMed

    Eisenstadt, M

    1985-07-02

    We have measured T1 and T2 of protein and water protons in hemoglobin solutions using broad-line pulse techniques; selective excitation and detection methods enabled the intrinsic protein and water relaxation rates, as well as the spin-transfer rate between them, to be obtained at 5, 10, and 20 MHz. Water and protein T1 data were also obtained at 100 and 200 MHz for hemoglobin in H2O/D2O mixtures by using commercial Fourier-transform instruments. The T1 data conform to a simple model of two well-mixed spin systems with single intrinsic relaxation times and an average spin-transfer rate, with each phase recovering from a radio-frequency excitation with a biexponential time dependence. At low frequencies, protein T1 and T2 agree reasonably with a model of dipolar relaxation of an array of fixed protons tumbling in solution, explicitly calculating methyl and methylene relaxation and using a continuum approximation for the others. Differing values in H2O and D2O are mainly ascribed to solvent viscosity. For water-proton relaxation, T1, T2, and spin transfer were measured for H2O and HDO, which enabled a separation of inter-and intramolecular contributions to relaxation. Despite such detail, few firm conclusions could be reached about hydration water. But it seems clear that few long-lived hydration sites are needed to explain T1 and T2, and the spin-transfer value mandates fewer than five sites with a lifetime longer than 10(-8) s.

  12. NMR studies on 4-thio-5-furan-modified and 4-thio-5-thiophene-modified nucleosides.

    PubMed

    Zhang, Xiao-Hui; Xu, Yao-Zhong

    2016-11-01

    Systematic NMR characterization of 4-thio-5-furan-pyrimidine nucleosides or 4-thio-5-thiophene-pyrimidine nucleosides (ribonucleosides and 2'-deoxynucleosides) was performed. All proton and carbon signals of 4-thio-5-thiophene-ribouridine and related analogues were unambiguously assigned. The orientations of the base (4-thiouridine or its deoxy analogue) relative to the ring (furan or thiophene) are explored by a NMR approach and further supported by X-ray crystallographic studies. The procedures presented here would be applicable to other modified nucleosides and nucleotides. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  13. Excited States of Nucleic Acids Probed by Proton Relaxation Dispersion NMR Spectroscopy

    PubMed Central

    Juen, Michael Andreas; Wunderlich, Christoph Hermann; Nußbaumer, Felix; Tollinger, Martin; Kontaxis, Georg; Konrat, Robert

    2016-01-01

    Abstract In this work an improved stable isotope labeling protocol for nucleic acids is introduced. The novel building blocks eliminate/minimize homonuclear 13C and 1H scalar couplings thus allowing proton relaxation dispersion (RD) experiments to report accurately on the chemical exchange of nucleic acids. Using site‐specific 2H and 13C labeling, spin topologies are introduced into DNA and RNA that make 1H relaxation dispersion experiments applicable in a straightforward manner. The novel RNA/DNA building blocks were successfully incorporated into two nucleic acids. The A‐site RNA was previously shown to undergo a two site exchange process in the micro‐ to millisecond time regime. Using proton relaxation dispersion experiments the exchange parameters determined earlier could be recapitulated, thus validating the proposed approach. We further investigated the dynamics of the cTAR DNA, a DNA transcript that is involved in the viral replication cycle of HIV‐1. Again, an exchange process could be characterized and quantified. This shows the general applicablility of the novel labeling scheme for 1H RD experiments of nucleic acids. PMID:27533469

  14. Excited States of Nucleic Acids Probed by Proton Relaxation Dispersion NMR Spectroscopy.

    PubMed

    Juen, Michael Andreas; Wunderlich, Christoph Hermann; Nußbaumer, Felix; Tollinger, Martin; Kontaxis, Georg; Konrat, Robert; Hansen, D Flemming; Kreutz, Christoph

    2016-09-19

    In this work an improved stable isotope labeling protocol for nucleic acids is introduced. The novel building blocks eliminate/minimize homonuclear (13) C and (1) H scalar couplings thus allowing proton relaxation dispersion (RD) experiments to report accurately on the chemical exchange of nucleic acids. Using site-specific (2) H and (13) C labeling, spin topologies are introduced into DNA and RNA that make (1) H relaxation dispersion experiments applicable in a straightforward manner. The novel RNA/DNA building blocks were successfully incorporated into two nucleic acids. The A-site RNA was previously shown to undergo a two site exchange process in the micro- to millisecond time regime. Using proton relaxation dispersion experiments the exchange parameters determined earlier could be recapitulated, thus validating the proposed approach. We further investigated the dynamics of the cTAR DNA, a DNA transcript that is involved in the viral replication cycle of HIV-1. Again, an exchange process could be characterized and quantified. This shows the general applicablility of the novel labeling scheme for (1) H RD experiments of nucleic acids. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Studying the Proton Spin Puzzle with PHENIX

    NASA Astrophysics Data System (ADS)

    Daugherity, Michael

    2012-03-01

    The proton spin puzzle remains one of the biggest mysteries in fundamental particle physics today. This talk will explore how the PHENIX Collaboration's forward W-boson program uses RHIC, the world's only polarized proton-proton collider, to probe the spin structure of the proton.

  16. 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.

  17. Conformation of the ATP binding peptide in actin revealed by proton NMR spectroscopy

    SciTech Connect

    Barden, J.A.

    1987-09-22

    The actin peptide 106-124 exists in a completely conserved region of the sequence and binds strongly to both ATP and tripolyphosphate. Binding particularly affects residues 116 and 118 and generally affects the two segments 115-118 and 121-124. One-dimensional nuclear Overhauser enhancement difference spectroscopy was used to detect molecular interactions between both adjacent and nonadjacent residues. The N-terminal segment 106-112 was found to be largely extended. A sharp bend was detected between Pro-112 and Lys-113. The triphosphate moiety binds to the strongly hydrophilic central segment of the peptide. Evidence was obtained for a reverse turn involving residues 121-124. Amide proton temperature coefficients and coupling constants provide evidence for a type I ..beta..-turn. A model of the ATP binding site is proposed together with its relationship to other parts of the actin structure and to the phalloidin binding site.

  18. Joint Experimental and Computational 17O and 1H Solid State NMR Study of Ba2In2O4(OH)2 Structure and Dynamics

    PubMed Central

    2015-01-01

    A structural characterization of the hydrated form of the brownmillerite-type phase Ba2In2O5, Ba2In2O4(OH)2, is reported using experimental multinuclear NMR spectroscopy and density functional theory (DFT) energy and GIPAW NMR calculations. When the oxygen ions from H2O fill the inherent O vacancies of the brownmillerite structure, one of the water protons remains in the same layer (O3) while the second proton is located in the neighboring layer (O2) in sites with partial occupancies, as previously demonstrated by Jayaraman et al. (Solid State Ionics2004, 170, 25−32) using X-ray and neutron studies. Calculations of possible proton arrangements within the partially occupied layer of Ba2In2O4(OH)2 yield a set of low energy structures; GIPAW NMR calculations on these configurations yield 1H and 17O chemical shifts and peak intensity ratios, which are then used to help assign the experimental MAS NMR spectra. Three distinct 1H resonances in a 2:1:1 ratio are obtained experimentally, the most intense resonance being assigned to the proton in the O3 layer. The two weaker signals are due to O2 layer protons, one set hydrogen bonding to the O3 layer and the other hydrogen bonding alternately toward the O3 and O1 layers. 1H magnetization exchange experiments reveal that all three resonances originate from protons in the same crystallographic phase, the protons exchanging with each other above approximately 150 °C. Three distinct types of oxygen atoms are evident from the DFT GIPAW calculations bare oxygens (O), oxygens directly bonded to a proton (H-donor O), and oxygen ions that are hydrogen bonded to a proton (H-acceptor O). The 17O calculated shifts and quadrupolar parameters are used to assign the experimental spectra, the assignments being confirmed by 1H–17O double resonance experiments. PMID:26321789

  19. Proton energy and scattering angle radiographs to improve proton treatment planning: a Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Biegun, A. K.; Takatsu, J.; Nakaji, T.; van Goethem, M. J.; van der Graaf, E. R.; Koffeman, E. N.; Visser, J.; Brandenburg, S.

    2016-12-01

    The novel proton radiography imaging technique has a large potential to be used in direct measurement of the proton energy loss (proton stopping power, PSP) in various tissues in the patient. The uncertainty of PSPs, currently obtained from translation of X-ray Computed Tomography (xCT) images, should be minimized from 3-5% or higher to less than 1%, to make the treatment plan with proton beams more accurate, and thereby better treatment for the patient. With Geant4 we simulated a proton radiography detection system with two position-sensitive and residual energy detectors. A complex phantom filled with various materials (including tissue surrogates), was placed between the position sensitive detectors. The phantom was irradiated with 150 MeV protons and the energy loss radiograph and scattering angles were studied. Protons passing through different materials in the phantom lose energy, which was used to create a radiography image of the phantom. The multiple Coulomb scattering of a proton traversing different materials causes blurring of the image. To improve image quality and material identification in the phantom, we selected protons with small scattering angles. A good quality proton radiography image, in which various materials can be recognized accurately, and in combination with xCT can lead to more accurate relative stopping powers predictions.

  20. A processing method enabling the use of peak height for accurate and precise proton NMR quantitation.

    PubMed

    Hays, Patrick A; Thompson, Robert A

    2009-10-01

    In NMR, peak area quantitation is the most common method used because the area under a peak or peak group is proportional to the number of nuclei at those frequencies. Peak height quantitation has not enjoyed as much utility because of poor precision and linearity as a result of inconsistent shapes and peak widths (measured at half height). By using a post-acquisition processing method employing a Gaussian or line-broadening (exponential decay) apodization (i.e. weighting function) to normalize the shape and width of the internal standard (ISTD) peak, the heights of an analyte calibration spectrum can be compared to the analyte peaks in a sample spectrum resulting in accurate and precise quantitative results. Peak height results compared favorably with 'clean' peak area results for several hundred illicit samples of methamphetamine HCl, cocaine HCl, and heroin HCl, of varying composition and purity. Using peak height and peak area results together can enhance the confidence in the reported purity value; a major advantage in high throughput, automated quantitative analyses. Published in 2009 by John Wiley & Sons, Ltd.

  1. Metabolic changes during cellular senescence investigated by proton NMR-spectroscopy.

    PubMed

    Gey, Claudia; Seeger, Karsten

    2013-03-01

    Cellular senescence is of growing interest due to its role in tumour suppression and its contribution to organismic ageing. This cellular state can be reached by replicative loss of telomeres or certain stresses in cell culture and is characterized by the termination of cell division; however, the cells remain metabolically active. To identify metabolites that are characteristic for senescent cells, extracts of human embryonic lung fibroblast (WI-38 cell line) have been investigated with NMR spectroscopy. Three different types of senescence have been characterized: replicative senescence, DNA damage-induced senescence (etoposide treatment) and oncogene-induced senescence (hyperactive RAF kinase). The metabolite pattern allows (I) discrimination of senescent and control cells and (II) discrimination of the three senescence types. Senescent cells show an increased ratio of glycerophosphocholine to phosphocholine independent from the type of senescence. The increase in glycerophosphocholine implicates a key role of phospholipid metabolism in cellular senescence. The observed changes in the choline metabolism are diametrically opposite to the well-known changes in choline metabolism of tumour cells. As tumours responding to chemotherapeutic agents show a "glycerophosphocholine-to-phosphocholine switch" i.e. an increase in glycerophosphocholine, our metabolic data suggests that these malignant cells enter a senescent state emphasizing the role of senescence in tumour suppression.

  2. Study of cultured fibroblasts in vivo using NMR

    SciTech Connect

    Karczmar, G.S.

    1984-08-01

    The goal was to study the compartmentation of phosphorylated glycolytic intermediates in intact Chicken Embryo Fibroblasts (CEFs) using /sup 31/P NMR at 109 MHz. A technique for maintaining functional cells at high densities in an NMR magnet is described. Signals were detected from cytoplasmic inorganic phosphate (P/sub i/), ATP, NAD, NADH, phosphorylcholine and phosphorylethanolamine. The effect of external glucose on cytoplasmic pools of phosphates was studied. When cells were perfused with glucose-free medium the rate of glycolysis decreased, the amplitudes of the ATP resonances decreased, and the P/sub i/ intensity increased. The quantity of NMR-detectable P/sub i/ produced was significantly greater than the quantity of NMR-detectable ATP which was lost. Experiments with /sup 32/P labeled P/sub i/ showed that as the concentration of glucose in the medium was increase, the amount of phosphate sequestered in the cells increased. We conclude that there is a pool of P/sub i/ which is not detected by high resolution NMR and that the size of this pool increases as the rate of glycolysis increase. Longtitudinal relaxation times of intracellular phosphates in normal, transformed, and primary CEFs were measured. The results demonstrate that relaxation times of phosphates are sensitive to structural and metabolic changes which occur when cells are grown in culture. 59 references. 31 figures.

  3. Hysteresis effect of ammonium and water protons by 1H MAS NMR in (NH4)2CuBr4·2H2O

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran; Cho, Jiung

    2017-10-01

    The chemical shifts, linewidths, and spin-lattice relaxation times for ammonium and water protons in (NH4)2CuBr4·2H2O were investigated by 1H magic angle spinning nuclear magnetic resonance (MAS NMR) with a focus on the roles of NH4+ and H2O at high temperatures. The changes in the temperature dependence of the data near Td (=360 K) were related to variations of the H environments; the mechanism above Td was related to hydrogen-bond transfer involving breakage of the weak part of the hydrogen bond. The hysteresis effects for the ammonium and water protons in (NH4)2CuBr4·2H2O by MAS NMR were described with respect to heating and cooling.

  4. Review of NMR studies of nanoscale molecular magnets composed of geometrically frustrated antiferromagnetic triangles

    DOE PAGES

    Furukawa, Yuji

    2016-10-01

    This paper presents a comprehensive review of nuclear magnetic resonance (NMR) studies performed on three nanoscale molecular magnets with different novel configurations of geometrically frustrated antiferromagnetic (AFM) triangles: (1) the isolated single AFM triangle K6[V15As6O42(H2O)]·8H2O (in short V15), (2) the spin ball [Mo72Fe30O252(Mo2O7(H2O))2(Mo2O8H2(H2O)) (CH3COO)12(H2O)91]·150H2O (in short Fe30 spin ball), and (3) the twisted triangular spin tube [(CuCl2tachH)3Cl]Cl2 (in short Cu3 spin tube). In V15t, from 51V NMR spectra, the local spin configurations were directly determined in both the nonfrustrated total spin ST = 3/2 state at higher magnetic fields (H ge; 2.7 T) and the two nearly degenerate ST =more » 1/2 ground states at lower magnetic fields (H ≤ 2.7 T). The dynamical magnetic properties of V15 were investigated by proton spin-lattice relaxation rate (1/T1) measurements. In the ST = 3/2 state, 1/T1 shows thermally activated behaviour as a function of temperature. On the other hand, the temperature independent behaviour of 1/T1 at very low temperatures is observed in the frustrated ST = 1/2 ground state. Possible origins for the peculiar behaviour of 1/T1 will be discussed in terms of magnetic fluctuations due to spin frustrations. In Fe30, static and dynamical properties of Fe3+ (s = 5/2) have been investigated by proton NMR spectra and 1/T1 measurements. From the temperature dependence of 1/T1, the fluctuation frequency of the Fe3+ spins is found to decrease with decreasing temperature, indicating spin freezing at low temperatures. The spin freezing is also evidenced by the observation of a sudden broadening of 1H NMR spectra below 0.6 K. Finally, 1H NMR data in Cu3 will be described. An observation of magnetic broadening of 1H NMR spectra at low temperatures below 1 K directly revealed a gapless ground state. The 1/T1 measurements revealed a usual slow spin dynamics in the Cu3 spin tube.« less

  5. 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.

  6. Solution NMR Spectroscopy for the Study of Enzyme Allostery

    PubMed Central

    Lisi, George P.; Loria, J. Patrick

    2016-01-01

    Allostery is a ubiquitous biological regulatory process in which distant binding sites within a protein or enzyme are functionally and thermodynamically coupled. Allosteric interactions play essential roles in many enzymological mechanisms, often facilitating formation of enzyme-substrate complexes and/or product release. Thus, elucidating the forces that drive allostery is critical to understanding the complex transformations of biomolecules. Currently, a number of models exist to describe allosteric behavior, taking into account energetics as well as conformational rearrangements and fluctuations. In the following review, we discuss the use of solution NMR techniques designed to probe allosteric mechanisms in enzymes. NMR spectroscopy is unequaled in its ability to detect structural and dynamical changes in biomolecules, and the case studies presented herein demonstrate the range of insights to be gained from this valuable method. We also provide a detailed technical discussion of several specialized NMR experiments that are ideally suited for the study of enzymatic allostery. PMID:26734986

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

    PubMed Central

    Sobolev, Anatoly P.; Capitani, Donatella; Giannino, Donato; Nicolodi, Chiara; Testone, Giulio; Santoro, Flavio; Frugis, Giovanna; Iannelli, Maria A.; Mattoo, Autar K.; Brosio, Elvino; Gianferri, Raffaella; D’Amico, Irene; Mannina, Luisa

    2010-01-01

    The 1H-NMR methodology used in the study of genetically modified (GM) foods is discussed. Transgenic lettuce (Lactuca sativa cv "Luxor") over-expressing the ArabidopsisKNAT1 gene is presented as a case study. Twenty-two water-soluble metabolites (amino acids, organic acids, sugars) present in leaves of conventional and GM lettuce were monitored by NMR and quantified at two developmental stages. The NMR spectra did not reveal any difference in metabolite composition between the GM lettuce and the wild type counterpart. Statistical analyses of metabolite variables highlighted metabolism variation as a function of leaf development as well as the transgene. A main effect of the transgene was in altering sugar metabolism. PMID:22253988

  8. (1)JCH NMR Profile: Identification of Key Structural Features and Functionalities by Visual Observation and Direct Measurement of One-Bond Proton-Carbon Coupling Constants.

    PubMed

    Marcó, Núria; Souza, Alexandre A; Nolis, Pau; Cobas, Carlos; Gil, Roberto R; Parella, Teodor

    2017-02-17

    A user-friendly NMR interface for the visual and accurate determination of experimental one-bond proton-carbon coupling constants ((1)JCH) in small molecules is presented. This intuitive (1)JCH profile correlates directly to δ((1)H), and (1)JCH facilitates the rapid identification and assignment of (1)H signals belonging to key structural elements and functional groups. Illustrative examples are provided for some target molecules, including terminal alkynes, strained rings, electronegative substituents, or lone-pair-bearing heteronuclei.

  9. Proton conduction in biopolymer exopolysaccharide succinoglycan

    NASA Astrophysics Data System (ADS)

    Kweon, Jin Jung; Lee, Kyu Won; Kim, Hyojung; Lee, Cheol Eui; Jung, Seunho; Kwon, Chanho

    2014-07-01

    Protonic currents play a vital role in electrical signalling in living systems. It has been suggested that succinoglycan plays a specific role in alfalfa root nodule development, presumably acting as the signaling molecules. In this regard, charge transport and proton dynamics in the biopolymer exopolysaccharide succinoglycan have been studied by means of electrical measurements and nuclear magnetic resonance (NMR) spectroscopy. In particular, a dielectric dispersion in the system has revealed that the electrical conduction is protonic rather electronic. Besides, our laboratory- and rotating-frame 1H NMR measurements have elucidated the nature of the protonic conduction, activation of the protonic motion being associated with a glass transition.

  10. Proton conduction in biopolymer exopolysaccharide succinoglycan

    SciTech Connect

    Kweon, Jin Jung; Lee, Kyu Won; Kim, Hyojung; Lee, Cheol Eui; Jung, Seunho; Kwon, Chanho

    2014-07-07

    Protonic currents play a vital role in electrical signalling in living systems. It has been suggested that succinoglycan plays a specific role in alfalfa root nodule development, presumably acting as the signaling molecules. In this regard, charge transport and proton dynamics in the biopolymer exopolysaccharide succinoglycan have been studied by means of electrical measurements and nuclear magnetic resonance (NMR) spectroscopy. In particular, a dielectric dispersion in the system has revealed that the electrical conduction is protonic rather electronic. Besides, our laboratory- and rotating-frame {sup 1}H NMR measurements have elucidated the nature of the protonic conduction, activation of the protonic motion being associated with a glass transition.

  11. Theoretical and experimental IR, Raman and NMR spectra in studying the electronic structure of 2-nitrobenzoates

    NASA Astrophysics Data System (ADS)

    Świsłocka, R.; Samsonowicz, M.; Regulska, E.; Lewandowski, W.

    2007-05-01

    The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-nitrobenzoic acid (2-NBA) was studied. Optimized geometrical structures of studied compounds were calculated by HF, B3PW91, B3LYP methods using 6-311++G ∗∗ basis set. The theoretical IR and NMR spectra were obtained. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-nitrobenzoic acid salts of alkali metals were also recorded. The assignment of vibrational spectra was done. Characteristic shifts of band wavenumbers and changes in band intensities along the metal series were observed. Good correlation between the wavenumbers of the vibrational bands in the IR and Raman spectra for 2-nitrobenzoates (2-NB) and ionic potential, electronegativity, atomic mass and affinity of metals were found. The chemical shifts of protons and carbons ( 1H, 13C NMR) in the series of studied alkali metal 2-nitrobenzoates were observed too. The calculated parameters were compared to experimental characteristic of studied compounds.

  12. A carbon-13 and proton nuclear magnetic resonance study of some experimental referee broadened-specification /ERBS/ turbine fuels

    NASA Technical Reports Server (NTRS)

    Dalling, D. K.; Pugmire, R. J.

    1982-01-01

    Preliminary results of a nuclear magnetic resonance (NMR) spectroscopy study of alternative jet fuels are presented. A referee broadened-specification (ERBS) aviation turbine fuel, a mixture of 65 percent traditional kerosene with 35 percent hydrotreated catalytic gas oil (HCGO) containing 12.8 percent hydrogen, and fuels of lower hydrogen content created by blending the latter with a mixture of HCGO and xylene bottoms were studied. The various samples were examined by carbon-13 and proton NMR at high field strength, and the resulting spectra are shown. In the proton spectrum of the 12.8 percent hydrogen fuel, no prominent single species is seen while for the blending stock, many individual lines are apparent. The ERBS fuels were fractionated by high-performance liquid chromatography and the resulting fractions analyzed by NMR. The species found are identified.

  13. Solvent and H/D isotope effects on the proton transfer pathways in heteroconjugated hydrogen-bonded phenol-carboxylic acid anions observed by combined UV-vis and NMR spectroscopy.

    PubMed

    Koeppe, Benjamin; Guo, Jing; Tolstoy, Peter M; Denisov, Gleb S; Limbach, Hans-Heinrich

    2013-05-22

    Heteroconjugated hydrogen-bonded anions A···H···X(-) of phenols (AH) and carboxylic/inorganic acids (HX) dissolved in CD2Cl2 and CDF3/CDF2Cl have been studied by combined low-temperature UV-vis and (1)H/(13)C NMR spectroscopy (UVNMR). The systems constitute small molecular models of hydrogen-bonded cofactors in proteins such as the photoactive yellow protein (PYP). Thus, the phenols studied include the PYP cofactor 4-hydroxycinnamic acid methyl thioester, and the more acidic 4-nitrophenol and 2-chloro-4-nitrophenol which mimic electronically excited cofactor states. It is shown that the (13)C chemical shifts of the phenolic residues of A···H···X(-), referenced to the corresponding values of A···H···A(-), constitute excellent probes for the average proton positions. These shifts correlate with those of the H-bonded protons, as well as with the H/D isotope effects on the (13)C chemical shifts. A combined analysis of UV-vis and NMR data was employed to elucidate the proton transfer pathways in a qualitative way. Dual absorption bands of the phenolic moiety indicate a double-well situation for the shortest OHO hydrogen bonds studied. Surprisingly, when the solvent polarity is low the carboxylates are protonated whereas the proton shifts toward the phenolic oxygens when the polarity is increased. This finding indicates that because of stronger ion-dipole interactions small anions are stabilized at high solvent polarity and large anions exhibiting delocalized charges at low solvent polarities. It also explains the large acidity difference of phenols and carboxylic acids in water, and the observation that this difference is strongly reduced in the interior of proteins when both partners form mutual hydrogen bonds.

  14. A structural study of epoxidized natural rubber (ENR-50) and its cyclic dithiocarbonate derivative using NMR spectroscopy techniques.

    PubMed

    Hamzah, Rosniza; Bakar, Mohamad Abu; Khairuddean, Melati; Mohammed, Issam Ahmed; Adnan, Rohana

    2012-09-12

    A structural study of epoxidized natural rubber (ENR-50) and its cyclic dithiocarbonate derivative was carried out using NMR spectroscopy techniques. The overlapping (1)H-NMR signals of ENR-50 at δ 1.56, 1.68-1.70, 2.06, 2.15-2.17 ppm were successfully assigned. In this work, the <(13)C-NMR chemical shift assignments of ENR-50 were consistent to the previously reported work. A cyclic dithiocarbonate derivative of ENR-50 was synthesized from the reaction of purified ENR-50 with carbon disulfide (CS(2)), in the presence of 4-dimethylaminopyridine (DMAP) as catalyst at reflux temperature. The cyclic dithiocarbonate formation involved the epoxide ring opening of the ENR-50. This was followed by insertion of the C-S moiety of CS(2) at the oxygen attached to the quaternary carbon and methine carbon of epoxidized isoprene unit, respectively. The bands due to the C=S and C-O were clearly observed in the FTIR spectrum while the (1)H-NMR spectrum of the derivative revealed the peak attributed to the methylene protons had split. The (13)C-NMR spectrum of the derivative further indicates two new carbon peaks arising from the >C=S and quaternary carbon of cyclic dithiocarbonate. All other (1)H- and (13)C-NMR chemical shifts of the derivative remain unchanged with respect to the ENR-50.

  15. 1H and 15N NMR Analyses on Heparin, Heparan Sulfates and Related Monosaccharides Concerning the Chemical Exchange Regime of the N-Sulfo-Glucosamine Sulfamate Proton

    PubMed Central

    Pomin, Vitor H.

    2016-01-01

    Heparin and heparan sulfate are structurally related glycosaminoglycans (GAGs). Both GAGs present, although in different concentrations, N-sulfo-glucosamine (GlcNS) as one of their various composing units. The conditional fast exchange property of the GlcNS sulfamate proton in these GAGs has been pointed as the main barrier to its signal detection via NMR experiments, especially 1H-15N HSQC. Here, a series of NMR spectra is collected on heparin, heparan sulfate and related monosaccharides. The N-acetyl glucosamine-linked uronic acid types of these GAGs were properly assigned in the 1H-15N HSQC spectra. Dynamic nuclear polarization (DNP) was employed in order to facilitate 1D spectral acquisition of the sulfamate 15N signal of free GlcNS. Analyses on the multiplet pattern of scalar couplings of GlcNS 15N has helped to understand the chemical properties of the sulfamate proton in solution. The singlet peak observed for GlcNS happens due to fast chemical exchange of the GlcNS sulfamate proton in solution. Analyses on kinetics of alpha-beta anomeric mutarotation via 1H NMR spectra have been performed in GlcNS as well as other glucose-based monosaccharides. 1D 1H and 2D 1H-15N HSQC spectra recorded at low temperature for free GlcNS dissolved in a proton-rich solution showed signals from all exchangeable protons, including those belonging to the sulfamate group. This work suits well to the current grand celebration of one-century-anniversary of the discovery of heparin. PMID:27618066

  16. NMR studies of the membrane bound form of filamentous bacteriophage fd and Pfl major coat proteins

    SciTech Connect

    Schiksnis, R.A.; Bogusky, M.J.; Opella, S.J.

    1987-05-01

    The major coat proteins of the fd (M13) and Pf1 filamentous bacteriophage exist as integral membrane proteins during the viral life cycle. These proteins adopt their membrane bound conformations when solubilized by a variety of detergents, and the protein-detergent micelle complexes can be studied using solution NMR techniques. Determination of the structure of the coat proteins in their membrane bound form has been accomplished by qualitative interpretation of 2-dimensional /sup 1/H-/sup 1/H NOE spectra (NOESY). The critical amide proton resonance assignments were made through biosynthetic /sup 15/N labeling and /sup 1/H//sup 15/N heteronuclear chemical shift correlation techniques. The data indicate that both proteins adopt helical conformations within the micelle. The /sup 15/N//sup 1/H heteronuclear NOE has been used to characterize the backbone dynamics of both proteins in micelles. The lipid associated residues of the proteins are rigid on the nanosecond timescale, while the hydrophilic solvent associated N- and C-termini are high mobile. These results complement previously reported protein dynamics studies of membrane bound coat proteins conducted using solid state NMR methods. Solid state NMR studies reported in the literature have also investigated the structure and dynamics of the fd and Pf1 major coat proteins when bound to intact phage. Therefore, structure/dynamics comparisons of the proteins in their structural versus membrane bound forms can be made.

  17. NMR study of a membrane protein in detergent-free aqueous solution.

    PubMed

    Zoonens, Manuela; Catoire, Laurent J; Giusti, Fabrice; Popot, Jean-Luc

    2005-06-21

    One of the major obstacles to membrane protein (MP) structural studies is the destabilizing effect of detergents. Amphipols (APols) are short amphipathic polymers that can substitute for detergents to keep MPs water-soluble under mild conditions. In the present work, we have explored the feasibility of studying the structure of APol-complexed MPs by NMR. As a test MP, we chose the 171-residue transmembrane domain of outer MP A from Escherichia coli (tOmpA), whose x-ray and NMR structures in detergent are known. 2H,15N-labeled tOmpA was produced as inclusion bodies, refolded in detergent solution, trapped with APol A8-35, and the detergent removed by adsorption onto polystyrene beads. The resolution of transverse relaxation-optimized spectroscopy-heteronuclear single-quantum correlation spectra of tOmpA/A8-35 complexes was found to be close to that of the best spectra obtained in detergent solutions. The dispersion of chemical shifts indicated that the protein had regained its native fold and retained it during the exchange of surfactants. MP-APol interactions were mapped by substituting hydrogenated for deuterated A8-35. The resulting dipolar broadening of amide proton linewidths was found to be limited to the beta-barrel region of tOmpA, indicating that A8-35 binds specifically to the hydrophobic transmembrane surface of the protein. The potential of this approach to MP studies by solution NMR is discussed.

  18. Relaxation dispersion NMR spectroscopy for the study of protein allostery.

    PubMed

    Farber, Patrick J; Mittermaier, Anthony

    2015-06-01

    Allosteric transmission of information between distant sites in biological macromolecules often involves collective transitions between active and inactive conformations. Nuclear magnetic resonance (NMR) spectroscopy can yield detailed information on these dynamics. In particular, relaxation dispersion techniques provide structural, dynamic, and mechanistic information on conformational transitions occurring on the millisecond to microsecond timescales. In this review, we provide an overview of the theory and analysis of Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion NMR experiments and briefly describe their application to the study of allosteric dynamics in the homeodomain from the PBX transcription factor (PBX-HD). CPMG NMR data show that local folding (helix/coil) transitions in one part of PBX-HD help to communicate information between two distant binding sites. Furthermore, the combination of CPMG and other spin relaxation data show that this region can also undergo local misfolding, reminiscent of conformational ensemble models of allostery.

  19. Dynamical properties of confined supercooled water: an NMR study

    NASA Astrophysics Data System (ADS)

    Mallamace, Francesco; Broccio, Matteo; Corsaro, Carmelo; Faraone, Antonio; Liu, Li; Mou, Chung-Yuan; Chen, Sow-Hsin

    2006-09-01

    We report a set of dynamical data of confined water measured in a very deeply supercooled regime (290-190 K). Water is contained in silica matrices (MCM-41-S) which consist of 1D cylindrical pores with diameters d = 14,18 and 24 Å. When confined in these tubular pores, water does not crystallize, and can be supercooled well below 200 K. We use the NMR technique to obtain the characteristic proton relaxation time-constants (the spin-lattice relaxation time-constant T1 and the spin-spin relaxation time-constant T2) and a direct measurement of the self-diffusion coefficient in the whole temperature range. We give evidence of the existence of a fragile-to-strong dynamic crossover (FSC) at TL = 225 K from the temperature dependence of the self-diffusion coefficient. A combination of the NMR self-diffusion coefficient with the average translational relaxation time, as measured by quasi-elastic neutron scattering, shows a well defined decoupling of transport coefficients, i.e. the breakdown of the Stokes-Einstein relation, on approaching the crossover temperature TL.

  20. NMR STUDY OF MOLECULAR REFORIENTATION UNDER FIVEFOLD SYMMETRY SOLID PERMETHYLFERROCENE

    SciTech Connect

    Wemmer, D.E.; Ruben, D.J.; Pines, A.

    1980-08-01

    The ring reorientation in permethylferrocene has been studied using high resolution solid state {sup 13}C NMR. The constraints which symmetry places upon the number and types of motional parameters which may be determined from the NMR spectrum are discussed. From comparison of the experimental lineshapes in the slow reorientation temperatures range with theoretical models for random rotations and symmetry related jumps, it is concluded that the reorientation occurs as jumps between symmetry related orientations with jumps of 2{pi}/5 highly favored over 4{pi}/5. The activation energy derived for the jump process is 13.5 kjoules/mole.

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

    PubMed

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

    2009-08-13

    The main species in the acid-base equilibria of two pyranoanthocyanins (vitisins B), pyranomalvidin-3-glucoside I and pyranomalvidin-3-O-coumaroylglucoside II, and the respective pK(a) were determined using NMR, visible spectroscopy, and mass spectrometry techniques. The three equilibria involve protonation of the pyranoflavylium cation of vitisin B (pK(a1)) and two deprotonations (pK(a2) and pK(a3)). For pigment I, the values obtained through the titration curves of the chemical shift of some protons versus pH were (pK(a1) < 0.68; pK(a2) = 4.40 +/- 0.08; pK(a3) = 7.45 +/- 0.09) very close to the values obtained by visible spectroscopy (pK(a1) < 0.63; pK(a2) = 4.43 +/- 0.02; pK(a3) = 7.34 +/- 0.03). For pigment II, it was only possible to calculate the pK(a) by visible spectroscopy (pK(a1) < 0.75; pK(a2) = 4.66 +/- 0.10; pK(a3) = 6.76 +/- 0.10). NMR studies have shown that pigment I does not undergo hydration, and the hypothesis of the occurrence of hemiacetal forms in equilibrium was discarded.

  2. Studies on solution NMR structure of brazzein : Secondary structure and molecular scaffold.

    PubMed

    Gao, G; Dai, J; Ding, M; Hellekant, G; Wang, J; Wang, D

    1999-08-01

    Brazzein is a sweet-tasting protein isolated from the fruit of West African plantPentadiplandra brazzeana Baillon. It is the smallest and the most water-soluble sweet protein discovered so far and is highly thermostable. The proton NMR study of brazzein at 600 MHz (pH 3.5, 300 K) is presented. The complete sequence specific assignments of the individual backbone and sidechain proton resonances were achieved using through-bond and through-space connectivities obtained from standard two-dimensional NMR techniques. The secondary structure of brazzein contains one alpha-helix (residues 21-29), one short 3(10)-helix (residues 14-17), two strands of antiparallel beta-sheet (residues 34-39, 44-50) and probably a third strand (residues 5-7) near the N-terminus. A comparative analysis found that brazzein shares a so-called 'cysteine-stabilized alpha-beta' (CSalphabeta) motif with scorpion neurotoxins, insect defensins and plant gamma - thionins. The significance of this multi-function motif, the possible active sites and the structural basis of themostability were discussed.

  3. 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.

  4. Study of the negative magneto-resistance of single proton-implanted lithium-doped ZnO microwires.

    PubMed

    Lorite, I; Zandalazini, C; Esquinazi, P; Spemann, D; Friedländer, S; Pöppl, A; Michalsky, T; Grundmann, M; Vogt, J; Meijer, J; Heluani, S P; Ohldag, H; Adeagbo, W A; Nayak, S K; Hergert, W; Ernst, A; Hoffmann, M

    2015-07-01

    The magneto-transport properties of single proton-implanted ZnO and of Li(7%)-doped ZnO microwires have been studied. The as-grown microwires were highly insulating and not magnetic. After proton implantation the Li(7%) doped ZnO microwires showed a non-monotonous behavior of the negative magneto-resistance (MR) at temperature above 150 K. This is in contrast to the monotonous NMR observed below 50 K for proton-implanted ZnO. The observed difference in the transport properties of the wires is related to the amount of stable Zn vacancies created at the near surface region by the proton implantation and Li doping. The magnetic field dependence of the resistance might be explained by the formation of a magnetic/non-magnetic heterostructure in the wire after proton implantation.

  5. Some perspectives on the interpretation of proton NMR spin diffusion data in terms of polymer morphologies.

    PubMed

    VanderHart, D L; McFadden, G B

    1996-08-01

    Proton spin diffusion data yield morphological information over dimensions covering approximately the 2-50 nm range. In this article, the interpretation of such data for polymers is emphasized, recognizing that the mathematical framework for much of this interpretation already exists in the literature. Practical issues are considered, for example, a useful scaling of plotted data is suggested, key attributes of the data are identified and ambiguities in the mapping of data into morphological models are spelled out. Discussion is limited to two-phase systems, where it is assumed that, by employing multiple-pulse methods polarization gradients can be generated, whose spunal sharpness is limited solety by the morphological definition of the interfaces. Interpretation of data in terms of morphology and stoichiometry is emphasized, where stoichiometric issues pertain only to chemically heterogeneous systems. Extraction of stoichiometric information from spin diffusion data is not commonly attempted; the discussion included herein allows for the possibility that the composition of phases may be chemically mixed. Methods for generating gradients are discussed only briefly. A standardized spin diffusion plot is proposed and the initial slope of this plot is tocussed on for providing information about morphology and stoichiometry. Ambiguities of interpretation considered include the dimensionality of the deduced morphology and, for systems with chemical heterogeneity the uniqueness of the compositional characterization of each phase. In addition, funite difference methods are used to simulate entire spin diffusion curves for idealized lamellar and hexagonal rod/matrix morphologies. Comparisons of these curves show that distinguishing 1-D and 2-D morphologies on the basis of experimental data is unlikely to be successful over the range of stoichiometrics where such morphologies are expected. Several examples of spin diffusion data are presented. Brief treatments of the

  6. Proton NMR assignments of heme contracts and catalytically implicated amino acids in cyanide-ligated cytochrome c peroxidase determined from one- and two-dimensional nuclear Overhauser effects

    SciTech Connect

    Satterlee, J.D. ); Erman, J.E. )

    1991-05-07

    Proton NMR assignments of the heme pocket and catalytically relevant amino acid protons have been accomplished for cyanide-ligated yeast cytochrome c peroxidase. This form of the protein, while not enzymatically active itself, is the best model available (that displays a resolvable proton NMR spectrum) for the six-coordinate low-spin active intermediates, compounds I and II. The assignments were made with a combination of one- and two-dimensional nuclear Overhauser effect methods and demonstrate the utility of NOESY experiments for paramagnetic proteins of relatively large size (M{sub r} 34,000). Assignments of both isotope exchangeable and nonexchangeable proton resonances were obtained by using enzyme preparations in both 90% H{sub 2}O/10% D{sub 2}O and, separately, in 99.9% D{sub 2}O solvent systems. Complete resonance assignments have been achieved for the proximal histidine, His-175, and His-52, which is a member of the catalytic triad on the distal side of the heme. In addition, partial assignments are reported for Trp-51 and Arg-48, catalytically important residues, both on the distal side. Aside from His-175, partial assignments for amino acids on the proximal side of the heme are proposed for the alanines at primary sequence positions 174 and 176 and for Thr-180 and Leu-232.

  7. Novel Dodecaarylporphyrins: Synthesis and Variable Temperature NMR Studies

    SciTech Connect

    Cancilla, Mark; Lebrilla, Carlito; Ma, Jian-Guo; Medforth, Craig J.; Muzzi, Cinzia M.; Shelnutt, John A.; Smith, Kevin M.; Voss, Lisa

    1999-05-05

    An investigation of the synthesis of novel dodecaarylporphyrins using the Suzuki coupling reaction of arylboronic acids with octabromotetraarylporphyrins is reported. Studies of the dynamic properties of these new porphyrins using variable temperature (VT) 1H NMR spectroscopy and molecular mechanics provide interesting insights into their dynamic properties, including the first determination of {beta} aryl rotation in a porphyrin system.

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

    SciTech Connect

    Millar, J.M.

    1986-02-01

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

  9. Evidence for DAPI intercalation in CG sites of DNA oligomer [d(CGACGTCG)]2: a 1H NMR study.

    PubMed Central

    Trotta, E; D'Ambrosio, E; Ravagnan, G; Paci, M

    1995-01-01

    The interaction between 4',6-diamidino-2-phenylindole (DAPI) and the DNA oligomer [d(CGACGTCG)]2 has been investigated by proton one- and two-dimensional NMR spectroscopy in solution. Compared with the minor groove binding of the drug to [d(GCGATCGC)]2, previously studied by NMR spectroscopy, the interaction of DAPI with [d(CGACGTCG)]2 appears markedly different and gives results typical of a binding mechanism by intercalation. C:G imino proton signals of the [d(CGACGTCG)]2 oligomer as well as DAPI resonances appear strongly upfield shifted and sequential dipolar connectivities between cytosine and guanine residues show a clear decrease upon binding. Moreover, protons lying in both the minor and major grooves of the DNA double helix appear involved in the interaction, as evidenced principally by intermolecular drug-DNA NOEs. In particular, the results indicate the existence of two stereochemically non-equivalent intercalation binding sites located in the central and terminal adjacent C:G base pairs of the palindromic DNA sequence. Different lifetimes of the complexes were also observed for the two sites of binding. Moreover, due to the fast exchange on the NMR timescale between free and bound species, different interactions in dynamic equilibrium with the observed intercalative bindings were not excluded. PMID:7753623

  10. Protonation of ninhydrin and indan-1,2,3-trione revisited: A combined theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Salnikov, George E.; Genaev, Alexander M.; Shernyukov, Andrey V.; Shubin, Vyacheslav G.

    2017-04-01

    The literature data on protonation of indan-1,2,3-trione and ninhydrin (indantrione hydrate) in acidic media are inconsistent, formation of dications at pH 3 and very low extent of protonation in superacid CF3SO3H were claimed. Our combined theoretical (DFT, MP2, CCSD) and experimental (NMR) study has shown that indantrione undergoes single protonation in CF3SO3H resulting in monocation formation. In more strong superacid FSO3H-SbF5 dication is formed, but, contrary to the literary data, trication is not formed even in this superacid. Significant dependence of 13C NMR chemical shifts of indantrione on media acidity allows using this compound as a convenient indicator of acidity in a broad range, from H0 -3 to -25.

  11. a Study of Molecular Dynamics in Water-Cellulose Systems Using NMR

    NASA Astrophysics Data System (ADS)

    Waana, Charles Musannyana

    This thesis presents the application of Nuclear Magnetic Resonance (NMR) to the study of the water dynamics in water-cellulose systems. Both H_2O and D_2O were used in polycrystalline Sigmacell 50 cellulose and in cellulose acetate films. Both the spectral lineshapes and various spin relaxation times were studied as functions of temperature and moisture content of the samples. ^1H and ^2 H NMR spectra of rm H_2O and rm D_2O absorbed in cellulose acetate films were observed while changing the angle between the plane of the film and the static magnetic field. ^1H-NMR spectra show dipolar splittings that vary depending on the angle. The splitting has a maximum when the surface of the film is perpendicular to the magnetic field. From the angular dependence of the dipolar splittings, it is deduced that the motionally averaged axis of the dipole moments is perpendicular to the film surface. ^2H NMR spectra show quadrupolar splittings which indicate that the motionally averaged axis of the electric quadrupole interaction is oriented perpendicular to the film. A number of NMR parameters were determined as a function of moisture content at 20^circ C for water adsorbed on Sigmacell 50 cellulose. The NMR parameters indicate that the cellulose swells as the water is added. Ninety-two percent of the cellulose is in crystalline domains and undergoes very little swelling indicating that it is largely inaccessible to water, whereas the remaining 8% is in paracrystalline or amorphous domains which are accessible to water and undergo considerable swelling. A three state model is applied for the protons in these samples, consisting of cellulose protons, water in intimate contact with these cellulose portons, and water which is not in intimate contact. Exchange and/or cross relaxation occurs between the three different proton groups. All the data are consistent with this model. An NMR relaxation study of water dynamics in hydrated Sigmacell 50 cellulose and cellulose acetate films has

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

    PubMed

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

    2010-03-01

    NMR spectroscopy is an established, versatile technique for the detection of molecular interactions, even when these interactions are weak. Signal enhancement by several orders of magnitude through dynamic nuclear polarization alleviates several practical limitations of NMR-based interaction studies. This enhanced non-equilibrium polarization contributes sensitivity for the detection of molecular interactions in a single NMR transient. We show that direct (13)C NMR ligand binding studies at natural isotopic abundance of (13)C gets feasible in this way. Resultant screens are easy to interpret and can be performed at (13)C concentrations below muM. In addition to such ligand-detected studies of molecular interaction, ligand binding can be assessed and quantified with enzymatic assays that employ hyperpolarized substrates at varying enzyme inhibitor concentrations. The physical labeling of nuclear spins by hyperpolarization thus provides the opportunity to devise fast novel in vitro experiments with low material requirement and without the need for synthetic modifications of target or ligands. Copyright (c) 2009 Elsevier Inc. All rights reserved.

  13. NMR study of the solution conformation of rat atrial natriuretic factor 7-23 in sodium dodecyl sulfate micelles

    SciTech Connect

    Olejniczak, E.T.; Gampe, R.T. Jr.; Rockway, T.W.; Fesik, S.W.

    1988-09-06

    The conformation of the cyclic portion (7-23) of naturally occurring rat atrial natriuretic factor, ANF(1-28), has been examined in sodium dodecyl sulfate (SDS) micelles using high-resolution NMR techniques. Evidence is presented which shows that ANF(7-23) has several regions of definable structure in SDS micelles which were not observed in earlier studies in bulk solvents. The /sup 1/H NMR resonances of ANF(7-23) in SDS micelles were assigned using sequential assignment techniques, and the conformational properties were analyzed primarily from proton-proton distances obtained from the quantitative analysis of two-dimensional nuclear Overhauser effect spectra. Three-dimensional structures consistent with the NMR data were generated by using distance geometry and constrained minimization/dynamics. Several similar but not identical structures were found which adequately satisfied the NMR constraints. Although none of the structures adopted a standard secondary structure, the conformations of three different sections of the peptide, 8-13, 14-17, and 18-21, were nearly identical in all of the predicted structures when individually superimposed.

  14. Urinary (1)H-NMR metabonomics study on intervention effects of soya milk in Africans.

    PubMed

    Ogegbo, Olumuyiwa L; Dissanyake, Wimal; Crowder, John; Asekun, Olayinka; Familoni, Oluwole; Branford-White, Christopher J; Annie Bligh, S W

    2012-01-01

    Metabonomics is an important tool in understanding the toxicological or therapeutic effects of interventions by analysing metabolic profiles and interpreting complex multi-dimensional spectroscopic/spectrometric data using multivariate data analysis. The objectives of this study were to evaluate the metabolic changes following a short-term 5 day soya milk intervention, and to investigate factors that influence soy-phytoestrogen metabolism focused on Africans based in either UK or Nigeria. (1)H-NMR metabonomics was applied to analyse urine samples collected at four phases I-IV (pre, days 3 and 5, and post) of the soy-intervention from African volunteers (n = 40 in total). Individual proton NMR spectra were visually and statistically assessed using multivariate analyses (MVA): principal component analysis (PCA) and (orthogonal-) partial-least square-discriminant analysis ((O-) PLS-DA). In addition, 22 endogenous metabolites were quantified using a Chenomx NMR suite. The results showed the levels of analysed endogenous metabolites (creatinine adjusted) present ranged from 4 µM to 12 mM with large inter-subject variances in acetate, acetone, lactate and trimethylamine. The MVA results showed high inter-individuality and sampling variances based on PCA score plots, and demonstrated soy metabolism to be significantly influenced by location and gender by both PLS-DA and O-PLS-DA. Copyright © 2011 John Wiley & Sons, Ltd.

  15. Studies of Transition Metal Complexes Using Dynamic NMR Techniques.

    NASA Astrophysics Data System (ADS)

    Coston, Timothy Peter John

    Available from UMI in association with The British Library. This Thesis is primarily concerned with the quantitative study of fluxional processes in, predominantly platinum(IV) complexes, with the ligands 1,1,2,2-tetrakis(methylthio)ethane (MeS)_2CHCH(SMe)_2 , and 1,1,2,2-tetrakis(methylthio)ethene (MeS) _2C=C(SMe)_2. Quantitative information relating to the energetics of these processes has been obtained by a combination of one- and two-dimensional NMR techniques. Chapter One provides an introduction to the background of fluxional processes in transition metal complexes together with data concerning the energetics of the processes that have already been studied by NMR techniques. Chapter Two provides a thorough grounding in NMR techniques, in particular those concerned with the quantitative measurement of rates involved in chemical exchange processes. A description of the use of 2D EXSY NMR spectroscopy in obtaining rate data is given. The properties of the magnetic isotope of platinum are given in Chapter Three. A general survey is also given of some additional compounds that have already been studied by platinum-195 spectroscopy. Chapter Four is concerned with the quantitative study of low temperature (<293 K) fluxionality (sulphur inversion) in the complexes (PtXMe_3 (MeS)_2CHCH(SMe) _2) (X = Cl, Br, I). These complexes were studied by dynamic nuclear magnetic resonance and the information regarding the rates of sulphur inversion was obtained by complete band-shape analysis. Chapter Five is concerned with high temperature (>333 K) fluxionality, of the previous complexes, as studied by a combination of one- and two -dimensional NMR techniques. Aside from obtaining thermodynamic parameters for all the processes, a new novel mechanism is proposed. Chapter Six is primarily concerned with the NMR investigation of the new dinuclear complexes ((PtXMe _3)_2(MeS) _2CHCH(SMe)_2) (X = Cl, Br, I). The solution properties have been established and thermo-dynamic parameters

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

    PubMed

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

    2015-06-15

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

  17. Porphyrin protonation studied by magnetic circular dichroism.

    PubMed

    Štěpánek, Petr; Andrushchenko, Valery; Ruud, Kenneth; Bouř, Petr

    2012-01-12

    Magnetic circular dichroism (MCD) spectroscopy provides valuable information about electronic excited states in molecules. The interpretation of spectra is however difficult, often requiring additional theoretical calculations to rationalize the observed signal. Recent developments in time-dependent density functional theory (TDDFT) bring hope that the applicability of MCD spectroscopy for chemical problems may be significantly extended. In this study, two modern analytical TDDFT implementations are compared and used to understand experimental MCD spectra of a model porphyrin system upon protonation. Changes in porphyrin geometry and electronic structure are related to MCD intensities by comparing the spectra of 5,10,15,20-tetraphenyl-21H,23H-porphyrintetrasulfonic acid (TPPS) measured at different pH values with the TDDFT calculations. Although the theoretical results slightly depended on the chosen exchange-correlation functional, the computations provided MCD curves that could well rationalize the experimental data. The protonation of the porphyrin core causes marked changes in the MCD spectrum, whereas the role of the substituents is limited. Also, different conformations of the porphyrin substituents cause relatively minor changes of the MCD pattern, mostly in the Soret region, where the porphine and phenyl electronic transitions start to mix. The solvent environment simulated by the dielectric model caused a shift (~20 nm) of the absorption bands but only minor variations in the absorption and MCD spectral shapes. The study thus demonstrates that the recently available first-principles interpretations of MCD spectra significantly enhance the applicability of the technique for molecular structural studies.

  18. Characterization of the Dynamics in the Protonic Conductor CsH2PO4 by 17O Solid-State NMR Spectroscopy and First-Principles Calculations: Correlating Phosphate and Protonic Motion

    PubMed Central

    2015-01-01

    17O NMR spectroscopy combined with first-principles calculations was employed to understand the local structure and dynamics of the phosphate ions and protons in the paraelectric phase of the proton conductor CsH2PO4. For the room-temperature structure, the results confirm that one proton (H1) is localized in an asymmetric H-bond (between O1 donor and O2 acceptor oxygen atoms), whereas the H2 proton undergoes rapid exchange between two sites in a hydrogen bond with a symmetric double potential well at a rate ≥107 Hz. Variable-temperature 17O NMR spectra recorded from 22 to 214 °C were interpreted by considering different models for the rotation of the phosphate anions. At least two distinct rate constants for rotations about four pseudo C3 axes of the phosphate ion were required in order to achieve good agreement with the experimental data. An activation energy of 0.21 ± 0.06 eV was observed for rotation about the P–O1 axis, with a higher activation energy of 0.50 ± 0.07 eV being obtained for rotation about the P–O2, P–O3d, and P–O3a axes, with the superscripts denoting, respectively, dynamic donor and acceptor oxygen atoms of the H-bond. The higher activation energy of the second process is most likely associated with the cost of breaking an O1–H1 bond. The activation energy of this process is slightly lower than that obtained from the 1H exchange process (0.70 ± 0.07 eV) (Kim, G.; Blanc, F.; Hu, Y.-Y.; Grey, C. P. J. Phys. Chem. C2013, 117, 6504−6515) associated with the translational motion of the protons. The relationship between proton jumps and phosphate rotation was analyzed in detail by considering uncorrelated motion, motion of individual PO4 ions and the four connected/H-bonded protons, and concerted motions of adjacent phosphate units, mediated by proton hops. We conclude that, while phosphate rotations aid proton motion, not all phosphate rotations result in proton jumps. PMID:25732257

  19. NMR studies of abasic sites in DNA duplexes: Deoxyadenosine stacks into the helix opposite acyclic lesions

    SciTech Connect

    Kalnik, M.W.; Chang, Chienneng; Johnson, F.; Grollman, A.P.; Patel, D.J. )

    1989-04-18

    Proton and phosphorus NMR studies are reported for two complementary nonanucleotide duplexes containing acyclic abasic sites. The first duplex, d(C-A-T-G-A-G-T-A-C){center dot}d(G-T-A-C-P-C-A-T-G), contains an acyclic propanyl moiety, P, located opposite a deoxyadenosine at the center of the helix (designated AP{sub P} 9-mer duplex). The second duplex, d(C-A-T-G-A-G-T-A-C-){center dot}d(G-T-A-C-E-C-A-T-G), contains a similarly located acyclic ethanyl moiety, E (designated AP{sub E} 9-mer duplex). The ethanyl moiety is one carbon shorter than the natural carbon-phosphodiester backbone of a single nucleotide unit of DNA. The majority of the exchangeable and nonexchangeable base and sugar protons in both the AP{sub P} 9-mer and AP{sub E} 9-mer duplexes, including those at the abasic site, have been assigned by recording and analyzing two-dimensional phase-sensitive NOESY data sets in H{sub 2}O and D{sub 2}O solution between -5 and 5{degree}C. These spectroscopic observations establish that A5 inserts into the helix opposite the abasic site (P14 and El14) and stacks between the flanking G4{center dot}C15 and G6{center dot}C13 Watson-Crick base pairs in both the AP{sub P} 9-mer and AP{sub E} 9-mer duplexes. Proton NMR parameters for the Ap{sub P} 9-mer and AP{sub E}9-mer duplexes are similar to those reported previously. These proton NMR experiments demonstrate that the structures at abasic sites are very similar whether the five-membered ring is open or closed or whether the phosphodiester backbone is shortened by one carbon atom. Phosphorus spectra of the AP{sub P} 9-mer and AP{sub E} 9-mer duplexes (5{degree}C) indicate that the backbone conformation is similarly perturbed at three phosphodiester backbone torsion angles.

  20. 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.

  1. Study of cultured fibroblasts in vivo using NMR

    SciTech Connect

    Karczmar, G.S.

    1984-01-01

    The goal of this thesis was to study the compartmentation of phosphorylated glycolytic intermediates in intact Chicken Embryo Fibroblasts (CEFs) using /sup 31/P NMR at 109 MHz. Because glycolysis is regulated differently in normal and virally transformed CEFs, NMR experiments were performed on both types of cells. A technique for maintaining functional cells at high densities in an NMR magnet is described. Signals were detected from cytoplasmic inorganic phosphate (P/sub i/), ATP, NAD, NADH, phosphorylcholine and phosphorylethanolamine. The effect of external glucose on cytoplasmic pools of phosphates was studied. However, experiments with /sup 32/P labelled P/sub i/ showed that as the concentration of glucose in the medium was increased, the amount of phosphate sequestered in the cells increased. They conclude that there is a pool of P/sub i/ which is not detected by high resolution of NMR and that the size of this pool increases as the rate of glycolysis increases. These effects were found only in cultured cells; the data for transformed and normal cells were similar. Longitudinal relaxation times of intracellular phosphates in normal, transformed, and primary CEFs were measured.

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

    SciTech Connect

    Tang, J.H.

    1981-11-01

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

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

    NASA Astrophysics Data System (ADS)

    Jankuru Hennadige, Sohan Roshel De Silva

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

  4. Multinuclear NMR study of silica fiberglass modified with zirconia.

    PubMed

    Lapina, O B; Khabibulin, D F; Terskikh, V V

    2011-01-01

    Silica fiberglass textiles are emerging as uniquely suited supports in catalysis, which offer unprecedented flexibility in designing advanced catalytic systems for chemical and auto industries. During manufacturing fiberglass materials are often modified with additives of various nature to improve glass properties. Glass network formers, such as zirconia and alumina, are known to provide the glass fibers with higher strength and to slow down undesirable devitrification processes. In this work multinuclear (1)H, (23)Na, (29)Si, and (91)Zr NMR spectroscopy was used to characterize the effect of zirconia on the molecular-level fiberglass structure. (29)Si NMR results help in understanding why zirconia-modified fiberglass is more stable towards devitrification comparing with pure silica glass. Internal void spaces formed in zirconia-silica glass fibers after acidic leaching correlate with sodium and water distributions in the starting bulk glass as probed by (23)Na and (1)H NMR. These voids spaces are important for stabilization of catalytically active species in the supported catalysts. Potentials of high-field (91)Zr NMR spectroscopy to study zirconia-containing glasses and similarly disordered systems are illustrated. Copyright © 2011 Elsevier Inc. All rights reserved.

  5. Studies on supramolecular gel formation using DOSY NMR.

    PubMed

    Nonappa; Šaman, David; Kolehmainen, Erkki

    2015-04-01

    Herein, we present the results obtained from our studies on supramolecular self-assembly and molecular mobility of low-molecular-weight gelators (LMWGs) in organic solvents using pulsed field gradient (PFG) diffusion ordered spectroscopy (DOSY) NMR. A series of concentration-dependent DOSY NMR experiments were performed on selected LMWGs to determine the critical gelation concentration (CGC) as well as to understand the behaviour of the gelator molecules in the gel state. In addition, variable-temperature DOSY NMR experiments were performed to determine the gel-to-sol transition. The PFG NMR experiments performed as a function of gradient strength were further analyzed using monoexponential DOSY processing, and the results were compared with the automated Bayesian DOSY transformation to obtain 2D plots. Our results provide useful information on the stepwise self-assembly of small molecules leading to gelation. We believe that the results obtained from these experiments are applicable in determining the CGC and gel melting temperatures of supramolecular gels.

  6. Pulsed NMR study of the curing process of epoxy resin.

    PubMed

    Kimoto, Hiroki; Tanaka, Chikako; Yaginuma, Michiko; Shinohara, Emi; Asano, Atsushi; Kurotsu, Takuzo

    2008-07-01

    To analyze a curing process of epoxy resin in terms of molecular motion, we adapted a pulsed NMR method. Three kinds of (1)H spin-spin relaxation times (T(2L) (long), T(2S) (short) and T(2M) (intermediate)) were estimated from observed solid echo train signals as the curing process proceeded. A short T(2S) value below 20 micros suggests the existence of a motion-restricted chain, that is, cured elements of resin, and its fraction, P(S), sigmoidally increased with the curing time. On the other hand, the fraction of T(2L), P(L), decreased with the reaction time reciprocally against P(S), suggesting the disappearance of highly mobile molecules raised from pre-cured resin. The spin-lattice relaxation time, T(1), was also measured to check another aspect of molecular motion in the process. T(1) of the mixed epoxy resin and curing agent gradually increased just after mixing both of them. This corresponds to an increment of a less-mobile fraction, of which the correction time is more than 10(-6) s, and also means that the occurrence of a network structure whose mobility is strongly restricted by chemically bonded bridges between the epoxy resin and curing agent. The time courses of these parameters coincided with those of IR peaks pertinent to the curing reaction. Therefore, pulsed NMR is a useful tool to monitor the hardening process of epoxy resin in real time non-distractively in terms of the molecular motion of protons.

  7. 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)

  8. 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)

  9. 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.

  10. Effect of gel firmness at cutting time, pH, and temperature on rennet coagulation and syneresis: an in situ 1H NMR relaxation study.

    PubMed

    Hansen, Christian Lyndgaard; Rinnan, Asmund; Engelsen, Søren Balling; Janhøj, Thomas; Micklander, Elisabeth; Andersen, Ulf; van den Berg, Frans

    2010-01-13

    The objective of this study was to monitor rennet-induced milk gel formation and mechanically induced gel syneresis in situ by low-field NMR. pH, temperature, and gel firmness at cutting time were varied in a factorial design. The new curve-fitting method Doubleslicing revealed that during coagulation two proton populations with distinct transverse relaxation times (T2,1=181, T2,2=465 ms) were present in fractions (f1=98.9%, f2=1.1%). Mechanical cutting of the gel in the NMR tube induced macrosyneresis, which led to the appearance of an additional proton population (T2,3=1500-2200 ms) identified as whey. On the basis of NMR quantification of whey water the syneresis rate was calculated and found to be significantly dependent on pH and temperature.

  11. NMR Studies of Some Plasma Proteins.

    NASA Astrophysics Data System (ADS)

    Lawrence, Mark P.

    Available from UMI in association with The British Library. Requires signed TDF. The work reported in this thesis consists of a study of the solution structure of a domain of protein structure found in some of the enzymes involved in blood coagulation. These domains, known as kringles, are of between 78 and 82 residues and contain three conserved disulphide bridges in their primary sequence. The study attempts to elucidate the nature of the lysine-binding site of the fourth kringle of human plasminogen to probe its physiological action, and a theory is developed to explain the overall fold of the protein in terms of its physiological role. The protein structure is found to contain only one small region of secondary structure, an antiparallel beta-sheet of about 8 residues, which provides the support for the binding site. The binding site itself consists of a hydrophobic channel provided by the aromatic residues at positions 61, 63, 71 and 73 in the beta-sheet and a negatively charged site at one end of this channel provided by the aspartic acid residues at positions 54 and 56. The beta-sheet appears to become more tightly defined on binding the kringle with alpha,omega -amino acids which are analogues of lysine and exhibit known anti-fibrinolytic properties. The rest of the solution structure appears to be less clearly defined and relies mainly on the three disulphide bridges and some rather isolated hydrogen bonding for maintenance of the fold. An explanation for this structure with a rigid binding site and a more flexible region for the remainder of the domain is proposed. Shorter studies are reported on the second kringle of bovine prothrombin and the first of human plasminogen which suggest strongly that the kringle fold is conserved.

  12. 1H NMR relaxometry, viscometry, and PFG NMR studies of magnetic and nonmagnetic ionic liquids.

    PubMed

    Daniel, Carla I; Chávez, Fabián Vaca; Feio, Gabriel; Portugal, Carla A M; Crespo, João G; Sebastião, Pedro J

    2013-10-03

    A study is presented of the molecular dynamics and of the viscosity in pure [Aliquat][Cl] ionic liquid and in a mixture of [Aliquat][Cl] with 1% (v/v) of [Aliquat][FeCl4]. The (1)H spin-lattice relaxation rate, R1, was measured by NMR relaxometry between 8 and 300 MHz. In addition, the translation self-diffusion, D, was measured by pulse field gradient NMR. The ILs' viscosity was measured as a function of an applied magnetic field, B, and it was found that the IL mixture's viscosity decreased with increasing B, whereas the [Aliquat][Cl] viscosity is independent of B. All experimental results were analyzed taking into account the viscosity's magnetic field dependence, assuming a modified Stokes-Einstein diffusion/viscosity relation. The main difference between the relaxation mechanisms responsible for R1 in the two IL systems is related to the additional paramagnetic relaxation contribution associated with the (1)H spins-[FeCl4] paramagnetic moments' interactions. Cross-relaxation cusps in the R1 dispersion, associated with (35)Cl and (1)H nuclear spins in the IL systems, were detected. The R1 model considered was successfully fitted to the experimental results, and it was possible to estimate the value of D at zero field in the case of the IL mixture which was consistent with the values of D measured at 7 and 14.1 T and with the magnetic field dependence estimated from the viscosity measurements. It was observed that a small concentration of [Aliquat][FeCl4] in the [Aliquat][Cl] was enough to produce a "superparamagnetic"-like effect and to change the IL mixture's molecular dynamics and viscosity and to allow for their control with an external magnetic field.

  13. Studying skin penetration by NMR imaging

    NASA Astrophysics Data System (ADS)

    Burg, J. M.; Voelker, M.; Schlupp, P.; Schmidts, T.; Maeder, U.; Bergmann, T.; Runkel, F.; Heverhagen, J. T.; Fiebich, M.

    2011-03-01

    Skin penetration studies are an important part for the development of dermal drug carrier systems. As a novel approach a 7-tesla Magnetic Resonance Imaging (MRI) Scanner was used to obtain information about the penetration of agents into the skin. The main advantage of this method is, that the properties of the skin does not influence the signals. Compared to optical assessments the MRI method is not limited to imaging depth. Furthermore, it is possible to analyze fat and water components of the skin separately. The aim of this work was to evaluate, if this method is a promising analysis tool for the visualization of the transport of substances across the skin. Gadobutrol (Gadovist®1.0), respresenting a coventional contrast agent in MRI, was used as a model drug for the visualization of the skin penetration. These first promising results showed that Gadobutrol, incorporated in an oil-in-water emulsion, could be detected across the skin tissue compared to an aqueous solution. After 24 hours, the pixel intensity value was increased about 4-fold compared to an untreated tissue.

  14. Protonation states and catalysis: Molecular dynamics studies of intermediates in tryptophan synthase.

    PubMed

    Huang, Yu-Ming M; You, Wanli; Caulkins, Bethany G; Dunn, Michael F; Mueller, Leonard J; Chang, Chia-En A

    2016-01-01

    The importance of protonation states and proton transfer in pyridoxal 5'-phosphate (PLP)-chemistry can hardly be overstated. Although experimental approaches to investigate pKa values can provide general guidance for assigning proton locations, only static pictures of the chemical species are available. To obtain the overall protein dynamics for the interpretation of detailed enzyme catalysis in this study, guided by information from solid-state NMR, we performed molecular dynamics (MD) simulations for the PLP-dependent enzyme tryptophan synthase (TRPS), whose catalytic mechanism features multiple quasi-stable intermediates. The primary objective of this work is to elucidate how the position of a single proton on the reacting substrate affects local and global protein dynamics during the catalytic cycle. In general, proteins create a chemical environment and an ensemble of conformational motions to recognize different substrates with different protonations. The study of these interactions in TRPS shows that functional groups on the reacting substrate, such as the phosphoryl group, pyridine nitrogen, phenolic oxygen and carboxyl group, of each PLP-bound intermediate play a crucial role in constructing an appropriate molecular interface with TRPS. In particular, the protonation states of the ionizable groups on the PLP cofactor may enhance or weaken the attractions between the enzyme and substrate. In addition, remodulation of the charge distribution for the intermediates may help generate a suitable environment for chemical reactions. The results of our study enhance knowledge of protonation states for several PLP intermediates and help to elucidate their effects on protein dynamics in the function of TRPS and other PLP-dependent enzymes. © 2015 The Protein Society.

  15. 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.

  16. 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.

  17. 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.

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

    SciTech Connect

    Jelinek, Raz

    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. 27Al and 23Na 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 27Al 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+ cations are directly involved in adsorption processes and reactions in zeolite cavities.

  19. Dosimetry of {sup 60}Co and {sup 192}Ir gamma-irradiated agarose gels by proton relaxation time measurement and NMR imaging, in a 0-100 Gy dose range

    SciTech Connect

    Chalansonnet, A.; Briguet, A.; Bonnat, J.L.

    1997-05-01

    Localized irradiation of the skin and subcutaneous tissues with large single doses of gamma rays can induce immediate effects characterized by erythema, desquamation, and necrosis. Correlations between the evolution of the lesions and dosimetry studies have to be established by biophysical methods. NMR studies of the effects of an irradiated Fricke solution might be a means of controlling the delivered irradiation doses. After exposition to ionizing radiations, ferrous ions are transformed into ferric ions. Both are paramagnetic ions, and proton spin-lattice relaxation is accelerated depending on the oxidation reaction. In this study, solution of ammonium ferrous sulfate in an acid environment was incorporated into a gelling substance made with agarose, so that T{sub 1} weighted image contrast could be used to detect ferric ion formation. Experiments with {sup 192}Ir and {sup 90}Co gamma rays with doses in the 0 to 100 Gy range were conducted with Fe{sup 2+} concentrations of 0.5, 1, 1.5, and 2 mM in a gelling substance containing 4% agarose. A relationship was established between the amount of Fe{sup 3+} created and the spin-lattice proton relaxation rate, which led to a straightforward dose-effect relation. The use of such high doses allowed us to reproduce realistic conditions of accidental overexposure. A linear relationship was obtained between the doses absorbed and the NMR parameters measured (T{sub 1} and relative image intensity). 17 refs., 3 figs., 1 tab.

  20. Determining hydrogen-bond interactions in spider silk with 1H-13C HETCOR fast MAS solid-state NMR and DFT proton chemical shift calculations.

    PubMed

    Holland, Gregory P; Mou, Qiushi; Yarger, Jeffery L

    2013-07-28

    Two-dimensional (2D) (1)H-(13)C heteronuclear correlation (HETCOR) solid-state NMR spectra collected with fast magic angle spinning (MAS) are used in conjunction with density functional theory (DFT) proton chemical shift calculations to determine the hydrogen-bonding strength for ordered β-sheet and disordered 310-helical structures in spider dragline silk. The hydrogen-bond strength is determined to be identical for both structures in spider silk with a 1.83-1.84 Å NH···OC hydrogen-bond distance.

  1. Proton Transport in Nanocrysttaline Bioceramic Materals:. AN Investigative Study of Synthetic Bone with that of Natural Bone

    NASA Astrophysics Data System (ADS)

    Jena, Hrudananda; Rambabu, B.; Saunders, Ramsey

    2006-06-01

    Hydroxy apatite (Ca10(PO4)6(OH)2) is a ceramic material. This has been used for biological applications such as bone and teeth enamel. In this paper various preparation methods including sonochemical followed by microwave sintering technique has been used to prepare the material. The material was characterized by XRD, TEM, SEM and its electrical transport (proton) is measured by impedance spectroscopy. The conductivity measured is 0.091×10-6 to 19.20×10-6 Scm-1 at 25 - 850°C range of temperature at 100 kHz applied frequency. Conductivity found to increase with increasing applied frequency at a given temperature of measurement. The prevalence of protons in the lattice has been confirmed by proton NMR studies. The results of the experimental observations on proton migration in the apatite lattice for electrical conduction are discussed.

  2. NMR Structural Studies of Antimicrobial Peptides: LPcin Analogs

    PubMed Central

    Jeong, Ji-Ho; Kim, Ji-Sun; Choi, Sung-Sub; Kim, Yongae

    2016-01-01

    Lactophoricin (LPcin), a component of proteose peptone (113–135) isolated from bovine milk, is a cationic amphipathic antimicrobial peptide consisting of 23 amino acids. We designed a series of N- or C-terminal truncated variants, mutated analogs, and truncated mutated analogs using peptide-engineering techniques. Then, we selected three LPcin analogs of LPcin-C8 (LPcin-YK1), LPcin-T2WT6W (LPcin-YK2), and LPcin-T2WT6W-C8 (LPcin-YK3), which may have better antimicrobial activities than LPcin, and successfully expressed them in E. coli with high yield. We elucidated the 3D structures and topologies of the three LPcin analogs in membrane environments by conducting NMR structural studies. We investigated the purity of the LPcin analogs and the α-helical secondary structures by performing 1H-15N 2D HSQC and HMQC-NOESY liquid-state NMR spectroscopy using protein-containing micelle samples. We measured the 3D structures and tilt angles in membranes by conducting 15N 1D and 2D 1H-15N SAMMY type solid-state NMR spectroscopy with an 800 MHz in-house-built 1H-15N double-resonance solid-state NMR probe with a strip-shield coil, using protein-containing large bicelle samples aligned and confirmed by molecular-dynamics simulations. The three LPcin analogs were found to be curved α-helical structures, with tilt angles of 55–75° for normal membrane bilayers, and their enhanced activities may be correlated with these topologies. PMID:26789765

  3. Estimating side-chain order in methyl-protonated, perdeuterated proteins via multiple-quantum relaxation violated coherence transfer NMR spectroscopy.

    PubMed

    Sun, Hechao; Godoy-Ruiz, Raquel; Tugarinov, Vitali

    2012-03-01

    Relaxation violated coherence transfer NMR spectroscopy (Tugarinov et al. in J Am Chem Soc 129:1743-1750, 2007) is an established experimental tool for quantitative estimation of the amplitudes of side-chain motions in methyl-protonated, highly deuterated proteins. Relaxation violated coherence transfer experiments monitor the buildup of methyl proton multiple-quantum coherences that can be created in magnetically equivalent spin-systems as long as their transverse magnetization components relax with substantially different rates. The rate of this build-up is a reporter of the methyl-bearing side-chain mobility. Although the build-up of multiple-quantum (1)H coherences is monitored in these experiments, the decay of the methyl signal during relaxation delays occurs when methyl proton magnetization is in a single-quantum state. We describe a relaxation violated coherence transfer approach where the relaxation of multiple-quantum (1)H-(13)C methyl coherences during the relaxation delay period is quantified. The NMR experiment and the associated fitting procedure that models the time-dependence of the signal build-up, are applicable to the characterization of side-chain order in [(13)CH(3)]-methyl-labeled, highly deuterated protein systems up to ~100 kDa in molecular weight. The feasibility of extracting reliable measures of side-chain order is experimentally verified on methyl-protonated, perdeuterated samples of an 8.5-kDa ubiquitin at 10°C and an 82-kDa Malate Synthase G at 37°C.

  4. 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.

  5. 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.

  6. Perspective Study of Charmonium and Exotics in Antiproton-Proton Annihilation and Proton-Proton Collisions

    NASA Astrophysics Data System (ADS)

    Barabanov, Mikhail; Olsen, Stephen; Vodopyanov, Alexander

    The spectroscopy of exotic states with hidden charm is discussed. Together with charmonium, these provide a good tool for testing theories of the strong interactions including both perturbative and non-perturbative QCD, lattice QCD, potential and other phenomenological models. An elaborated analysis of exotics spectrum is given, and attempts to interpret recent experimentally observed states with masses above the Dbar{D} threshold region are considered. Experimental results from different collaborations (BES, BaBar, Belle, LHCb) are analyzed with special attention given to recently discovered hidden charm states. Some of these states can be interpreted as higher-lying charmonium states and others as tetraquarks with hidden charm. It has been shown that charged/neutral tetraquarks must have their neutral/charge partners with mass values differ by at most a few MeV/c2, hypotheses that tend to coincide with those proposed by Maiani and Polosa. However, measurements of different decay modes are needed before firm conclusions can be made. These data can be derived directly from the experiments using a high quality antiproton beam with momentum up to 15 GeV/c and proton-proton collisions with momentum up to 26 GeV/c.

  7. A Magic-Angle Spinning NMR Method for the Site-Specific Measurement of Proton Chemical-Shift Anisotropy in Biological and Organic Solids.

    PubMed

    Hou, Guangjin; Gupta, Rupal; Polenova, Tatyana; Vega, Alexander J

    2014-02-01

    Proton chemical shifts are a rich probe of structure and hydrogen bonding environments in organic and biological molecules. Until recently, measurements of (1)H chemical shift tensors have been restricted to either solid systems with sparse proton sites or were based on the indirect determination of anisotropic tensor components from cross-relaxation and liquid-crystal experiments. We have introduced an MAS approach that permits site-resolved determination of CSA tensors of protons forming chemical bonds with labeled spin-1/2 nuclei in fully protonated solids with multiple sites, including organic molecules and proteins. This approach, originally introduced for the measurements of chemical shift tensors of amide protons, is based on three RN-symmetry based experiments, from which the principal components of the (1)H CS tensor can be reliably extracted by simultaneous triple fit of the data. In this article, we expand our approach to a much more challenging system involving aliphatic and aromatic protons. We start with a review of the prior work on experimental-NMR and computational-quantum-chemical approaches for the measurements of (1)H chemical shift tensors and for relating these to the electronic structures. We then present our experimental results on U-(13)C,(15)N-labeled histdine demonstrating that (1)H chemical shift tensors can be reliably determined for the (1)H(15)N and (1)H(13)C spin pairs in cationic and neutral forms of histidine. Finally, we demonstrate that the experimental (1)H(C) and (1)H(N) chemical shift tensors are in agreement with Density Functional Theory calculations, therefore establishing the usefulness of our method for characterization of structure and hydrogen bonding environment in organic and biological solids.

  8. A Magic-Angle Spinning NMR Method for the Site-Specific Measurement of Proton Chemical-Shift Anisotropy in Biological and Organic Solids

    PubMed Central

    Hou, Guangjin; Gupta, Rupal; Polenova, Tatyana; Vega, Alexander J.

    2014-01-01

    Proton chemical shifts are a rich probe of structure and hydrogen bonding environments in organic and biological molecules. Until recently, measurements of 1H chemical shift tensors have been restricted to either solid systems with sparse proton sites or were based on the indirect determination of anisotropic tensor components from cross-relaxation and liquid-crystal experiments. We have introduced an MAS approach that permits site-resolved determination of CSA tensors of protons forming chemical bonds with labeled spin-1/2 nuclei in fully protonated solids with multiple sites, including organic molecules and proteins. This approach, originally introduced for the measurements of chemical shift tensors of amide protons, is based on three RN-symmetry based experiments, from which the principal components of the 1H CS tensor can be reliably extracted by simultaneous triple fit of the data. In this article, we expand our approach to a much more challenging system involving aliphatic and aromatic protons. We start with a review of the prior work on experimental-NMR and computational-quantum-chemical approaches for the measurements of 1H chemical shift tensors and for relating these to the electronic structures. We then present our experimental results on U-13C,15N-labeled histdine demonstrating that 1H chemical shift tensors can be reliably determined for the 1H15N and 1H13C spin pairs in cationic and neutral forms of histidine. Finally, we demonstrate that the experimental 1H(C) and 1H(N) chemical shift tensors are in agreement with Density Functional Theory calculations, therefore establishing the usefulness of our method for characterization of structure and hydrogen bonding environment in organic and biological solids. PMID:25484446

  9. NMR of lignins

    Treesearch

    John Ralph; Larry L. Landucci

    2010-01-01

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

  10. Proton NMR for detection, identification and quantification of adulterants in 160 herbal food supplements marketed for weight loss.

    PubMed

    Hachem, Rabab; Assemat, Gaëtan; Martins, Nathalie; Balayssac, Stéphane; Gilard, Véronique; Martino, Robert; Malet-Martino, Myriam

    2016-05-30

    One hundred and sixty food supplements (FS) marketed for weight loss and mainly purchased on the Internet were analyzed. All the FS were claimed as 100% natural containing only natural compounds, plant extracts and/or vitamins and the presence of an active pharmaceutical ingredient (API) was never mentioned. (1)H NMR spectroscopy was used for detecting the presence of adulterants and for their identification and quantification. Mass spectrometry was used as a complementary method for supporting their identification. Among the 164 samples considered because capsules from 5 different blisters of the same FS were analyzed, 56% were tainted with six API. Forty three contained sibutramine as single adulterant (26%), 9 phenolphthalein (6%) and 23 a mixture of these API (14%) that were both withdrawn from the market several years ago because of toxicity concerns. Sildenafil was found in 12 samples, either as a single adulterant (n=5) or in combination with sibutramine (n=3), phenolphthalein (n=3) and both sibutramine and phenolphthalein (n=1). Fluoxetine was present in 4 formulations, alone (n=3) or in combination with sibutramine and orlistat (n=1). At last, lorcaserine was detected in one FS. The content of sibutramine per dosage unit was comprised between 0.1 and 22 mg and that of phenolphthalein between 0.05 and 56 mg. The study also highlights poor manufacturing practices as evidenced for instance by the variability of API in capsules from different blisters of the same box. This paper demonstrates the need for more effective quality control of weight loss FS and the efficiency of (1)H NMR spectroscopy for the detection of tainted FS.

  11. Advanced solids NMR studies of coal structure and chemistry. Progress report, March 1 - September 1, 1996

    SciTech Connect

    Zilm, K.W.

    1996-12-31

    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 utili- zation 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 NNM 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 29}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 coals, and their suitability for possible correlations with the oil sourcing potential 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.

  12. Feasibility study of proton-based quality assurance of proton range compensator

    NASA Astrophysics Data System (ADS)

    Park, S.; Jeong, C.; Min, B. J.; Kwak, J.; Lee, J.; Cho, S.; Shin, D.; Lim, Y. K.; Park, S. Y.; Lee, S. B.

    2013-06-01

    All patient specific range compensators (RCs) are customized for achieving distal dose conformity of target volume in passively scattered proton therapy. Compensators are milled precisely using a computerized machine. In proton therapy, precision of the compensator is critical and quality assurance (QA) is required to protect normal tissues and organs from radiation damage. This study aims to evaluate the precision of proton-based quality assurance of range compensator. First, the geometry information of two compensators was extracted from the DICOM Radiotherapy (RT) plan. Next, RCs were irradiated on the EBT film individually by proton beam which is modulated to have a photon-like percent depth dose (PDD). Step phantoms were also irradiated on the EBT film to generate calibration curve which indicates relationship between optical density of irradiated film and perpendicular depth of compensator. Comparisons were made using the mean absolute difference (MAD) between coordinate information from DICOM RT and converted depth information from the EBT film. MAD over the whole region was 1.7, and 2.0 mm. However, MAD over the relatively flat regions on each compensator selected for comparison was within 1 mm. These results shows that proton-based quality assurance of range compensator is feasible and it is expected to achieve MAD over the whole region less than 1 mm with further correction about scattering effect of proton imaging.

  13. NMR study of a membrane protein in detergent-free aqueous solution

    PubMed Central

    Zoonens, Manuela; Catoire, Laurent J.; Giusti, Fabrice; Popot, Jean-Luc

    2005-01-01

    One of the major obstacles to membrane protein (MP) structural studies is the destabilizing effect of detergents. Amphipols (APols) are short amphipathic polymers that can substitute for detergents to keep MPs water-soluble under mild conditions. In the present work, we have explored the feasibility of studying the structure of APol-complexed MPs by NMR. As a test MP, we chose the 171-residue transmembrane domain of outer MP A from Escherichia coli (tOmpA), whose x-ray and NMR structures in detergent are known. 2H,15N-labeled tOmpA was produced as inclusion bodies, refolded in detergent solution, trapped with APol A8-35, and the detergent removed by adsorption onto polystyrene beads. The resolution of transverse relaxation-optimized spectroscopy–heteronuclear single-quantum correlation spectra of tOmpA/A8-35 complexes was found to be close to that of the best spectra obtained in detergent solutions. The dispersion of chemical shifts indicated that the protein had regained its native fold and retained it during the exchange of surfactants. MP–APol interactions were mapped by substituting hydrogenated for deuterated A8-35. The resulting dipolar broadening of amide proton linewidths was found to be limited to the β-barrel region of tOmpA, indicating that A8-35 binds specifically to the hydrophobic transmembrane surface of the protein. The potential of this approach to MP studies by solution NMR is discussed. PMID:15956183

  14. (1)H-NMR-based metabolomic studies of bisphenol A in zebrafish (Danio rerio).

    PubMed

    Yoon, Changshin; Yoon, Dahye; Cho, Junghee; Kim, Siwon; Lee, Heonho; Choi, Hyeonsoo; Kim, Suhkmann

    2017-04-03

    Proton nuclear magnetic resonance ((1)H-NMR) spectroscopy was used to study the response of zebrafish (Danio rerio) to increasing concentrations of bisphenol A (4,4'-(propane-2,2-diyl)diphenol, BPA). Orthogonal partial least squares discriminant analysis (OPLS-DA) was applied to detect aberrant metabolomic profiles after 72 h of BPA exposure at all levels tested (0.01, 0.1, and 1.0 mg/L). The OPLS-DA score plots showed that BPA exposure caused significant alterations in the metabolome. The metabolomic changes in response to BPA exposure generally exhibited nonlinear patterns, with the exception of reduced levels of several metabolites, including glutamine, inosine, lactate, and succinate. As the level of BPA exposure increased, individual metabolite patterns indicated that the zebrafish metabolome was subjected to severe oxidative stress. Interestingly, ATP levels increased significantly at all levels of BPA exposure. In the present study, we demonstrated the applicability of (1)H-NMR-based metabolomics to identify the discrete nature of metabolic changes.

  15. Proton Exchange in a Paramagnetic Chemical Exchange Saturation Transfer Agent from Experimental Studies and ab Initio Metadynamics Simulation.

    PubMed

    Pollet, Rodolphe; Bonnet, Célia S; Retailleau, Pascal; Durand, Philippe; Tóth, Éva

    2017-03-27

    The proton-exchange process between water and a carbamate has been studied experimentally and theoretically in a lanthanide-based paramagnetic chemical exchange saturation transfer agent endowed with potential multimodality detection capabilities (optical imaging, or T1 MRI for the Gd(III) analogue). In addition to an in-depth structural analysis by a combined approach (using X-ray crystallography, NMR, and molecular dynamics), our ab initio simulation in aqueous solution sheds light on the reaction mechanism for this proton exchange, which involves structural Grotthuss diffusion.

  16. 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

  17. 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.

  18. 35Cl NQR and 1H NMR Studies of Molecular Motions in Guanidinium Salt of Chloroacetic Acid

    NASA Astrophysics Data System (ADS)

    Zdanowska-Fnjczek, Maria; Grottel, Małgorzata; Jakubas, Ryszard

    1998-07-01

    Multinuclear NQR and NMR techniques have been applied in order to study the molecular dynamics in [C(NH2)3](ClH2CCOO). The 35Cl NQR frequency was measured over a wide range of temperature. The experimental results were described by using the theories of Bayer and Brown which take into account the torsional oscillations of the CClH2 -group of the anion. A study of the proton NMR second moment as well as relaxation times T1, and T1p performed in a wide temperature range revealed an onset of the guanidinium cation reorientation around its two-fold symmetry axis. Activation parameters for this motion were determined.

  19. Heterogeneity of polyelectrolyte diffusion in polyelectrolyte-protein coacervates: a 1H pulsed field gradient NMR study.

    PubMed

    Menjoge, Amrish R; Kayitmazer, A Basak; Dubin, Paul L; Jaeger, Werner; Vasenkov, Sergey

    2008-04-24

    Proton pulsed field gradient (PFG) NMR was used to study the diffusion of poly(diallyldimethylammonium chloride) (PDADMAC) in coacervates formed from this polycation and the protein bovine serum albumin (BSA). Application of high (up to 30 T/m) magnetic field gradients in PFG NMR measurements allowed probing the diffusion of PDADMAC on a length scale of displacements as small as 100 nm in coacervates formed at different pH's and ionic strengths, i.e., conditions of varying protein-polycation interaction energy. Studies were carried out for a broad range of diffusion times and corresponding values of the mean square displacements. Several ensembles of PDADMAC polycations with different diffusivities were observed in the measured range of diffusion times. The existence of these ensembles and the pattern of their changes with increasing diffusion time support the hypothesis about the microscopic heterogeneity of PDADMAC-BSA coacervates and also provide evidence for the dynamic disintegration and reformation of dense domains.

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

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

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

  1. Understanding CO2 capture mechanisms in aqueous hydrazine via combined NMR and first-principles studies.

    PubMed

    Lee, Byeongno; Stowe, Haley M; Lee, Kyu Hyung; Hur, Nam Hwi; Hwang, Son-Jong; Paek, Eunsu; Hwang, Gyeong S

    2017-09-13

    Aqueous amines are currently the most promising solution for large-scale CO2 capture from industrial sources. However, molecular design and optimization of amine-based solvents have proceeded slowly due to a lack of understanding of the underlying reaction mechanisms. Unique and unexpected reaction mechanisms involved in CO2 absorption into aqueous hydrazine are identified using (1)H, (13)C, and (15)N NMR spectroscopy combined with first-principles quantum-mechanical simulations. We find production of both hydrazine mono-carbamate (NH2-NH-COO(-)) and hydrazine di-carbamate ((-)OOC-NH-NH-COO(-)), with the latter becoming more populated with increasing CO2 loading. Exchange NMR spectroscopy also demonstrates that the reaction products are in dynamic equilibrium under ambient conditions due to CO2 exchange between mono-carbamate and di-carbamate as well as fast proton transfer between un-protonated free hydrazine and mono-carbamate. The exchange rate rises steeply at high CO2 loadings, enhancing CO2 release, which appears to be a unique property of hydrazine in aqueous solution. The underlying mechanisms of these processes are further evaluated using quantum mechanical calculations. We also analyze and discuss reversible precipitation of carbamate and conversion of bicarbonate to carbamates. The comprehensive mechanistic study provides useful guidance for optimal design of amine-based solvents and processes to reduce the cost of carbon capture. Moreover, this work demonstrates the value of a combined experimental and computational approach for exploring the complex reaction dynamics of CO2 in aqueous amines.

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

    PubMed

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

    2011-03-24

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

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

    SciTech Connect

    Black, Bruce Elmer

    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 11B and 27Al NQR resonances. The scope of this study was increased to include 23Na, 51V, and 55Mn NQR transitions. Also, a technique was presented to observe 14N 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 14N 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.

  4. Proton Conductivity Studies on Biopolymer Electrolytes

    SciTech Connect

    Harun, N. I.; Sabri, N. S.; Rosli, N. H. A.; Taib, M. F. M.; Saaid, S. I. Y.; Kudin, T. I. T.; Ali, A. M. M.; Yahya, M. Z. A.

    2010-07-07

    Proton conducting solid biopolymer electrolyte membranes consisting of methyl cellulose (MC) and different wt.% of ammonium nitrate (NH{sub 4}NO{sub 3}) were prepared by solution cast technique. Impedance spectroscopy was carried out to study electrical characteristics of bulk materials. The ionic conductivity of the prepared samples was calculated using the bulk resistance (R{sub b}) obtained from impedance spectroscopy plot. The highest ionic conductivity obtained was 1.17x10{sup -4} Scm{sup -1} for the sample with composition ratio of MC(50): NH{sub 4}NO{sub 3}(50). To enhance the ionic conductivity, propylene carbonate (PC) and ethylene carbonate (EC) plasticizers were introduced. It was found that the ionic conductivity of polymer electrolyte membranes increased with the increase in plasticizers concentration. The ionic conductivities of solid polymer electrolytes based on MC-NH{sub 4}NO{sub 3}-PC was enhanced up to 4.91x10{sup -3} Scm{sup -1} while for the MC-NH{sub 4}NO{sub 3}-EC system, the highest conductivity was 1.74x10{sup -2} Scm{sup -1}. The addition of more plasticizer however decreases in mechanical stability of the membranes.

  5. Assignment of NMR data and relative stereochemistry determination of paraconic acid derivatives

    NASA Astrophysics Data System (ADS)

    Rodrigues, Shirley Muniz Machado; Nardini, Viviani; Moral, Raphael Fernando; Constantino, Mauricio Gomes; da Silva, Gil Valdo José

    2013-12-01

    γ-Butyrolactones 4a1, 4a2, 4b1 and 4b2 were carefully studied through NMR experiments. 1H NMR, 13C {1H} NMR, COSY, HMQC, HMBC and J-res experiments were performed to provide the needed structure information. NOE between protons distributed around the stereocenters were thus used to determine the relative configuration of the molecules.

  6. Active site dynamics in NADH oxidase from Thermus thermophilus studied by NMR spin relaxation.

    PubMed

    Miletti, Teresa; Farber, Patrick J; Mittermaier, Anthony

    2011-09-01

    We have characterized the backbone dynamics of NADH oxidase from Thermus thermophilus (NOX) using a recently-developed suite of NMR experiments designed to isolate exchange broadening, together with (15)N R (1), R (1ρ ), and {(1)H}-(15)N steady-state NOE relaxation measurements performed at 11.7 and 18.8 T. NOX is a 54 kDa homodimeric enzyme that belongs to a family of structurally homologous flavin reductases and nitroreductases with many potential biotechnology applications. Prior studies have suggested that flexibility is involved in the catalytic mechanism of the enzyme. The active site residue W47 was previously identified as being particularly important, as its level of solvent exposure correlates with enzyme activity, and it was observed to undergo "gating" motions in computer simulations. The NMR data are consistent with these findings. Signals from W47 are dynamically broadened beyond detection and several other residues in the active site have significant R ( ex ) contributions to transverse relaxation rates. In addition, the backbone of S193, whose side chain hydroxyl proton hydrogen bonds directly with the FMN cofactor, exhibits extensive mobility on the ns-ps timescale. We hypothesize that these motions may facilitate structural rearrangements of the active site that allow NOX to accept both FMN and FAD as cofactors.

  7. 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.

  8. NMR spectroscopy study of local correlations in water

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  9. NMR spectroscopy study of local correlations in water.

    PubMed

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

    2016-12-07

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

  10. Review of NMR studies of nanoscale molecular magnets composed of geometrically frustrated antiferromagnetic triangles

    SciTech Connect

    Furukawa, Yuji

    2016-10-01

    This paper presents a comprehensive review of nuclear magnetic resonance (NMR) studies performed on three nanoscale molecular magnets with different novel configurations of geometrically frustrated antiferromagnetic (AFM) triangles: (1) the isolated single AFM triangle K6[V15As6O42(H2O)]·8H2O (in short V15), (2) the spin ball [Mo72Fe30O252(Mo2O7(H2O))2(Mo2O8H2(H2O)) (CH3COO)12(H2O)91]·150H2O (in short Fe30 spin ball), and (3) the twisted triangular spin tube [(CuCl2tachH)3Cl]Cl2 (in short Cu3 spin tube). In V15t, from 51V NMR spectra, the local spin configurations were directly determined in both the nonfrustrated total spin ST = 3/2 state at higher magnetic fields (H ge; 2.7 T) and the two nearly degenerate ST = 1/2 ground states at lower magnetic fields (H ≤ 2.7 T). The dynamical magnetic properties of V15 were investigated by proton spin-lattice relaxation rate (1/T1) measurements. In the ST = 3/2 state, 1/T1 shows thermally activated behaviour as a function of temperature. On the other hand, the temperature independent behaviour of 1/T1 at very low temperatures is observed in the frustrated ST = 1/2 ground state. Possible origins for the peculiar behaviour of 1/T1 will be discussed in terms of magnetic fluctuations due to spin frustrations. In Fe30, static and dynamical properties of Fe3+ (s = 5/2) have been investigated by proton NMR spectra and 1/T1 measurements. From the temperature dependence of 1/T1, the fluctuation frequency of the Fe3+ spins is found to decrease with decreasing temperature, indicating spin freezing at low temperatures. The

  11. Review of NMR studies of nanoscale molecular magnets composed of geometrically frustrated antiferromagnetic triangles

    SciTech Connect

    Furukawa, Yuji

    2016-10-01

    This paper presents a comprehensive review of nuclear magnetic resonance (NMR) studies performed on three nanoscale molecular magnets with different novel configurations of geometrically frustrated antiferromagnetic (AFM) triangles: (1) the isolated single AFM triangle K6[V15As6O42(H2O)]·8H2O (in short V15), (2) the spin ball [Mo72Fe30O252(Mo2O7(H2O))2(Mo2O8H2(H2O)) (CH3COO)12(H2O)91]·150H2O (in short Fe30 spin ball), and (3) the twisted triangular spin tube [(CuCl2tachH)3Cl]Cl2 (in short Cu3 spin tube). In V15t, from 51V NMR spectra, the local spin configurations were directly determined in both the nonfrustrated total spin ST = 3/2 state at higher magnetic fields (H ge; 2.7 T) and the two nearly degenerate ST = 1/2 ground states at lower magnetic fields (H ≤ 2.7 T). The dynamical magnetic properties of V15 were investigated by proton spin-lattice relaxation rate (1/T1) measurements. In the ST = 3/2 state, 1/T1 shows thermally activated behaviour as a function of temperature. On the other hand, the temperature independent behaviour of 1/T1 at very low temperatures is observed in the frustrated ST = 1/2 ground state. Possible origins for the peculiar behaviour of 1/T1 will be discussed in terms of magnetic fluctuations due to spin frustrations. In Fe30, static and dynamical properties of Fe3+ (s = 5/2) have been investigated by proton NMR spectra and 1/T1 measurements. From the temperature dependence of 1/T1, the fluctuation frequency of the Fe3+ spins is found to decrease with decreasing temperature, indicating spin freezing at low temperatures. The

  12. Chemical behavior of methylpyranomalvidin-3-O-glucoside in aqueous solution studied by NMR and UV-visible spectroscopy.

    PubMed

    Oliveira, Joana; Petrov, Vesselin; Parola, A Jorge; Pina, Fernando; Azevedo, Joana; Teixeira, Natércia; Brás, Natércia F; Fernandes, Pedro A; Mateus, Nuno; Ramos, Maria João; de Freitas, Victor

    2011-02-17

    In the present work, the proton-transfer reactions of the methylpyranomalvidin-3-O-glucoside pigment in water with different pH values was studied by NMR and UV-visible spectroscopies. The results showed four equilibrium forms: the methylpyranomalvidin-3-O-glucoside cation, the neutral quinoidal base, the respective anionic quinoidal base, and a dianionic base unprotonated at the methyl group. According to the NMR data, it seems that for methylpyranomalvidin-3-O-glucoside besides the acid-base equilibrium between the pyranoflavylium cation and the neutral quinoidal base, a new species is formed at pD 4.88-6.10. This is corroborated by the appearance of a new set of signals in the NMR spectrum that may be assigned to the formation of hemiketal/cis-chalcone species to a small extent. The two ionization constants (pK(a1) and pK(a2)) obtained by both methods (NMR and UV-visible) for methylpyranomalvidin-3-O-glucoside are in agreement (pK(a1) = 5.17 ± 0.03; pK(a2) = 8.85 ± 0.08; and pK(a1) = 4.57 ± 0.07; pK(a2) = 8.23 ± 0.04 obtained by NMR and UV-visible spectroscopies, respectively). Moreover, the fully dianionic unprotonated form (at the methyl group) of the methylpyranomalvidin-3-O-glucoside is converted slowly into a new structure that displays a yellow color at basic pH. On the basis of the results obtained through LC-MS and NMR, the proposed structure was found to correspond to the flavonol syringetin-3-glucoside.

  13. 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.

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

    PubMed

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

    2015-12-01

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

  15. NMR studies of electrostatic potential distribution around biologically important molecules.

    PubMed Central

    Likhtenshtein, G I; Adin, I; Novoselsky, A; Shames, A; Vaisbuch, I; Glaser, R

    1999-01-01

    A new experimental approach has been developed to study the distribution of local electrostatic potential around specific protons in biologically important molecules. The approach is the development of a method denoted as "spin label/spin probe," which was proposed by one of us (. Mol. Biol. 6:498-507). The proposed method is based upon the quantitative measurement of the contribution of differently charged nitroxide probes to the spin lattice relaxation rate (1/T1) of protons in the molecule of interest, followed by calculation of local electrostatic potential using the classical Debye equation. In parallel, the theoretical calculation of potential distribution with the use of the MacSpartan Plus 1.0 program has been performed. Application of the method to solutions of simple organic molecules (aliphatic and aromatic alcohols, aliphatic carboxylates (propionate anion), and protonated ethyl amine and imidazole) allowed us to estimate the effective potential around the molecules under investigation. These were found to be in good agreement with theoretically expected values. This technique was then applied to zwitterionic amino acids bearing neutral and charged side chains (glycine, lysine, histidine, and aspartic acid). The reliability of the general approach is proved by the data presented in this paper. Application of this new methodology can afford insight into the biochemical significance of electrostatic effects in biological systems. PMID:10388770

  16. Ultrasound Devulcanization of Natural Rubber, Studied by NMR Relaxation and Diffusion

    NASA Astrophysics Data System (ADS)

    von Meerwall, E.

    2005-03-01

    In support of recycling of industrial rubbers, we have studied the effect of intense ultrasound on unfilled natural rubber networks using proton and carbon transverse NMR relaxation and diffusion, sol extraction, and bulk characterization. At 70.5^o C the proton echo decay exhibits three components, due to entangled sol and crosslinked network; unentangled polymeric sol plus dangling chain ends; and oligomer remnants. Contrary to the 13C results which indicate backbone mobilities decreasing with sonication (hence with increasing sol fraction), all 1H component T2 values, hence intermolecular mobilities, increase by similar modest factors; the network component amplitude decreases strongly. Diffusion of unentangled sol is sharply bimodal, arising from intermediate fractions and unreactive oligomers. Both diffusion rates decrease slightly with sonication in spite of plasticization by sol, because degradation adds sol primarily of intermediate molecular weights. We compare these results with our earlier work in SBR. Although ultrasound devulcanization does not recover many properties of the virgin melt, recyclability is not compromised.

  17. Experimental NMR spin-lattice relaxometry study in the liquid crystalline nematic phase of propylcyano-phenylcyclohexane.

    PubMed

    Acosta, R H; Pusiol, D J

    2001-01-01

    The NMR spin-lattice proton relaxation dispersion T1(nu(L)) of the liquid crystal propylcyano-phenylcyclohexane is studied over several decades of Larmor frequencies and at different temperatures in the nematic mesophase. The results show that the order fluctuation of the local nematic director contribution to T1(nu(L)) undergoes a transition between two power regimes: from T1(nu(L)) protional to nu(1/2)L to nu(alpha)L (alpha approximately 1/3) on going from low to high Larmor frequencies.

  18. 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.

  19. (1)H, (13)C NMR and X-ray crystallographic studies of highly polyhalogenated derivatives of costunolide lactone.

    PubMed

    Corona, D; Díaz, E; Nava, J L; Guzmán, A; Barrios, H; Fuentes, A; Hernandez-Plata, S A; Allard, J; Jankowski, C K

    2005-11-01

    The costunolide lactone, a sesquiterpene compound isolated from Zaluzania triiloba species, reacted with several dihalocarbene sources produced by trihaloform-NaOH under successive phase transfer reactions yielding mono-, bis- and tris-dihalocyclopropane adducts. The structures, as well as the configurational assignments of the different derivatives, were established by (1)H and (13)C NMR spectroscopy and assisted by X-ray crystallographic and molecular modelling studies. The specific shielding of protons in the neighbourhood of different halogens on the cyclopropane moieties was correlated to the pseudocontact interactions.

  20. Studies of a Proton Bunch Phase Monitor for Range Verification in Proton Therapy

    SciTech Connect

    Werner, T.; Golnik, C.; Enghardt, W.; Petzoldt, J.; Kormoll, T.; Pausch, G.; Straessner, A.; Roemer, K.; Dreyer, A.; Hueso-Gonzalez, F.; Enghardt, W.

    2015-07-01

    A primary subject of the present research in particle therapy is to ensure the precise irradiation of the target volume. The prompt gamma timing (PGT) method provides one possibility for in vivo range verification during the irradiation of patients. Prompt gamma rays with high energies are emitted promptly due to nuclear reactions of protons with tissue. The arrival time of these gammas to the detector reflects the stopping process of the primary protons in tissue and is directly correlated to the range. Due to the time resolution of the detector and the proton bunch time spread, as well as drifts of the bunch phase with respect to the accelerator frequency, timing spectra are smeared out and compromise the accuracy of range information intended for future clinical applications. Nevertheless, counteracting this limitation and recovering range information from the PGT measured spectra, corrections using a bunch phase monitor can be performed. A first prototype of bunch phase monitor was tested at GSI Darmstadt, where measurements of the energy correlation profile of the ion bunches were performed. At the ELBE accelerator at Helmholtz-Zentrum Dresden-Rossendorf (HZDR), set up to provide bremsstrahlung photons in very short pulses, a constant fraction algorithm for the incoming digital signals was evaluated, which is used for optimizing the time resolution. Studies of scattering experiments with different thin targets and detector positions are accomplished at Onco Ray Dresden, where a clinical proton beam is available. These experiments allow a basic characterization of the proton bunch structure and the detection yield. (authors)

  1. Studies of a proton phase beam monitor for range verification in proton therapy

    SciTech Connect

    Werner, T.; Golnik, C.; Enghardt, W.; Petzoldt, J.; Kormoll, T.; Pausch, G.; Straessner, A.; Roemer, K.; Dreyer, A.; Hueso-Gonzalez, F.; Enghardt, W.

    2015-07-01

    A primary subject of the present research in particle therapy is to ensure the precise irradiation of the target volume. The prompt gamma timing (PGT) method provides one possibility for in vivo range verification during the irradiation of patients. Prompt gamma rays with high energies are emitted promptly due to nuclear reactions of protons with tissue. The arrival time of these gammas to the detector reflects the stopping process of the primary protons in tissue and are directly correlated to the range. Due to the time resolution of the detector and the proton bunch time spread, as well as drifts of the bunch phase with respect to the accelerator frequency, timing spectra are smeared out and compromise the accuracy of range information intended for future clinical applications. Nevertheless, counteracting this limitation and recovering range information from the PGT measured spectra, corrections using a phase beam monitor can be performed. A first prototype of phase beam monitor was tested at GSI Darmstadt, where measurements of the energy profile of the ion bunches were performed. At the ELBE accelerator Helmholtz-Zentrum Dresden-Rossendorf (HZDR), set up to provide bremsstrahlung photons in very short pulses, a constant fraction algorithm for the incoming digital signals was evaluated, which is used for optimizing the time resolution. Studies of scattering experiments with different thin targets and detector positions are accomplished at Oncoray Dresden, where a clinical proton beam is available. These experiments allow a basic characterization of the proton bunch structure and the detection yield. (authors)

  2. Solid-state NMR relaxation studies of Australian spider silks.

    PubMed

    Kishore, A I; Herberstein, M E; Craig, C L; Separovic, F

    Solid-state NMR techniques were used to study two different types of spider silk from two Australian orb-web spider species, Nephila edulis and Argiope keyserlingi. A comparison of (13)C-T(1) and (1)H-T(1rho) solid-state NMR relaxation data of the Ala Calpha, Ala Cbeta, Gly Calpha, and carbonyl resonances revealed subtle differences between dragline and cocoon silk. (13)C-T(1rho) and (1)H-T(1) relaxation experiments showed significant differences between silks of the two species with possible structural variations. Comparison of our data to previous (13)C-T(1) relaxation studies of silk from Nephila clavipes (A. Simmons et al., Macromolecules, 1994, Vol. 27, pp. 5235-5237) also supports the finding that differences in molecular mobility of dragline silk exist between species. Interspecies differences in silk structure may be due to different functional properties. Relaxation studies performed on wet (supercontracted) and dry silks showed that the degree of hydration affects relaxation properties, and hence changes in molecular mobility are correlated with functional properties of silk. Copyright 2002 Wiley Periodicals, Inc.

  3. 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.

  4. Assignment of selected hyperfine proton NMR resonances in the met forms of Glycera dibranchiata monomer hemoglobins and comparisons with sperm whale metmyoglobin

    SciTech Connect

    Constantinidis, I.; Satterlee, J.D.; Pandey, R.K.; Leung, H.K.; Smith, K.M.

    1988-04-19

    This work indicates a high degree of purity for our preparations of all three of the primary Glycera dibranchiata monomer hemoglobins and details assignments of the heme methyl and vinyl protons in the hyperfine shift region of the ferric (aquo.) protein forms. The assignments were carried out by reconstituting the apoproteins of each component with selectively deuteriated hemes. The results indicate that even though the individual component preparations consist of essentially a single protein, the proton NMR spectra indicate spectroscopic heterogeneity. Evidence is presented for identification and classification of major and minor protein forms that are present in solutions of each component. Finally, in contrast to previous results, a detailed analysis of the proton hyperfine shift patterns of the major and minor forms of each component, in comparison to the major and minor forms of metmyoglobin, leads to the conclusions that the corresponding forms of the proteins from each species have strikingly similar heme-globin contacts and display nearly identical heme electronic structures and coordination numbers.

  5. Experimental Studies Of An Exotic Decay Mode At The Proton Drip-Line: The Two-Proton Radioactivity

    NASA Astrophysics Data System (ADS)

    Audirac, L.; Adimi, N.; Ascher, P.; Blank, B.; Brown, B. A.; Borcea, C.; Canchel, G.; Companis, I.; Delalee, F.; Demonchy, C. E.; de Oliveira Santos, F.; Dossat, C.; Giovinazzo, J.; Grévy, S.; Grigorenko, L. V.; Hay, L.; Huikari, J.; Kurtukian-Nieto, T.; Leblanc, S.; Matea, I.; Pedroza, J.-L.; Perrot, L.; Pibernat, J.; Serani, L.; Stodel, C.; Strivastava, P.; Thomas, J.-C.

    2011-10-01

    Two-proton radioactivity is an exotic decay mode for very proton-rich nuclei. It was observed experimentally for the first time in 2002 for the nucleus 45Fe but the two protons could not be directly detected. So a new detector has been developed, a Time Projection Chamber, to individually observe the two protons emitted. It was used successfully during two experiments for the study of 45Fe and 54Zn. Energy correlations have been studied and the relative angle between the two protons is calculated.

  6. Location of protons in anhydrous Keggin heteropolyacids H(3)PMo(12)O(40) and H(3)PW(12)O(40) by (1)H[(31)P]/(31)P[(1)H] REDOR NMR and DFT quantum chemical calculations.

    PubMed

    Ganapathy, S; Fournier, M; Paul, J F; Delevoye, L; Guelton, M; Amoureux, J P

    2002-07-03

    HeteroPolyAcids (HPA's) are a class of solid acids that have broad applications in many fields of science and technology, including catalysis and chemical engineering. The proton locations within the thermally stable and commonly known Keggin unit, which is the primary structure building unit/block, has remained undetermined in anhydrous HPAs, despite numerous theoretical and experimental efforts. However, Rotational Echo DOuble Resonance (REDOR) NMR and Density Functional Theory (DFT) quantum chemical calculations offer a new opportunity to determine the exact locations of protons within the Keggin unit. The crucial experimental evidence is provided for the basic and very extensively studied acidic form of H(8-n)X(n+)M(12)O(40), X = Si, P and M = Mo, W, belonging to the Keggin structure. While showing that the acidic protons are located in the bridging oxygen positions (R(P-H) = 520 +/- 20 pm) in H(3)PMo(12)O(40) and in the terminal oxygen positions (R(P-H) = 570 +/- 20 pm) in H(3)PW(12)O(40), REDOR measurements also provide for the first time the structural basis to consistently rank the acid strength for the important class of Keggin solid catalysts.

  7. Phenol-formaldehyde resins: A quantitative NMR study of molecular structure and molecular dynamics

    NASA Astrophysics Data System (ADS)

    Ottenbourgs, Benjamin Tony

    Phenol-formaldehyde (PF) resins have been the subject of this work. 13C liquid-state and solid-state NMR has been used to investigate the molecular structure of mainly novolak and partially of resole resins. 1H wideline in combination with 13C solid-state NMR relaxometry has been applied to study the curing and the molecular dynamics of phenolic resins. It was the intention to provide an insight in the relationship between resin composition, resin structure and subsequent resin properties (by means of the molecular dynamics). An improved 13C liquid-state NMR quantification technique of novolaks in THF-CDCl3 solutions is demonstrated. Full quantitative 13C liquid-state spectra of phenol-formaldehyde resins with high signal- to-noise ratio were obtained by using chromium acetylacetonate under optimized spectral conditions within a few hours spectrometer time. Attached proton test (APT) spectra enabled proper peak assignments in the region with significant overlap. For several novolaks, prepared under different catalytic conditions, the degree of polymerization, degree of branching, number average molecular weight, isomeric distribution, and the number of unreacted ortho and para phenol ring positions was determined with a reduced margin of error, by analyzing and integrating the 13C spectra. The power of 13C solid-state NMR in the analysis of cured PF resins is shown. Particular importance was ascribed to the question of the quantifiability of the experiments when it was desired to measure the degree of conversion by means of a 13C CP/MAS contact time study. The network structure present, and thus also the mechanical properties, is critically dependent upon the final degree of conversion obtained after curing. The degree of conversion, which depended on the cure conditions (cure temperature, cure pressure and cure time), was limited by vitrification as was demonstrated by DSC experiments. Changes in the spin-lattice relaxation time T 1H were observed, providing

  8. Nuclear magnetic resonance (NMR) studies of nickel-iron hybrid hemoglobins (Hb)

    SciTech Connect

    Shibayama, N.; Inubushi, T.; Ikeda-Saito, M.; Yonetani, T.

    1986-05-01

    Ni-Fe hybrid Hbs, ..cap alpha..(Ni)/sub 3/..beta..(Fe)/sup 2/ and ..cap alpha..(Fe)/sub 2/..beta..(Ni)/sub 2/, have been studied by proton NMR. ..cap alpha..(Fe)/sub 2/..beta..(Ni)/sub 2/, ..cap alpha..(Ni)/sub 2/..beta..(Fe)/sub 2/, and ..cap alpha..(Ni)/sub 2/..beta..(Ni)/sub 2/ show exchangeable proton resonances at +14 and +11 ppm, T-state markers. Upon binding of CO to ..cap alpha..(Fe)/sub 2/..beta..(Ni)/sub 2/, these T-state markers disappear with a concomitant appearance of a R-state marker at +10.8 ppm at pH 6.5 to 8.5. On the other hand, the complementary hybrid, ..cap alpha..(Ni)/sub 2/..beta..(Fe-CO)/sub 2/, shows the two T-state markers at low pHs. Upon raising pH, the amplitude of the T-state markers is decreased and accompanied by an appearance of the R-state marker. Electronic absorption spectra and hyperfine-shifted proton resonances at different pHs indicate that these ligand-induced structural changes are accompanied by the changes in the coordination and spin states of Ni-PP in ..cap alpha..(Ni)/sub 2/-subunits. In the deoxy T-state, the ..cap alpha..(Ni)/sub 2/-subunits are dominantly in a tetra-coordinated (S = 0) state, whereas, in the R-state, the penta-coordinated (S = 1) state is markedly increased in the ..cap alpha..(Ni)/sub 2/-subunits. Thus, hyperfine-shifted proximal His NH proton resonances of the ..cap alpha..(Ni)/sub 2/-subunits are observable only in the R-state. The Ni-PP in the ..beta..(Ni)/sub 2/-subunits, however, always takes a penta-coordinated (S = 1) state regardless of the medium conditions and the state of ligation in the partner ..cap alpha..(Fe)/sub 2/-subunits. Thus, hyperfine-shifted proximal His NH proton resonances of the ..beta..(Ni)/sub 2/-subunits are always observable.

  9. NMR Study of Organic Counterion Binding to Perfluorinated Micellar Structures

    NASA Astrophysics Data System (ADS)

    Bossev, Dobrin; Matsumoto, Mustuo; Nakahara, Masaru

    2008-03-01

    In this study we have applied our previously developed NMR method to study the adsorption of tetramethylammonium (TMA^+) and tetraethylammonium (TEA^+) counterions to micelles formed by perfluorooctylsulfonate (FOS^-) surfactant in water at 30 C. These two counterions induce formation of threadlike surfactant structures that result in well pronounced viscoelastic properties of the solution. To selectively probe the degree of counterion binding we have used ^1H and ^19F NMR chemical shifts and self-diffusion coefficients that are sensitive to the Stern and diffuse double layers, respectively. The competitive adsorption of TMA^+ and TEA^+ was examined as a function of the TMA^+/TEA^+ ratio at a constant FOS^- concentration of 100 mM. The two counterions were found to form Stern layer around the FOS^- micelles with comparable packing; about one counterion per two micellized FOS molecules. When mixed at intermediate proportions, however, the TEA^+ counterion shows preferential binding; the concentration of TEA^+ in the Stern layer is found to be twice higher than that of TMA^+ at equal total respective concentrations in the solution. These results are discussed in terms of counterion size and hydrophobicity and presented in parallel with those that involved the smaller and more hydrophilic lithium counterion.

  10. Tricritical point in ferroelastic ammonium titanyl fluoride: NMR study

    SciTech Connect

    Kavun, V.Ya.; Kozlova, S.G.; Laptash, N.M; Tkachenko, I.A.; Gabuda, S.P

    2010-09-15

    Ionic mobility and phase transitions in ammonium titanyl pentafluoride (NH{sub 4}){sub 3}TiOF{sub 5} were studied using the {sup 19}F and {sup 1}H NMR data. The high-temperature phase (I) is characterized by spherically symmetric (isotropic) reorientation of [TiOF{sub 5}]{sup 3-} anions and by uniaxial reorientation of these anions in the ferroelastic phase II. A previously unknown second-order phase transition to the low-temperature modification (NH{sub 4}){sub 3}TiOF{sub 5}(III) was found at 205 K. The transition is accompanied by hindering of uniaxial rotations of [TiOF{sub 5}]{sup 3-} anions and by noticeable change of {sup 19}F magnetic shielding tensor associated with the influence of pseudo-Jahn-Teller effect. A pressure-induced tricritical point with coordinates p{sub TCR{approx}}2 kbar and T{sub TCR{approx}}170 K is estimated on the base of {sup 19}F NMR chemical shift data, and previously studied p-T diagram of (NH{sub 4}){sub 3}TiOF{sub 5}. - Graphical abstract: p-T phase diagram of (NH{sub 4}){sub 3}TiOF{sub 5}.

  11. T.C.G triplet in an antiparallel purine.purine.pyrimidine DNA triplex. Conformational studies by NMR.

    PubMed

    Dittrich, K; Gu, J; Tinder, R; Hogan, M; Gao, X

    1994-04-12

    The antiparallel purine.purine.pyrimidine DNA triplex, RRY6, which contains a T.C.G inverted triplet in the center of the sequence, was examined by proton and phosphorous two-dimensional NMR spectroscopy. The local conformation of the T.C.G triplet (T4.C11.G18) and the effect of this triplet on the global helical structure were analyzed in detail. The formation of the T.C.G triplet is confirmed by a set of cross-strand NOEs, including unusual cross-strand NOEs between the third strand and the pyrimidine strand as opposed to the purine strand of the duplex. NMR data suggest that the T.C.G triplet may be present in an equilibrium between a non-hydrogen-bonded form and a T(O4)-C(NH2) hydrogen-bonded form and that there is a distortion of the in-plane alignment of the three bases. The flanking G.G.C base triplets are well-defined on the 5'-side of T4, but somewhat interrupted on the 3'-side of T4. The effect of the third strand binding on the Watson-Crick duplex was probed by an NMR study of the free duplex RY6. NMR parameters are affected mostly around the T.C.G inversion site. The perturbations extend to at least two adjacent base triplets on either side. The binding of the third purine strand and the accommodation of a central T.C.G inversion in RRY6 does not require a readjustment in sugar pucker, which remains in the range of C2'-endo. 31P resonances of RRY6 distribute over a range of 2.2 ppm. The H-P coupling patterns of the third strand differ from those of the duplex. General spectral patterns defined by the marker protons of the RRY and YRY triplexes are compared.

  12. In vivo localized proton spectroscopic studies of human gastrocnemius muscle

    SciTech Connect

    Narayana, P.A.; Jackson, E.F.; Hazle, J.D.; Fotedar, L.K.; Kulkarni, M.V.; Flamig, D.P.

    1988-10-01

    In vivo proton magnetic resonance spectroscopy studies of gastrocnemius muscle were performed in six normal volunteers. Both spatially resolved spectroscopy (SPARS) and stimulated echo acquisition mode (STEAM) sequences were used for volume localization. A number of water suppression sequences have been combined with these localization schemes. Among the various techniques investigated in these studies, STEAM with an inversion pulse (T1-discriminated spectrum) seems to have the best potential for in vivo localized high-resolution proton spectroscopy studies of human muscle.

  13. Scaling Studies of Laser Proton Acceleration by Radiation Pressure Sail

    NASA Astrophysics Data System (ADS)

    Liu, T. C.; Dudinkova, G.; Liu, Chuan S.; Shao, X.; Sagdeev, R. Z.

    2010-02-01

    We present scaling studies of proton acceleration by short pulse, intense lasers in the region of radiation pressure acceleration of ultra thin foil. By defining the monoenergetic proton as having energy spread less than 10 percent in 2D PIC simulation, we studied the proton mono-energy profile as a function of the laser power and peak intensity, thin foil thickness and target density ratio to critical density. We found that the energy of monoenergetic proton scales linearly with the square root of laser power after fixing the target density ratio to critical density. The Rayleigh-Taylor (R-T) instability plays significant role in increasing the energy spread of accelerated protons. But, there are parameter regimes for instability remediation or suppression. Parameters of interest are for lasers in sub-Peta Watt range and producing quasi energetic protons to 250 Mev and carbon ion to 1 Gev. The simulation results are able to provide experimentalists with suggestion for optimal scaling for laser acceleration of thin foils for instability avoidance and optimal ion acceleration. Possible medical applications of the technology in proton cancer therapy is also discussed. )

  14. Effects of nucleotide binding to LmrA: A combined MAS-NMR and solution NMR study.

    PubMed

    Hellmich, Ute A; Mönkemeyer, Leonie; Velamakanni, Saroj; van Veen, Hendrik W; Glaubitz, Clemens

    2015-12-01

    ABC transporters are fascinating examples of fine-tuned molecular machines that use the energy from ATP hydrolysis to translocate a multitude of substrates across biological membranes. While structural details have emerged on many members of this large protein superfamily, a number of functional details are still under debate. High resolution structures yield valuable insights into protein function, but it is the combination of structural, functional and dynamic insights that facilitates a complete understanding of the workings of their complex molecular mechanisms. NMR is a technique well-suited to investigate proteins in atomic resolution while taking their dynamic properties into account. It thus nicely complements other structural techniques, such as X-ray crystallography, that have contributed high-resolution data to the architectural understanding of ABC transporters. Here, we describe the heterologous expression of LmrA, an ABC exporter from Lactococcus lactis, in Escherichia coli. This allows for more flexible isotope labeling for nuclear magnetic resonance (NMR) studies and the easy study of LmrA's multidrug resistance phenotype. We use a combination of solid-state magic angle spinning (MAS) on the reconstituted transporter and solution NMR on its isolated nucleotide binding domain to investigate consequences of nucleotide binding to LmrA. We find that nucleotide binding affects the protein globally, but that NMR is also able to pinpoint local dynamic effects to specific residues, such as the Walker A motif's conserved lysine residue.

  15. Studies related to primitive chemistry. A proton and nitrogen-14 nuclear magnetic resonance amino acid and nucleic acid constituents and a and their possible relation to prebiotic

    NASA Technical Reports Server (NTRS)

    Manatt, S. L.; Cohen, E. A.; Shiller, A. M.; Chan, S. I.

    1973-01-01

    Preliminary proton nuclear magnetic resonance (NMR) studies were made to determine the applicability of this technique for the study of interactions between monomeric and polymeric amino acids with monomeric nucleic acid bases and nucleotides. Proton NMR results for aqueous solutions (D2O) demonstrated interactions between the bases cytosine and adenine and acidic and aromatic amino acids. Solutions of 5'-AMP admixed with amino acids exhibited more complex behavior but stacking between aromatic rings and destacking at high amino acids concentration was evident. The multisite nature of 5'-AMP was pointed out. Chemical shift changes for adenine and 5'-AMP with three water soluble polypeptides demonstrated that significant interactions exist. It was found that the linewidth-pH profile of each amino acid is unique. It is concluded that NMR techniques can give significant and quantitative data on the association of amino acid and nucleic acid constituents.

  16. NMR study of oligonucleotides containing base pair mismatches and a human growth hormone peptide for the determination of solution structures

    SciTech Connect

    Roongta, V.A.

    1989-01-01

    Formation of unusual basepairs in DNA for random mutations in DNA was proposed in the sixties. These mismatches arise due to errors in replication, and from deamination of the 5-methylcytosine. The author's interest in studying mismatches and other oligonucleotides has been two fold. One is related to {sup 31}P chemical shifts and the backbone structure of oligonucleotides. He wanted to find out the significance of the dispersion of {sup 31}p chemical shifts in oligonucleotides. He wished to address whether this dispersion in {sup 31}P chemical shifts is related to global structural parameters of oligonucleotides like helix twist and whether he can prove the relationship between {sup 31}P chemical shifts and the backbone torsional angles epsilon and zeta. How does a mismatch affect {sup 31}P chemical shifts and the backbone torsional angle The second interest is related to solving the three dimensional structure of these biopolymers by using NMR data (NOESY distances) and computer simulations. His major study of these mismatches has been in the assignments of the protons resonances and the phosphorus resonances by 2D NMR. He has also tried to answer the question about the relationships between {sup 31}P chemical shifts and global parameters for DNA such as the helix twist. He has made substantial progress in determination of J(H3{prime}-P) coupling constants by 2D NMR and also in determining the relationship between the SIP chemical shifts and the backbone torsional angles by using the mismatch dodecamer sequences and the tetradecamer sequences. The 2D NMR data for the GG and GT mismatch have been used to determine three dimensional structures by using distance restrained molecular dynamics. The second project involved studying a 28 residue synthetic peptide by NMR.

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

    PubMed

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

    2017-08-01

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

  18. Study of Proton Transfer in E. Coli Photolyase

    NASA Astrophysics Data System (ADS)

    Zhang, Meng; Liu, Zheyun; Li, Jiang; Wang, Lijuan; Zhong, Dongping

    2013-06-01

    Photolyase is a flavoprotein which utilizes blue-light energy to repair UV-light damaged DNA. The catalytic cofactor of photolyase, flavin adenine dinucleotide (FAD), has five redox states. Conversions between these redox states involve intraprotein electron transfer and proton transfer, which play important role in protein function. Here we systematically studied proton transfer in E. coli photolyase in vitro by site-directed mutagenesis and steady-state UV-vis spectroscopy, and proposed the proton channel in photolyase. We found that in the mutant N378C/E363L, proton channel was completely eliminated when DNA substrate was bound to the protein. Proton is suggested to be transported from protein surface to FAD by two pathways: the proton relay pathway through E363 and surface water to N378 and then to FAD; and the proton diffusion pathway through the substrate binding pocket. In addition, reaction kinetics of conversions between the redox states was then solved and redox potentials of the redox states were determined. These results described a complete picture of FAD redox changes, which are fundamental to the functions of all flavoenzymes.

  19. Synthesis and NMR studies of (13)C-labeled vitamin D metabolites.

    PubMed

    Okamura, William H; Zhu, Gui-Dong; Hill, David K; Thomas, Richard J; Ringe, Kerstin; Borchardt, Daniel B; Norman, Anthony W; Mueller, Leonard J

    2002-03-08

    Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar

  20. NMR structural studies of PECVD amorphous silicon films

    NASA Astrophysics Data System (ADS)

    Cull, Thomas Sidley, Jr.

    The properties of plasma enhanced chemical vapor deposition (PECVD) amorphous semiconductor films vary depending upon preparation conditions and doping. Hydrogenated amorphous silicon films (a-Si:H) have some properties that make these films desirable for use in solar cells and photoreceptor devices. Maximizing electronic and structural properties of such films is key to their success. Nuclear magnetic resonance, and in particular deuterium magnetic resonance (DMR) for a-Si:H,D films, is a useful means to study the morphology of such samples. The location and motions of hydrogen and the chemically equivalent deuterium within an amorphous semiconductor film can be observed with NMR. The information from the NMR studies can be correlated with electronic properties studies to determine whether a given sample would make a successful photovoltaic device. This thesis focuses on three aspects of study: comparison of two samples that differ in the bias applied to the substrate upon which the amorphous films were grown; derivation of relaxation parameters for covalently bonded deuterium; development of a new pulse sequence "incremental spin echo double resonance (SEDOR)" to study the number of unlike spins that contribute to the local field of a given nuclei. Four significant conclusions can be drawn. First, the electronic quality as measured by the photoresponse product etamutau correlates with the broad Gaussian DMR spectral feature which arises from molecular hydrogen in sites that restrict motion. Second, the relaxation of nuclear magnetization under extreme inhomogeneous broadening can be modeled very well as the relaxation without spin diffusion to faster relaxing species within a sample. Third, incremental SEDOR has either a quantum mechanical or classical behavior depending upon the length of the pulse spacing in comparison to the spin-spin relaxation time. Fourth, the local field at the hydrogen of an HD pair within an a-Si:H,D sample is determined on average by

  1. 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.

  2. Unilateral NMR study of a XVI century wall painted

    NASA Astrophysics Data System (ADS)

    Proietti, N.; Capitani, D.; Rossi, E.; Cozzolino, S.; Segre, A. L.

    2007-06-01

    Wall paintings in the XVI century Serra Chapel in the "Chiesa di Nostra Signora del Sacro Cuore" Rome, have been studied using unilateral NMR. In order to map the distribution of moisture content in the wall painted, a large number of Hahn echo measurements, covering large areas of the wall painting were performed. Because the intensity of the Hahn echo is proportional to the amount of moisture in the area under study, the experimental data were transformed into 2D gradient colour maps which allowed an easy visualization of the moisture content of the wall. The state of conservation of the wall painting was monitored using T2 measurements specially with regards to outcropping salt.

  3. 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.

  4. NMR Studies of Protein Hydration and Protein-Ligand Interactions

    NASA Astrophysics Data System (ADS)

    Chong, Yuan

    Water on the surface of a protein is called hydration water. Hydration water is known to play a crucial role in a variety of biological processes including protein folding, enzymatic activation, and drug binding. Although the significance of hydration water has been recognized, the underlying mechanism remains far from being understood. This dissertation employs a unique in-situ nuclear magnetic resonance (NMR) technique to study the mechanism of protein hydration and the role of hydration in alcohol-protein interactions. Water isotherms in proteins are measured at different temperatures via the in-situ NMR technique. Water is found to interact differently with hydrophilic and hydrophobic groups on the protein. Water adsorption on hydrophilic groups is hardly affected by the temperature, while water adsorption on hydrophobic groups strongly depends on the temperature around 10 C, below which the adsorption is substantially reduced. This effect is induced by the dramatic decrease in the protein flexibility below 10 C. Furthermore, nanosecond to microsecond protein dynamics and the free energy, enthalpy, and entropy of protein hydration are studied as a function of hydration level and temperature. A crossover at 10 C in protein dynamics and thermodynamics is revealed. The effect of water at hydrophilic groups on protein dynamics and thermodynamics shows little temperature dependence, whereas water at hydrophobic groups has stronger effect above 10 C. In addition, I investigate the role of water in alcohol binding to the protein using the in-situ NMR detection. The isotherms of alcohols are first measured on dry proteins, then on proteins with a series of controlled hydration levels. The free energy, enthalpy, and entropy of alcohol binding are also determined. Two distinct types of alcohol binding are identified. On the one hand, alcohols can directly bind to a few specific sites on the protein. This type of binding is independent of temperature and can be

  5. ¹H NMR and hyperpolarized ¹³C NMR assays of pyruvate-lactate: a comparative study.

    PubMed

    Hill, Deborah K; Jamin, Yann; Orton, Matthew R; Tardif, Nicolas; Parkes, Harold G; Robinson, Simon P; Leach, Martin O; Chung, Yuen-Li; Eykyn, Thomas R

    2013-10-01

    Pyruvate-lactate exchange is mediated by the enzyme lactate dehydrogenase (LDH) and is central to the altered energy metabolism in cancer cells. The measurement of exchange kinetics using hyperpolarized (13) C NMR has provided a biomarker of response to novel therapeutics. However, the observable signal is restricted to the exchanging hyperpolarized (13) C pools and the endogenous pools of (12) C-labelled metabolites are invisible in these measurements. In this study, we investigated an alternative in vitro (1) H NMR assay, using [3-(13) C]pyruvate, and compared the measured kinetics with a hyperpolarized (13) C NMR assay, using [1-(13) C]pyruvate, under the same conditions in human colorectal carcinoma SW1222 cells. The apparent forward reaction rate constants (kPL ) derived from the two assays showed no significant difference, and both assays had similar reproducibility (kPL  = 0.506 ± 0.054 and kPL  = 0.441 ± 0.090 nmol/s/10(6) cells; mean ± standard deviation; n = 3); (1) H, (13) C assays, respectively). The apparent backward reaction rate constant (kLP ) could only be measured with good reproducibility using the (1) H NMR assay (kLP  = 0.376 ± 0.091 nmol/s/10(6) cells; mean ± standard deviation; n = 3). The (1) H NMR assay has adequate sensitivity to measure real-time pyruvate-lactate exchange kinetics in vitro, offering a complementary and accessible assay of apparent LDH activity.

  6. [NMR study of complex formation of aromatic ligands with heptadeoxynucleotide 5'-d(GCGAAGC) forming stable hairpin structure in aqueous solution].

    PubMed

    Veselkov, A N; Eaton, R J; Semanin, A V; Pakhomov, V I; Dymant, L N; Karavaev, L; Davies, D V

    2002-01-01

    Complex formation of hairpin-producing heptadeoxynucleotide 5'-d(GCGAAGC) with aromatic molecules: acridine dye proflavine and anthracycline antibiotic daunomycin was studied by one-dimensional 1H NMR and two-dimensional correlation 1H-1H (2M-TOCSY, 2M-NOESY), 1H-31P (2M-HMBC) NMR spectroscopy (500 and 600 MHz) in aqueous solution. Concentration and temperature dependences for the chemical shifts of ligand protons were measured, molecular models of equilibrium in solution were developed, and equilibrium thermodynamic parameters for the formation of intercalation complexes were calculated. Spatial structures of dye and antibiotic complexes with the heptamer hairpin were constructed on the basis of 2M-NOE data and the calculated values of limiting chemical shifts of ligand protons.

  7. Ion transport in porous media studied by NMR.

    PubMed

    Pel, L; Huinink, H P; Kopinga, K; Rijniers, L A; Kaasschieter, E F

    2001-01-01

    Moisture and salt transport in masonry can give rise to damages. Therefore a detailed knowledge of the moisture and salt transport is essential for understanding the durability of masonry. A special NMR apparatus has been made allowing quasi-simultaneous measurements of both moisture and Na profiles in porous building materials. Using this apparatus both the absorption of a 4 M NaCl solution in a calcium silicate brick and the drying of a 3 M NaCl capillary saturated fired-clay brick have been studied. It was found that during the absorption process the Na ions clearly stay behind, which this is caused by adsorption of these ions to the pore surface. For the drying it was found that at the beginning of the drying process the ions accumulate near the surface. As the drying rate decreases, diffusion becomes dominant and the ion profile levels off again.

  8. Mass transfer in chromatographic columns studied by PFG NMR.

    PubMed

    Tallarek, U; van Dusschoten, D; Van As, H; Guiochon, G; Bayer, E

    1998-01-01

    Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) is applied to study convective and diffusional transport in chromatographic columns packed with totally porous support particles. Here stagnant zones exist in the particle pores, and diffusional mass-transfer limitations between fluid molecules diffusing in the intraparticle pore network and flowing in the interparticle void space are detected quantitatively. Axial displacement probability distributions were measured for water over a range of Peclet numbers and observation times, with diffusion lengths between 0.15 and 0.91 times the average support particle diameter. The transition towards complete diffusional exchange is demonstrated, thereby also revealing the development of the classical convective dispersion process in a packed bed of (porous) particles.

  9. 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

  10. Low-temperature IR and NMR studies of the interaction of group 8 metal dihydrides with alcohols.

    PubMed

    Gutsul, Evgenii I; Belkova, Natalia V; Sverdlov, Maria S; Epstein, Lina M; Shubina, Elena S; Bakhmutov, Vladimir I; Gribanova, Tatiana N; Minyaev, Ruslan M; Bianchini, Claudio; Peruzzini, Maurizio; Zanobini, Fabrizio

    2003-05-23

    The reactions of the octahedral dihydrido complexes [MH(2)(PP(3))] [M=Fe, Ru, Os; PP(3)=P(CH(2)CH(2)PPh(2))(3)] with a variety of weak ROH acids have been studied by IR and NMR methods in either CH(2)Cl(2) or THF in the temperature range from 190 to 290 K. This study has allowed the determination of the spectral and thermodynamic properties associated with the formation of dihydrogen bonds (DHB) between the terminal hydrides and the OH group. Both the DHB enthalpy values and the hydride basicity factors (E(j)) have been found to increase in the order Fe < Ru < Os. The proton transfer process, leading to the DHB complexes, and eventually to eta(2)-H(2) products, has been found to depend on the acidic strength of the alcohol as well as the nature of the solvent. Low temperature IR and NMR techniques have been used to trace the complete energy profile of the proton transfer process involving the osmium complex [OsH(2)(PP(3))] with trifluoroethanol.

  11. NMR properties of human median nerve at 3 T: proton density, T1, T2, and magnetization transfer.

    PubMed

    Gambarota, Giulio; Mekle, Ralf; Mlynárik, Vladimír; Krueger, Gunnar

    2009-04-01

    To measure the proton density (PD), the T1 and T2 relaxation time, and magnetization transfer (MT) effects in human median nerve at 3 T and to compare them with the corresponding values in muscle. Measurements of the T1 and T2 relaxation time were performed with an inversion recovery and a Carr-Purcell-Meiboom-Gill (CPMG) imaging sequence, respectively. The MT ratio was measured by acquiring two sets of 3D spoiled gradient-echo images, with and without a Gaussian saturation pulse. The median nerve T1 was 1410 +/- 70 msec. The T2 decay consisted of two components, with average T2 values of 26 +/- 2 msec and 96 +/- 3 msec and normalized amplitudes of 78 +/- 4% and 22 +/- 4%, respectively. The dominant component is likely to reflect myelin water and connective tissue, and the less abundant component originates possibly from intra-axonal water protons. The value of proton density of MRI-visible protons in median nerve was 81 +/- 3% that of muscle. The MT ratio in median nerve (40.3 +/- 2.0%) was smaller than in muscle (45.4 +/- 0.5%). MRI-relevant properties, such as PD, T1 and T2 relaxation time, and MT ratio were measured in human median nerve at 3 T and were in many respects similar to those of muscle.

  12. Temperature dependence of (+)-catechin pyran ring proton coupling constants as measured by NMR and modeled using GMMX search methodology

    Treesearch

    Fred L. Tobiason; Stephen S. Kelley; M. Mark Midland; Richard W. Hemingway

    1997-01-01

    The pyran ring proton coupling constants for (+)-catechin have been experimentally determined in deuterated methanol over a temperature range of 213 K to 313 K. The experimental coupling constants were simulated to 0.04 Hz on the average at a 90 percent confidence limit using a LAOCOON method. The temperature dependence of the coupling constants was reproduced from the...

  13. Overcoming the Solubility Limit with Solubility-Enhancement Tags: Successful Applications in Biomolecular NMR Studies

    PubMed Central

    Zhou, Pei; Wagner, Gerhard

    2010-01-01

    Although the rapid progress of NMR technology has significantly expanded the range of NMR-trackable systems, preparation of NMR-suitable samples that are highly soluble and stable remains a bottleneck for studies of many biological systems. The application of solubility-enhancement tags (SETs) has been highly effective in overcoming solubility and sample stability issues and has enabled structural studies of important biological systems previously deemed unapproachable by solution NMR techniques. In this review, we provide a brief survey of the development and successful applications of the SET strategy in biomolecular NMR. We also comment on the criteria for choosing optimal SETs, such as for differently charged target proteins, and recent new developments on NMR-invisible SETs. PMID:19731047

  14. Imino proton NMR guides the reprogramming of A•T specific minor groove binders for mixed base pair recognition

    PubMed Central

    Harika, Narinder K.; Paul, Ananya; Stroeva, Ekaterina; Chai, Yun; Boykin, David W.; Germann, Markus W.; Wilson, W. David

    2016-01-01

    Sequence-specific binding to DNA is crucial for targeting transcription factor-DNA complexes to modulate gene expression. The heterocyclic diamidine, DB2277, specifically recognizes a single G•C base pair in the minor groove of mixed base pair sequences of the type AAAGTTT. NMR spectroscopy reveals the presence of major and minor species of the bound compound. To understand the principles that determine the binding affinity and orientation in mixed sequences of DNA, over thirty DNA hairpin substrates were examined by NMR and thermal melting. The NMR exchange dynamics between major and minor species shows that the exchange is much faster than compound dissociation determined from biosensor–surface plasmon resonance. Extensive modifications of DNA sequences resulted in a unique DNA sequence with binding site AAGATA that binds DB2277 in a single orientation. A molecular docking result agrees with the model representing rapid flipping of DB2277 between major and minor species. Imino spectral analysis of a 15N-labeled central G clearly shows the crucial role of the exocyclic amino group of G in sequence-specific recognition. Our results suggest that this approach can be expanded to additional modules for recognition of more sequence-specific DNA complexes. This approach provides substantial information about the sequence-specific, highly efficient, dynamic nature of minor groove binding agents. PMID:27131382

  15. SLOW-MAS NMR METHODS TO STUDY METABOLIC PROCESSES IN VIVO AND IN VITRO

    SciTech Connect

    Wind, Robert A.; Bertram, Hanne Christine; Hu, Jian Zhi

    2005-09-25

    In vitro and in vivo 1H NMR spectroscopy is widely used to measure metabolic profiles in cells, tissues, animals, and humans and to use them, e.g., for diagnosis and therapy response evaluations. However, the spectra often suffer from poor resolution due to variations in the isotropic bulk magnetic susceptibility present in biological objects, resulting in a broadening of the NMR lines. In principle this broadening can be averaged to zero by the technique of magic angle spinning (MAS), where the sample is rotated about an axis making an angle of 54o44’ relative to the external magnetic field. However, a problem is that in a standard MAS experiment spinning speeds of a kHz or more are required in order to avoid the occurrence of spinning sidebands (SSBs) in the spectra, which renders analysis of the spectra difficult again. At these spinning speeds the large centrifugal forces cause severe structural damage in larger biological objects, so that this method cannot be used to study metabolic processes in intact samples. In solid state NMR several methods have been developed where slow MAS is combined with special radio frequency pulse sequences to eliminate spinning side bands or separate them from the isotropic spectrum so that a SSB-free high-resolution isotropic spectrum is obtained. It has been shown recently that two methods, phase-adjusted spinning sidebands (PASS) and phase-corrected magic angle turning (PHORMAT), can successfully be modified for applications in biological materials (1, 2). With PASS MAS speeds as low as 40 Hz can be employed, allowing non or minimally invasive in vitro studies of excised tissues and organs. This method was used, amongst other things, to study post mortem changes in the proton metabolite spectra in excised rabbit muscle tissue (3). With PHORMAT the NMR sensitivity is reduced and longer measuring times are required, but with this methodology the MAS speed can be reduced to ~1 Hz. This makes PHORMAT amenable for in vivo

  16. NMR studies of multiple conformations in complexes of Lactobacillus casei dihydrofolate reductase with analogues of pyrimethamine.

    PubMed

    Birdsall, B; Tendler, S J; Arnold, J R; Feeney, J; Griffin, R J; Carr, M D; Thomas, J A; Roberts, G C; Stevens, M F

    1990-10-16

    1H and 19F 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 (including pyrimethamine [1, 2,4-diamino-5-(4'-chlorophenyl)-6-ethylpyrimidine], fluoropyrimethamine [2, 2,4-diamino-5-(4'-fluorophenyl)-6-ethylpyrimidine], fluoronitropyrimethamine [3, 2,4-diamino-5-(4'-fluoro-3'-nitrophenyl) -6-ethylpyrimidine], and methylbenzoprim [4, 2,4-diamino-5-[4'- (methylbenzylamino)-3'-nitrophenyl]-6-ethylpyrimidine]). The signals were identified mainly by correlating signals from bound and free ligands by using 2D exchange experiments. Analogues (such as 1 and 2) with symmetrically substituted phenyl rings give rise to 1H signals from four nonequivalent aromatic protons, clearly indicating the presence of hindered rotation about the pyrimidine-phenyl bond. Analogues containing asymmetrically substituted aromatic rings (such as 3 and 4) 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 phenyl ring protons in each of the two forms experience essentially the same protein environment (same shielding) as that experienced by the corresponding protons in bound pyrimethamine: this confirms that forms A and B correspond to two rotational isomers resulting from approximately 180 degrees rotation about the pyrimidine-phenyl bond, with the 2,4-diaminopyrimidine ring being bound similarly in both forms. The relative orientations of the two forms have been determined from NOE through-space connections between protons on the ligand and protein.(ABSTRACT TRUNCATED AT 250 WORDS)

  17. 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.

  18. 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.

  19. NMR studies of abasic sites in DNA duplexes: deoxyadenosine stacks into the helix opposite the cyclic analog of 2-deoxyribose

    SciTech Connect

    Kalnik, M.W.; Chang, C.N.; Grollman, A.P.; Patel, D.J.

    1988-02-09

    Proton and phosphorus NMR studies are reported for the complementary d(C-A-T-G-A-G-T-A-C) x d(G-T-A-C-F-C-A-T-G) nonanucleotide duplex (designated AP/sub F/ 9-mer duplex) which contains a stable abasic site analog, F, in the center of the helix. This oligodeoxynucleotide contains a modified tetrahydrofuran moiety, isosteric with 2-deoxyribofuranose, which serves as a structural analog of a natural apurinic/apyrimidinic site. Exchangeable and nonexchangeable base and sugar protons, including those located at the abasic site, have been assigned in the complementary AP/sub F/ 9-mer duplex by recording and analyzing two-dimensional phase-sensitive NOESY data sets in H/sub 2/O and D/sub 2/O solution at low temperature (0/sup 0/C). These studies indicate that A5 inserts into the helix opposite the abasic site F14 and stacks with flanking G4 x C15 and G6 x C13 Watson-Crick base pairs. Base-sugar proton NOE connectivities were measured through G4-A5-G6 on the unmodified strand and between the base protons of C15 and the sugar protons of the 5'-flanking residue F14 on the modified strand. These studies establish that all glycosidic torsion angles are anti and that the helix is right-handed at and adjacent to the abasic site in the AP/sub F/ 9-mer duplex. Two of the 16 phosphodiester groups exhibit phosphorus resonances outside the normal spectral dispersion indicative of altered torsion angles at two of the phosphate groups in the backbone of the AP/sub F/ 9-mer duplex.

  20. Proton transfer studies in CGC+ assembly

    NASA Astrophysics Data System (ADS)

    Żabicki, Michał; Gudowska-Nowak, Ewa; Fischer, Sighart F.

    2009-12-01

    We have designed and analyzed a molecular model of a generic triple helix DNA base structure - the cytosine-guanine-cytosine (CGC+) assembly. The complex has been investigated for the ability of a concerted proton transfer from cytosine to guanine. Ab initio calculations have been preformed using Unrestricted Hartree-Fock (UHF) method with 6-31G ∗+ basis set. In order to determine possible reaction paths, the potential map has been constructed pointing the most stable configuration for the process to occur. Based on this observation, we have estimated a transmission coefficient for the transfer and found no support for a concerted motion. The effect of fluctuations of the barrier height on the kinetics is also discussed.

  1. Large scale human metabolic phenotyping and molecular epidemiological studies via 1H NMR spectroscopy of urine: Investigation of borate preservation

    PubMed Central

    Smith, Leon M.; Maher, Anthony D.; Want, Elizabeth J.; Elliott, Paul; Stamler, Jeremiah; Hawkes, Geoffrey E.; Holmes, Elaine; Lindon, John C.; Nicholson, Jeremy K.

    2009-01-01

    Borate is an antibacterial preservative widely used in clinical and large scale epidemiological studies involving urine sample analysis. Since it readily forms covalent adducts and reversible complexes with hydroxyl and carboxylate groups, the effects of borate preservation in 1H NMR spectroscopy-based metabolic profiling of human urine samples have been assessed. Effects of various concentrations of borate (range 0–30 mM) on 1H NMR spectra of urine were observed at sequential time points over a 12 month period. Consistent with known borate chemistry, the principal alterations in the 1H resonance metabolite patterns were observed for compounds such as mannitol, citrate and α-hydroxyisobutyrate and confirmed by ESI-MS analysis. These included line-broadening, T1 and T2 relaxation and chemical shift changes consistent with complex formation and chemical exchange processes. To further investigate complexation behavior in the urinary metabolite profiles, a new tool for visualization of multi-component relaxation variations in which the spectra were color-coded according to the T1 and T2 proton relaxation times respectively (T1 or T2 Ordered Projection SpectroscopY, TOPSY) was also developed and applied. Addition of borate caused a general decrease in 1H T1 values consistent with non-specific effects such as solution viscosity changes. Minor changes in proton T2 relaxation rates were observed for the most strongly complexing metabolites. From a molecular phenotyping and epidemiologic viewpoint, typical interpersonal biological variation was shown to be vastly greater than any variation introduced by the borate complexation which had a negligible effect on the metabolic mapping and classification of samples. Whilst caution is indicated in the assignment of biomarker signals where metabolites have diol groupings or where there are adjacent hydroxyl and carboxylate functions, it is concluded that borate preservation is “fit-forpurpose” for 1H NMR

  2. 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.

  3. NMR studies of G:A mismatches in oligodeoxyribonucleotide duplexes modelled after ribozymes.

    PubMed Central

    Katahira, M; Sato, H; Mishima, K; Uesugi, S; Fujii, S

    1993-01-01

    The structures of two oligodeoxyribonucleotide duplexes, the base sequences of which were modelled after both a hammerhead ribozyme and a small metalloribozyme, were studied by NMR. Both duplexes contain adjacent G:A mismatches; one has a PyGAPu:PyGAPu sequence and the other a PyGAPy:PuGAPu sequence. It is concluded on the basis of many characteristic NOEs that in both duplexes G:A base pairs are formed in the unique 'sheared' form, where an amino proton instead of an imino proton of G is involved in the hydrogen bonding, and G and A bases are arranged 'side by side' instead of 'head to head'. A photo-CIDNP experiment, which gives unique and independent information on the solvent accessibility of nucleotide bases, also supports G:A base pairing rather than a bulged-out structure of G and A residues. This is the first demonstration that not only the PyGAPu:PyGAPu sequence but also the PyGAPy:PuGAPu sequence can form the unique sheared G:A base pairs. Taking the previous studies on G:A mismatches into account, the idea is suggested that a PyGA:GAPu sequence is a minimum and essential element for the formation of the sheared G:A base pairs. The sheared G:A base pairs in the PyGAPu:PyGAPu sequence are suggested to be more stable than those in the PyGAPy:PuGAPu sequence. This is explained rationally by the idea proposed above. PMID:8265358

  4. Water or realistic compositions in proton radiotherapy? An analytical study.

    PubMed

    Rasouli, Fatemeh S; Masoudi, S Farhad

    2017-03-01

    Pre-clinical tests and simulation studies for radiotherapy are generally carried out using water or simplified materials. Investigating the effects of defining compositionally realistic media in proton transport studies was the objective of this work. Accurate modeling of the Bragg curve is a fundamental requirement for such a study. An equation previously validated by experiments provides an appropriate analytical method for proton dose calculation in depth of the target. Owing to the dependency on protons ranges and the probability of undergoing non-elastic nuclear interactions (NNI), this formula comprises three parameters with values specified for initial proton energy and for the target material. As a result, knowledge of the depth-dose distribution using this analytical model is limited to the materials for which the data has been provided in nuclear data tables. In this study, we used our general formulas for calculating the protons ranges and the probability of undergoing NNI in desired compounds and mixtures with an arbitrary number of constituent elements. Furthermore, the protons dose distribution in the depth of these targets was leading off with determining the parameters appeared in the employed model using our mathematically easy to handle relations. For a number of tissues which may be of interest in proton radiotherapy studies but are missing in reference data tables, the mentioned parameters were calculated. Moreover, the resultant values for the protons ranges and the probability of undergoing NNIs were compared with those in water. The results showed that the differences between the position of Bragg peaks in water and realistic media considered in this study were energy dependent, and ranged between a few millimeters. For proton beams of arbitrary chosen initial energies, the maximum dose delivered to the realistic media varied between about -0.02-4.42% in comparison with that to water. The effects observed (both in penetration and in the

  5. 200 MeV Proton Radiography Studies with a Hand Phantom Using a Prototype Proton CT Scanner

    PubMed Central

    Plautz, Tia; Bashkirov, V.; Feng, V.; Hurley, F.; Johnson, R.P.; Leary, C.; Macafee, S.; Plumb, A.; Rykalin, V.; Sadrozinski, H.F.-W.; Schubert, K.; Schulte, R.; Schultze, B.; Steinberg, D.; Witt, M.; Zatserklyaniy, A.

    2014-01-01

    Proton radiography has applications in patient alignment and verification procedures for proton beam radiation therapy. In this paper, we report an experiment which used 200 MeV protons to generate proton energy-loss and scattering radiographs of a hand phantom. The experiment used the first-generation proton CT scanner prototype, which was installed on the research beam line of the clinical proton synchrotron at Loma Linda University Medical Center (LLUMC). It was found that while both radiographs displayed anatomical details of the hand phantom, the energy-loss radiograph had a noticeably higher resolution. Nonetheless, scattering radiography may yield more contrast between soft and bone tissue than energy-loss radiography, however, this requires further study. This study contributes to the optimization of the performance of the next-generation of clinical proton CT scanners. Furthermore, it demonstrates the potential of proton imaging (proton radiography and CT), which is now within reach of becoming available as a new, potentially low-dose medical imaging modality. PMID:24710156

  6. Multinuclear NMR study of the effect of acid concentration on ion transport in phosphoric acid doped poly(benzimidazole) membranes.

    PubMed

    Suarez, Sophia; Kodiweera, N K A C; Stallworth, P; Yu, Seonghan; Greenbaum, S G; Benicewicz, B C

    2012-10-18

    (1)H and (31)P NMR spectra, line widths, spin-lattice relaxation times (T(1)), and (1)H self-diffusion coefficients (D) were determined for two distinct poly(benzimidazole) (PBI) proton exchange membranes (PEM), para-PBI and dihydroxy-PBI (2OH-PBI), both incorporating varying concentrations of phosphoric acid. The study was performed over the temperature range of 20-180 °C, for phosphoric acid concentrations of 30, 50, and 70 wt %. Of the two samples, less mobility was indicated for the 2OH-PBI compared with the para-PBI at all acid concentrations. It was also observed that increasing the acid content resulted in an increase in the temperature at which the T(1) minimum or plateau occurred. (31)P spectra reveal the presence of pyrophosphates and in the case of the 50 and 70 wt % para-PBI samples higher oligomers such as tripolyphosphates. (1)H D data showed the 30 wt % para-PBI having almost identical values as the 70 wt % 2OH-PBI over the entire temperature range. In general, stronger short- and long-range interactions were observed in the 2OH-PBI matrix, yielding reduced translational proton transport compared to that of para-PBI. While these stronger interactions hinder translational proton diffusion, they could enhance proton transport by the Grotthuss or structure diffusion mechanism, the more favorable transport mechanism. Activation energies obtained from the (1)H D data supports a proton-hopping mechanism, with possible assistance from fast exchange between phosphate groups.

  7. 1H-NMR comparative study of the active site in shark (Galeorhinus japonicus), horse, and sperm whale deoxy myoglobins.

    PubMed

    Yamamoto, Y; Iwafune, K; Chûjô, R; Inoue, Y; Imai, K; Suzuki, T

    1992-09-01

    1H-NMR spectra of deoxy myoglobins (Mbs) from shark (Galeorhinus japonicus), horse, and sperm whale have been studied to gain insights into their active site structure. It has been demonstrated for the first time that nuclear Overhauser effect (NOE) can be observed between heme peripheral side-chain proton resonances of these paramagnetic complexes. Val-E11 methyl and His-F8 C delta H proton resonances of these Mbs were also assigned from the characteristic shift and line width. The hyperfine shift of the former resonance was used to calculate the magnetic anisotropy of the protein. The shift analysis of the latter resonance, together with the previously assigned His-F8 N delta H proton resonance, revealed that the strain on the Fe-N epsilon bond is in the order horse Mb approximately whale Mb < shark Mb and that the hydrogen bond strength of the His-F8 N delta H proton to the main-chain carbonyl oxygen in the preceding turn of the F helix is in the order shark Mb < horse Mb < whale Mb. Weaker Feporphyrin interaction in shark Mb was manifested in a smaller shift of the heme methyl proton resonance and appears to result from distortion of the coordination geometry in this Mb. Larger strain on the Fe-N epsilon bond in shark Mb should be to some extent attributed to its lowered O2 affinity (P50 = 1.1 mmHg at 20 degrees C), compared to whale and horse Mbs.

  8. In-Cell Solid-State NMR: An Emerging Technique for the Study of Biological Membranes

    PubMed Central

    Warnet, Xavier L.; Arnold, Alexandre A.; Marcotte, Isabelle; Warschawski, Dror E.

    2015-01-01

    Biological molecular processes are often studied in model systems, which simplifies their inherent complexity but may cause investigators to lose sight of the effects of the molecular environment. Information obtained in this way must therefore be validated by experiments in the cell. NMR has been used to study biological cells since the early days of its development. The first NMR structural studies of a protein inside a cell (by solution-state NMR) and of a membrane protein (by solid-state NMR) were published in 2001 and 2011, respectively. More recently, dynamic nuclear polarization, which has been used to enhance the signal in solid-state NMR, has also been applied to the study of frozen cells. Much progress has been made in the past 5 years, and in this review we take stock of this new technique, which is particularly appropriate for the study of biological membranes. PMID:26682804

  9. Progress in Fast Ignition Studies with Electrons and Protons

    SciTech Connect

    MacKinnon, A. J.; Chen, H.; Hey, D.; Key, M. H.; MacPhee, A. G.; Patel, P. K.; Ping, Y.; Akli, K. U.; Stephens, R. B.; Bartal, T.; Beg, F. N.; Chawla, S.; Chen, S.; Higginson, D.; King, J. A.; Ma, T.; Wei, M. S.; Chen, C. D.; Chowdhury, E.; Link, A.

    2009-09-10

    Isochoric heating of inertially confined fusion plasmas by laser driven MeV electrons or protons is an area of great topical interest in the inertial confinement fusion community, particularly with respect to the fast ignition (FI) concept for initiating burn in a fusion capsule. In order to investigate critical aspects needed for a FI point design, experiments were performed to study 1) laser-to-electrons or protons conversion issues and 2) laser-cone interactions including prepulse effects. A large suite of diagnostics was utilized to study these important parameters. Using cone--wire surrogate targets it is found that pre-pulse levels on medium scale lasers such as Titan at Lawrence Livermore National Laboratory produce long scale length plasmas that strongly effect coupling of the laser to FI relevant electrons inside cones. The cone wall thickness also affects coupling to the wire. Conversion efficiency to protons has also been measured and modeled as a function of target thickness, material. Conclusions from the proton and electron source experiments will be presented. Recent advances in modeling electron transport and innovative target designs for reducing igniter energy and increasing gain curves will also be discussed. In conclusion, a program of study will be presented based on understanding the fundamental physics of the electron or proton source relevant to FI.

  10. 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.

  11. PFG NMR study of hydrodynamic dispersion in porous media

    NASA Astrophysics Data System (ADS)

    Ding, Aimin

    We have studied hydrodynamic dispersion in plastic bead packs using the pulsed field gradient (PFG) NMR technique. The bead diameter was varied from 15 to 138 mum and the Peclet number Pe varied from 0 to 10sp3 (the Peclet number is a dimensionless measure of the flow velocity). We studied the time dependence of both the longitudinal dispersion coefficient Dsb{||} and the transverse dispersion coefficient Dsb{⊥}. We observed transitions from decreasing with time at low Pe to increasing with time at high Pe for both Dsb{||} and Dsb{⊥}. We used our data to find the transition time tsb0 the time required for dispersion coefficient to reach its long time value. For both Dsb{||} and Dsb{⊥}, we found a power-law dependence of tsb0 on Pe, as has been predicted by Koch and Brady. The Pe dependence of tsb0 provides information on the operative dispersion mechanisms. Our results show that both convection dispersion and boundary layer dispersion contribute to longitudinal dispersion in our experiments. However, the Pe dependence of tsb0 for transverse dispersion does not agree with the theoretical prediction of Koch and Brady. We measured Dsb{||} and Dsb{⊥} as a function of Pe. Our experimental results are consistent with previous results measured using conventional methods. We found that the results for longitudinal dispersion agree with Saffman's capillary tube model in our observation range. The results for transverse dispersion agree with Koch and Brady's fixed bed model to some extent, but at low Pe, the disagreement is significant. We obtained the wave-number and frequency dependent nonlocal dispersion coefficient {buildrel{≈}/{D}}sb{| |,⊥}(q,omega) from our PFG NMR data. In the local (long time and distance) limit, our results agree with previous results obtained with conventional methods and for no flow they agree with a simple model of restricted diffusion. Our results for nonlocal dispersion with flow are in reasonable agreement with Koch and Brady

  12. 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.

  13. Comparative proton nuclear magnetic resonance studies of amantadine complexes formed in aqueous solutions with three major cyclodextrins.

    PubMed

    Lis-Cieplak, Agnieszka; Sitkowski, Jerzy; Kolodziejski, Waclaw

    2014-01-01

    Host-guest complexes of alpha-, beta-, and gamma-cyclodextrins (α-CD, β-CD, and γ-CD, respectively) with amantadine (1-aminoadamantane, AMA; an antiviral agent) were characterized in aqueous solutions using proton nuclear magnetic resonance (NMR) spectroscopy. Host-guest molecular interactions were manifested by changes in the chemical shifts of AMA protons. NMR Job's plots showed that the stoichiometry of all the studied complexes was 1:1. Two-dimensional T-ROESY experiments demonstrated that the complexes were formed by different degrees of incorporation of the adamantyl group of AMA into the CD cavity. The mode of AMA binding was proposed. The AMA molecule came into the α-CD cavity (the smallest size) or β-CD cavity (the intermediate size) through its wide entrance to become shallowly or deeply accommodated, respectively. In the complex of AMA with γ-CD (the largest cavity size), the adamantyl group was also quite deeply inserted into the CD cavity, but it arrived there through the narrow cavity entrance. It was found that the adamantyl group of AMA was best accommodated by the β-CD cavity. The binding constants Kaa of the studied complexes (in M(-1) ), determined from DOSY NMR, were fairly high; their values in an ascending order were: α-CD (183) < γ-CD (306) ≪ β-CD (5150).

  14. Fundamental studies of supported bimetallic catalysts by NMR spectroscopy

    SciTech Connect

    Savargaonkar, Nilesh

    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.

  15. Quantum-chemical simulation of 1H NMR spectra. 2. Comparison of DFT-based procedures for computing proton-proton coupling constants in organic molecules.

    PubMed

    Bally, Thomas; Rablen, Paul R

    2011-06-17

    The performance of 250 different computational protocols (combinations of density functionals, basis sets and methods) was assessed on a set of 165 well-established experimental (1)H-(1)H nuclear coupling constants (J(H-H)) from 65 molecules spanning a wide range of "chemical space". Thereby we found that, if one uses core-augmented basis sets and allows for linear scaling of the raw results, calculations of only the Fermi contact term yield more accurate predictions than calculations where all four terms that contribute to J(H-H) are evaluated. It turns out that B3LYP/6-31G(d,p)u+1s is the best (and, in addition, one of the most economical) of all tested methods, yielding predictions of J(H-H) with a root-mean-square deviation from experiment of less than 0.5 Hz for our test set. Another method that does similarly well, without the need for additional 1s basis functions, is B3LYP/cc-pVTZ, which is, however, ca. 8 times more "expensive" in terms of CPU time. A selection of the better methods was tested on a probe set comprising 61 J(H-H) values from 37 molecules. In this set we also included five molecules where conformational averaging is required. The rms deviations were better than or equal to those with the training set, which indicates that the method we recommend is generally applicable for organic molecules. We give instructions on how to carry out calculations of (1)H chemical shifts and J(H-H) most economically and provide scripts to extract the relevant information from the outputs of calculations with the Gaussian program in clearly arranged form, e.g., to feed them into programs for simulating entire (1)H NMR spectra.

  16. Studies of Molecular Dynamics by Solid State Deuterium NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhao, Baiyi

    The rotational dynamics of molecules in a number of solid systems were followed by variable temperature deuterium (^2H), nuclear magnetic resonance (NMR) spectroscopy via changes in the spectral lineshapes and spin-lattice relaxation times (T _1). First the pure solid trimethylamine-borane adduct, (CH_3)_3NBH_3, was studied. For a methyl deuterated sample, T _1 measurements yielded two T_1 minima, 6.9 ms and 4.3 ms corresponding to the slowing of methyl and trimethyl rotation, respectively, with decreasing temperature. Activation energies for methyl and trimethyl rotation, obtained from fitting the T _1 curve as a function of temperature, were 32.8 and 15.0 kJ/mol, respectively; simulations of the spectral lineshapes gave 26.6 and 18.9 kT/mol, respectively. Fitting of the ^2H T_1 curve for the borane deuterated sample gave a BH _3 rotation activation energy of 14.1 kT/mol and a ^2H quadrupolar coupling constant, chi, of 101 kHz. The activation energy for BH_3 rotation obtained from the spectral lineshape simulations gave 12.6 kT/mol. A series of deuterated organic chalcogen cations: (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, were ion exchanged into the cavities of sodium Mordenite LZ-M5 and the dynamics of these guests within the hydrated zeolite were followed by ^2H NMR. All three undergo isotropic motion above about -80 to -90^circC. Below this temperature two superimposed ^2H powder spectra appear; the broad lineshape is consistent with only methyl rotation in a hindered, coordinated site, and the other narrow lineshape is due to both methyl and trimethyl rotation in a less hindered, uncoordinated site. As the temperature is lowered the population of the lower energy coordinated site increases. Relative peak areas yield adsorption enthalpies of 6.7, 7.8 and 10.0 kJ/mol for (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, respectively. The series of methyl deuterated ammonium and phosphonium cations: (CH_3)NH_3^+ , (CH_3)_2NH^+ , (CH_3)_3NH^+ and (CH_3)_4P^+ , were

  17. Nuclear magnetic resonance and potentiometric studies of the protonation scheme of a triaza triacetic macrocycle and its complexes with lanthanum and lutetium

    SciTech Connect

    Geraldes, C.F.G.C.; Alpoim, M.C.; Marques, M.P.M.; Sherry, A.D.; Singh, M.

    1985-11-06

    The protonation constants of the macrocyclic ligand 1,4,7-triazacyclononane-N,N',N''-triacetic acid (NOTA) have been measured by potentiometry, and the protonation sequence of the various amino and carboxylate groups of NOTA has been studied in D/sub 2/O as a function of pD from the chemical shifts of the nonlabile protons. Shielding constants for protonation of the amino groups were determined in a NMR study of the triaza macrocyclic amine, its trimethylated analogue, and NOTA and compared with values reported for linear polyamino polycarboxylates and cyclic tetraaza tetracarboxylate ligands. The results indicate that two nitrogens of NOTA are protonated at higher pH than the carboxylate groups. The last nitrogen is protonated only at very low pH. The sequence of protonation of NOTA supports the formation of hydrogen bonds between two protonated nitrogens and the adjacent two nonprotonated carboxylates. The /sup 1/H and /sup 13/C spectra of the La(NOTA) and Lu(NOTA) species were studied as a function of pH and temperature. 33 references, 5 figures, 4 tables.

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

    PubMed

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

    2016-01-01

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

  19. Proton nuclear magnetic resonance studies of mast cell histamine

    SciTech Connect

    Rabenstein, D.L.; Ludowyke, R.; Lagunoff, D.

    1987-11-03

    The state of histamine in mast cells was studied by /sup 1/H NMR spectroscopy. Spectra were measured for histamine in situ in intact mast cells, for histamine in suspensions of mast cell granule matrices that had been stripped of their membranes, and for histamine in solutions of heparin. The /sup 1/H NMR spectrum of intact mast cells is relatively simple, consisting predominantly of resonances for intracellular histamine superimposed on a weaker background of resonances from heparin and proteins of the cells. All of the intracellular histamine contributes of the NMR signals, indicating it must be relatively mobile and not rigidly associated with the negatively charged granule matrix. Spectra for intracellular histamine and for histamine in granule matrices are similar, indicating the latter to be a reasonable model for the in situ situation. The dynamics of binding of histamine by granule matrices and by heparin are considerably different; exchange of histamine between the bulk water and the granule matrices is slow on the /sup 1/H NMR time scale, whereas exchange between the free and bound forms in heparin solution is fast. The chemical shifts of resonances for histamine in mast cells are pH dependent, decreasing as the intragranule pH increases without splitting or broadening. The results are interpreted to indicate that histamine in mast cells is relatively labile, with rapid exchange between histamine and pools of free histamine in water compartments confined in the granule matrix.

  20. Proton Transfer Reactions Studied Using the VANDLE Neutron Detector Array

    NASA Astrophysics Data System (ADS)

    Thornsberry, C. R.; Burcher, S.; Gryzwacz, R.; Jones, K. L.; Paulauskas, S. V.; Smith, K.; Vostinar, M.; Allen, J.; Bardayan, D. W.; Blankstein, D.; Deboer, J.; Hall, M.; O'Malley, P. D.; Reingold, C.; Tan, W.; Cizewski, J. A.; Lepailleur, A.; Walter, D.; Febbraro, M.; Pain, S. D.; Marley, S. T.

    2016-09-01

    Proton transfer reactions, such as (d,n), are powerful tools for the study of single particle proton states of exotic nuclei. Measuring the outgoing neutron allows for the extraction of spectroscopic information from the recoil nucleus. With the development of new radioactive ion beam facilities, such as FRIB in the U.S., comes the need for new tools for the study of reactions involving radioactive nuclei. Neutron detectors, such as VANDLE, are sensitive to gamma rays in addition to neutrons. This results in high background rates for measurements with high external trigger rates. The use of discriminating recoil particle detectors, such as phoswich detectors, allow for the selection of a clean recoil tag by separating the recoil nucleus of interest from unreacted RIB components. Developments of low energy proton transfer measurements in inverse kinematics and recent (d,n) results will be presented. This work supported in part by the U.S. Department of Energy and the National Science Foundation.

  1. NMR study of small molecule adsorption in MOF-74-Mg

    NASA Astrophysics Data System (ADS)

    Lopez, M. G.; Canepa, Pieremanuele; Thonhauser, T.

    2013-04-01

    We calculate the carbon nuclear magnetic resonance (NMR) shielding for CO2 and the hydrogen shieldings for both H2 and H2O inside the metal organic framework MOF-74-Mg. Our ab initio calculations are at the density functional theory level using the van der Waals including density functional vdW-DF. The shieldings are obtained while placing the small molecules throughout the structure, including the calculated adsorption site for various loading scenarios. We then explore relationships between loading, rotational and positional characteristics, and the NMR shieldings for each adsorbate. Our NMR calculations show a change in the shielding depending on adsorbate, position, and loading in a range that is experimentally observable. We further provide a simple model for the energy and the NMR shieldings throughout the cavity of the MOF. By providing this mapping of shielding to position and loading for these adsorbates, we argue that NMR probes could be used to provide additional information about the position at which these small molecules bind within the MOF, as well as the loading of the adsorbed molecule.

  2. NMR study of small molecule adsorption in MOF-74-Mg.

    PubMed

    Lopez, M G; Canepa, Pieremanuele; Thonhauser, T

    2013-04-21

    We calculate the carbon nuclear magnetic resonance (NMR) shielding for CO2 and the hydrogen shieldings for both H2 and H2O inside the metal organic framework MOF-74-Mg. Our ab initio calculations are at the density functional theory level using the van der Waals including density functional vdW-DF. The shieldings are obtained while placing the small molecules throughout the structure, including the calculated adsorption site for various loading scenarios. We then explore relationships between loading, rotational and positional characteristics, and the NMR shieldings for each adsorbate. Our NMR calculations show a change in the shielding depending on adsorbate, position, and loading in a range that is experimentally observable. We further provide a simple model for the energy and the NMR shieldings throughout the cavity of the MOF. By providing this mapping of shielding to position and loading for these adsorbates, we argue that NMR probes could be used to provide additional information about the position at which these small molecules bind within the MOF, as well as the loading of the adsorbed molecule.

  3. 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. Copyright © 2015 John Wiley & Sons, Ltd.

  4. Studies of electron and proton isochoric heating for fast ignition

    SciTech Connect

    Mackinnon, A; Key, M; Akli, K; Beg, F; Clarke, R; Clarke, D; Chen, M; Chung, H; Chen, S; Freeman, R; Green, J; Gu, P; Gregori, G; Highbarger, K; Habara, H; Hatchett, S; Hey, D; Heathcote, R; Hill, J; King, J; Kodama, R; Koch, J; Lancaster, K; Langdon, B; Murphy, C; Norreys, P; Neely, D; Nakatsutsumi, M; Nakamura, H; Patel, N; Patel, P; Pasley, J; Snavley, R; Stephens, R; Stoeckl, C; Foord, M; Tabak, M; Theobald, W; Storm, M; Tanaka, K; Tempo, M; Toley, M; Town, R; Wilks, S; VanWoerkom, L; Weber, R; Yabuuchi, T; Zhang, B

    2006-10-02

    Isochoric heating of inertially confined fusion plasmas by laser driven MeV electrons or protons is an area of great topical interest in the inertial confinement fusion community, particularly with respect to the fast ignition (FI) proposal to use this technique to initiate burn in a fusion capsule. Experiments designed to investigate electron isochoric heating have measured heating in two limiting cases of interest to fast ignition, small planar foils and hollow cones. Data from Cu K{alpha} fluorescence, crystal x-ray spectroscopy of Cu K shell emission, and XUV imaging at 68eV and 256 eV are used to test PIC and Hybrid PIC modeling of the interaction. Isochoric heating by focused proton beams generated at the concave inside surface of a hemi-shell and from a sub hemi-shell inside a cone have been studied with the same diagnostic methods plus imaging of proton induced K{alpha}. Conversion efficiency to protons has also been measured and modeled. Conclusions from the proton and electron heating experiments will be presented. Recent advances in modeling electron transport and innovative target designs for reducing igniter energy and increasing gain curves will also be discussed.

  5. Protonated Forms of Monoclinic Zirconia: A Theoretical Study

    SciTech Connect

    Mantz, Yves A.; Gemmen, Randall S.

    2010-05-06

    In various materials applications of zirconia, protonated forms of monoclinic zirconia may be formed, motivating their study within the framework of density-functional theory. Using the HCTH/120 exchange-correlation functional, the equations of state of yttria and of the three low-pressure zirconia polymorphs are computed, to verify our approach. Next, the favored charge state of a hydrogen atom in monoclinic zirconia is shown to be positive for all Fermilevel energies in the band gap, by the computation of defect formation energies.This result is consistent with a single previous theoretical prediction at midgap as well as muonium spectroscopy experiments. For the formally positively (+1e) charged system of a proton in monoclinic zirconia (with a homogeneous neutralizing background charge densityimplicitly included), modeled using up to a 3 x 3 x 3 arrangement of unit cells, different stable and metastable structures are identified. They are similar to those structures previously proposed for the neutral system of hydrogen-doedmonoclinic zirconia, at a similar level of theory. As predicted using the HCTH/120 functional, the lowest energy structure of the proton bonded to one of the two available oxygen atom types, O1, is favored by 0.39 eV compared to that of the proton bonded to O2. The rate of proton transfer between O1 ions is slower than that for hydrogen-dopedmonoclinic zirconia, whose transition-state structures may be lowered in energy by the extra electron.

  6. Deciphering the Conformational Choreography of Zinc Coordination Complexes with Standard and Novel Proton NMR Techniques Combined with DFT Methods.

    PubMed

    Pucheta, Jose Enrique Herbert; Prim, Damien; Gillet, Jean Michel; Farjon, Jonathan

    2016-04-04

    The presence of water has been shown to deeply impact the stability and geometry of Zn complexes in solution. Evidence for tetra- and penta-coordinated species in a pyridylmethylamine-Zn(II) model complex is presented. Novel (1) H NMR tools such as T1 -filtered selective exchange spectroscopy and pure shifted gradient-encoded selective refocusing as well as classical 2D ((1) H-(1) H) exchange spectroscopy, diffusion-ordered spectroscopy and T1 ((1) H) measurements, in combination with density functional theory methods allow the full conformational dynamics of a pyridylmethylamine-Zn(II) complex to be revealed. Four conformers and two families of complexes depending on the hydration states are elucidated.

  7. Proton-detected solid-state NMR spectroscopy of a zinc diffusion facilitator protein in native nanodiscs

    PubMed Central

    Bersch, Beate; Dörr, Jonas M.; Hessel, Audrey; Killian, J. Antoinette; Schanda, Paul

    2017-01-01

    The structure, dynamics and function of membrane proteins are intimately linked to the properties of the membrane environment in which the proteins are embedded. For structural and biophysical characterization, membrane proteins generally need to be extracted from the membrane, and reconstituted in a suitable membrane-mimicking environment. Ensuring functional and structural integrity in these environments is often a major concern. The styrene/maleic acid co-polymer has recently been shown to be able to extract lipid/membrane protein patches directly from native membranes, forming nanosize discoidal proteolipid particles, also referred to as native nanodiscs. Here we show, for the first time, that high-resolution solid-state NMR spectra can be obtained from an integral membrane protein in native nanodiscs, as exemplified with the 2 x 34 kDa-large bacterial cation diffusion facilitator CzcD from Cupriavidus metallidurans CH34. PMID:28128538

  8. What's new in the proton transfer reaction from pyranine to water? A femtosecond study of the proton transfer dynamics

    SciTech Connect

    Prayer, C.; Gustavsson, T.; Tran-Thi, T.-H.

    1996-04-01

    The proton transfer from excited pyranine to water is studied by the femtosecond fluorescence upconversion technique. It is shown for the first time that the proton transfer reaction in water proceeds by three successive steps: the solvent cage relaxation, the specific solute-solvent hydrogen-bond formation and finally the ion pair dissociation/diffusion.

  9. A Deuterium NMR Study of Bent-Core Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Dingemans, Theo J.; Madsen, Louis A.; Samulski, Edward T.

    2002-10-01

    We have synthesized two deuterated boomerang-shaped liquid crystals based on 2,5-bis(4-hydroxyphenyl)-1,3,4-oxadiazole (ODBP). Deuterium was introduced in the rigid 2,5-diphenyl-1,3,4-oxadiazole core and in the aromatic ring of the terminal 4-dodecyloxyphenyl moiety using standard acid catalyzed deuterium exchange conditions. Both compounds, (4,4'(1,3,4-oxadiazole-2,5-diyl-d4) di-4-dodecyloxybenzoate: ODBP-d4-Ph-O-C12) and (4,4'(1,3,4-oxadiazole-2,5-diyl) di-4-dodecyloxy-benzoate-d4; ODBP-Ph-d4-O-C12) were investigated by nuclear magnetic resonance, optical microscopy and differential scanning calorimetry. The optical textures and thermal behavior of both compounds were found to be identical to the non-deuterated analog 4,4(1,3,4-oxadiazole-2,5-diyl) di-4-dodecyloxybenzoate (ODBP-Ph-O-C12) which we reported earlier. These compounds exhibit behavior indicative of a biaxial nematic liquid crystal phase, which we hope to confirm using deuterium NMR spectroscopy in the next phase of this study.

  10. Vibrational and NMR probe studies of S Az-1 montmorillonite

    SciTech Connect

    Johnston, C.T.; Erickson, C.; Earl, W.L.

    1992-09-01

    This paper reports a study of the interactions of exchangeable metal cations with mineral surfaces using a combined spectroscopic/macroscopic approach. Objectives were to examine the use of water molecules and metal cations as molecular probes of smectite water interactions. The {nu}{sub 2} mode of water is used as a diagnostic vibrational band. An FTIR-gravimetric cell is used to examine the FTIR spectra of water on homoionic smectites. The {sup 23}Na NMR resonance is used to probe metal-water interactions on the surface. Results show that there are strong changes in both position and absorption coefficient of the H-O-H bending mode of water sorbed on SAz-1 montmorillonite as a function of water content. These changes are attributed to strong electrostatic forces and mobility changes that occur when the water in the interlammelar space is associated with the metal ion. The clay surface is viewed as having at least two distinct sites to which a hydrated Na{sup +} can bind. 32 refs, 5 figs. (DLC)

  11. Vibrational and NMR probe studies of S Az-1 montmorillonite

    SciTech Connect

    Johnston, C.T.; Erickson, C. . Dept. of Soil Science); Earl, W.L. )

    1992-01-01

    This paper reports a study of the interactions of exchangeable metal cations with mineral surfaces using a combined spectroscopic/macroscopic approach. Objectives were to examine the use of water molecules and metal cations as molecular probes of smectite water interactions. The {nu}{sub 2} mode of water is used as a diagnostic vibrational band. An FTIR-gravimetric cell is used to examine the FTIR spectra of water on homoionic smectites. The {sup 23}Na NMR resonance is used to probe metal-water interactions on the surface. Results show that there are strong changes in both position and absorption coefficient of the H-O-H bending mode of water sorbed on SAz-1 montmorillonite as a function of water content. These changes are attributed to strong electrostatic forces and mobility changes that occur when the water in the interlammelar space is associated with the metal ion. The clay surface is viewed as having at least two distinct sites to which a hydrated Na{sup +} can bind. 32 refs, 5 figs. (DLC)

  12. Protonation of carbon single-walled nanotubes studied using 13C and 1H-13C cross polarization nuclear magnetic resonance and Raman spectroscopies.

    PubMed

    Engtrakul, Chaiwat; Davis, Mark F; Gennett, Thomas; Dillon, Anne C; Jones, Kim M; Heben, Michael J

    2005-12-14

    The reversible protonation of carbon single-walled nanotubes (SWNTs) in sulfuric acid and Nafion was investigated using solid-state nuclear magnetic resonance (NMR) and Raman spectroscopies. Magic-angle spinning (MAS) was used to obtain high-resolution 13C and 1H-13C cross polarization (CP) NMR spectra. The 13C NMR chemical shifts are reported for bulk SWNTs, H2SO4-treated SWNTs, SWNT-Nafion polymer composites, SWNT-AQ55 polymer composites, and SWNTs in contact with water. Protonation occurs without irreversible oxidation of the nanotube substrate via a charge-transfer process. This is the first report of a chemically induced change in a SWNT 13C resonance brought about by a reversible interaction with an acidic proton, providing additional evidence that carbon nanotubes behave as weak bases. Cross polarization was found to be a powerful technique for providing an additional contrast mechanism for studying nanotubes in contact with other chemical species. The CP studies confirmed polarization transfer from nearby protons to nanotube carbon atoms. The CP technique was also applied to investigate water adsorbed on carbon nanotube surfaces. Finally, the degree of bundling of the SWNTs in Nafion films was probed with the 1H-13C CP-MAS technique.

  13. Ultrasound Treatment of Polyisoprene Rubber, Studied by NMR Relaxation and Diffusion.

    NASA Astrophysics Data System (ADS)

    von Meerwall, E.; Sun, X. M.; Joshi, T.; Isayev, A. I.

    2006-10-01

    In support of rubber recycling, we have studied the effect of intense ultrasound on unfilled cis-polyisoprene (PI) melts and networks using proton NMR T2 relaxation and pulsed-gradient diffusion. At 70.5 deg.C the echo decays show two components, due to entangled sol and crosslinked network; and unentangled sol, dangling ends, and oligomers. Component T2 values, hence intermolecular mobilities, increase with sonication, with modest changes in relative amplitudes. The high melt molecular weight(M) without a low-M tail precluded diffusion measurements. We then examined PI melts degraded by ultrasound with and without subsequent vulcanization. Here the T2 decays are consistent with three components. Sonication shifts and broadens the M-distribution but produces no network. Curing generates at least 94% network, lowers all mobilities, and decreases the proportions of unentangled sol and of oligomers. The diffusion spectrum is bimodal, arising from intermediate fractions and oligomeric species. Both diffusion rates and all T2 values increase slightly with ultrasound amplitude. We compare these results with our earlier work in natural rubber.

  14. Ultrasound Treatment of Butyl Gum and Rubber, Studied by NMR Relaxation

    NASA Astrophysics Data System (ADS)

    von Meerwall, E. D.; Feng, Wenlai; Isayev, A. I.

    2004-10-01

    We have examined the effects of intense ultrasound on butyl gum and unfilled vulcanizates using proton transverse NMR relaxation, sol extraction, GPC analysis, and glass transition measurements. At 100 deg.C the spin echo decays exhibit three components, due to entangled molecules and network, unentangled sol plus dangling chain ends, and oligomer remnants; two components suffice to describe most vulcanizates. Compared to other rubbers we have studied, all component spin relaxation times are shorter and less sensitive to ultrasound, and the fraction of the short-T2 component is significantly higher. In the gums sonication produces chain scission but no significant crosslinking. In sol extracted from sonicated rubber, the T2 component amplitudes correlate well with the trimodal molecular-weight distribution. In spite of the low glass transition temperatures (near -60 deg.C) even the longest T2 up to 120 deg.C was too short to permit pulsed-gradient diffusion measurements. The low extractable sol fraction at standard ultrasound settings confirms the conclusion that in butyl rubber sonication is less effective for network destruction than in other rubbers.

  15. 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.

  16. 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.

  17. NMR study of black-phase in SmS

    NASA Astrophysics Data System (ADS)

    Koyama, T.; Yamada, H.; Ueda, K.; Mito, T.; Haga, Y.

    2015-03-01

    We report the result of the 33S nuclear magnetic resonance (NMR) measurement on the nonmagnetic semiconductor SmS at ambient pressure. For this measurement, the 33S isotope enriched powder sample of SmS was prepared to increase the 33S NMR intensity. We have attempted 33S NMR measurement on SmS and successfully observed the signal of it. With decreasing temperature, the spectrum measured at the constant magnetic field shifted to lower frequency and became weakly temperature dependent below 50 K. The presence of the energy gap was microscopically established by the rapid decrease in the nuclear spin-lattice relaxation rate 1/T1. The activation energy was deduced to be 625 K from an Arrhenius plot of T1.

  18. Al NMR study of molten aluminum oxide compounds and mixtures, measured at ultra high temperatures.

    NASA Astrophysics Data System (ADS)

    Piwowarczyk, J.; Marzke, R. F.; Wolf, G. H.; Petuskey, W. T.; Takulapalli, B.

    2002-10-01

    The technique of ultra high-temperature nuclear magnetic resonance (NMR) has provided insight into the chemical structure and properties of molten aluminum-bearing refractory ceramics, at temperatures in excess of 2000 ^oC. Through application of standard NMR measurements we have studied molten aluminum-bearing ceramics via ^27Al NMR. We have measured spin-lattice (T_1) and spin-spin (T_2) relaxation times, have studied Al-O-P chemical bonding within molten aluminua-monazite (Al_2O3 + LaPO_4) samples and have begun to measure Al diffusivity as a function of temperature and composition. To overcome the limitations of standard NMR heating systems a specially designed NMR probe was developed. Application of levitation technology and a laser heating system permit controlled, containerless heating of samples over a wide range of temperatures. Supported by NSF DMR 0116361, DMR 9818133 and by Research Corp. RA 0276

  19. Structural studies of. cap alpha. -bungarotoxin. 1. Sequence-specific /sub 1/H NMR resonance assignments

    SciTech Connect

    Basus, V.J.; Billeter, M.; Love, R.A.; Stroud, R.M.; Kuntz, I.D.

    1988-04-19

    The authors report the complete sequence-specific assignment of the backbone resonances and most of the side-chain resonances in the /sup 1/H NMR spectrum of ..cap alpha..-bungarotoxin by two-dimensional NMR. Problems with resonance overlap were resolved with the assistance of the HRNOESY experiment described in an accompanying paper. Significant differences exist between the solution structure described here and the crystal structure of ..cap alpha..-bungarotoxin, on the basis of the proton to proton distances obtained by nuclear Overhauser enhancement spectroscopy (NOESY) and the corresponding distances from the X-ray crystal structure. These differences include a larger ..beta..-sheet in solution and a different orientation of the invariant tryptophan, Trp-28, making the solution structure more consistent with the crystal structure of the homologous neurotoxin ..cap alpha..-cobratoxin. Four errors in the order of the amino acids in the primary sequence were indicated by the NMR data. These errors were confirmed by chemical means, as described in an accompanying paper.

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

    PubMed Central

    Kolehmainen, E.

    2016-01-01

    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

  1. 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.

  2. Solid-state NMR studies for DC 745: April--May 2000

    SciTech Connect

    Stephens, T.; Labouriau, A.

    2000-12-01

    Powles et al. reported in 1961 that pdydimethyl siloxane melts exhibit a transverse decay of nuclear spin magnetization (T{sub 2}) that is nonexponential. This observation was interpreted in terms of the proton NMR signal from the melt having characteristics of a broad line. Since then, similar findings were obtained for other polymer melts too. Accordingly to Powles et al. this peculiar proton line shape was the result of an intramolecular direct dipole-dipole interaction between a pair of protons. They also suggested that this dipolar interaction was weak because the dipolar interaction was motionally averaged since the orientation-dependent local dipolar field is modulated by molecular dynamics. In sum, the consequences and the origins of nuclear spin correlations in viscous polymer melts were recognized almost 4 decades ago. In the 1970s, Cohen-Addad suggested that these weak proton dipolar interactions could be used to characterize polymer melts and network