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At least 451 records · Page 25Linked to original sources
PubMed1998

The effect of Magic Angle Spinning on proton spin-lattice relaxation times in some organic solids.

Proton spectra of solids are usually broadened by strong proton homonuclear dipolar interactions. However, substantial line narrowing may be achieved by Magic Angle Spinning (MAS) in systems of low proton density or in systems in which rapid molecular motions occur. In such conditions, T1(H) measurements are often used to characterise the dynamics of each resolved proton site. We show that T1(H) values measured for solid organic compounds with high proton abundance, such as adamantane and glycine, may be strongly dependent on the spinning rate employed, so that care is required when values are compared. The effects of molecular motion and proton density on T1(H) and its dependence on spinning rate were investigated. We found that an increase in molecular motion leads to an increase of T1(H) at higher spinning rates. The opposite is found for systems with low proton densities which show relatively lower T1(H), at higher spinning rates. A possible interpretation is suggested in terms of the reduced spin diffusion efficiency at higher spinning rates.

Adamantane↗
PubMed1998

13C CP (cross-polarization) MAS (magic angle spinning) NMR and GIAO-CHF calculations of buspirone analogues. Part 1. 3a,4,7,7a-Tetrahydro-2-[4-[4-(2-quinolinyl)-1-piperazinyl]butyl ]-4,7-ethane-1H-isoindole-1,3(2H)-dione hydrochloride and hydrobromide.

13C CP (cross-polarization) MAS (magic angle spinning) solid state NMR spectra of buspirone analogue 3a,4,7,7a-tetrahydro-2-[4-[4-(2-quinolinyl)-1-piperazinyl]butyl]-4,7-eth ane-1H-isoindole-1,3(2H)-dione were recorded. In the spectra of hydrochloride and hydrobromide, two sets of signals appeared, in agreement with single crystal X-ray diffraction data indicating that in each of the salts two independent cations were present in the crystal unit. The largest shielding differences of 3.2-4.6 ppm between two sets of signals were found for quinoline aromatic carbons C3 and C2. Ab initio calculations of the carbon and nitrogen shielding constants were performed with the use of the GIAO-CHF method for structural fragments: N-butylsuccinimide, quinoline-(N-methyl) piperazine hydrochloride and hydrobromide. Linear correlations between theoretical and solid state results were obtained, thus enabling a reasonable assignment of carbon resonances of the conformations present in the solid state. Due to the fast dynamics in solution, the carbon chemical shifts corresponded to the averaged values of the forms present in the solid state.

Anti-Anxiety Agents↗
PubMed1999

Application of 29Si and 27Al magic angle spinning nuclear magnetic resonance to studies of the building materials of historical monuments.

We report the application of 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) studies on building stones from historical monuments to obtain direct information about the degree of degradation and to observe the changes in the consolidated material after treatment with tetraethoxysilane (TEOS). Using the data obtained from deteriorated materials, a diagnostic laboratory, a suitable treatment and recommendations for building conservation may infer. A case study is presented using stones from Guanajuato City Main Church (Central Mexico). X-ray diffraction patterns to characterize the species present in the stones agree with the solid state NMR results.

Aluminum↗
PubMed1999

19F/29Si distance determination in fluoride-containing octadecasil by Hartmann-Hahn cross-polarization under fast magic-angle spinning.

19F/29Si Hartmann-Hahn continuous wave cross-polarization (CP) has been applied under fast magic-angle spinning (MAS) to a powder sample of octadecasil. Strong oscillations occur during CP on a sideband matching condition between the isolated 29Si-19F spin pairs formed by the silicons in the D4R units and the fluoride anions. The magnitude of the dipolar coupling constant was deduced directly from the line-splitting between the intense singularities of the Pake-like patterns obtained by Fourier transformation of the oscillatory polarization transfer. The corresponding Si-F internuclear distance, r = 2.62 +/- 0.05 A, is found to be in very good agreement with the X-ray crystal structure and the value of 2.69 +/- 0.04 A recently reported from rotational echo double resonance (REDOR) and transferred echo double resonance (TEDOR) nuclear magnetic resonance (NMR) experiments. Furthermore, the CP technique is still reliable under fast MAS where both REDOR and TEDOR sequences suffer from severe artefacts due to finite pulse lengths. In octadecasil, a spinning frequency of approximately 14 kHz is shown to be necessary for an effective suppression of 19F-19F spin diffusion. The influences of experimental missettings and radiofrequency (RF) field inhomogeneity are taken into account.

Fluorides↗
PubMed1999

13C-1H dipolar recoupling under very fast magic-angle spinning using virtual pulses.

A new solid-state NMR pulse sequence for recoupling 13C-1H dipolar interactions under magic-angle spinning is proposed, which works under a spinning speed of a few to several tens kilohertz. The sequence is composed of two different frequency switched Lee-Goldburg sequences, and the modulation of the spin part of the 13C-1H dipolar interaction is introduced by a virtual pulse sequence consisting of unitary operators connecting the rotating frame and the tilted rotating frame. When the cycle time of the spinning is equal to or twice the cycle time of the sequence, the 13C-1H dipolar interactions can be recoupled. The sequence is insensitive to experimental imperfections such as rf inhomogeneity or frequency offset, and the resulting lineshape can be represented by a simple analytical equation based on the zeroth-order average Hamiltonian. Experimental results for [2-(13)C] L-valine x HCl are reported.

Carbon Isotopes↗
PubMed1999

Multiple-quantum relaxation in the magic-angle-spinning NMR of 13C spin pairs.

We determine the decay rate constants of zero-, double- and single-quantum coherence for 13C spin pairs in magic-angle-spinning solid-state NMR. The double-quantum coherence is excited by a C7 pulse sequence and converted into zero-quantum coherence by a frequency-selective pair of pi/2 pulses. The zero-quantum coherence is reconverted into observable magnetization by a second pair of pi/2 pulses followed by a second C7 sequence. In a magnetically dilute system where the 13C-13C distance is 0.296 nm, the relaxation rate constants are consistent with a model of uncorrelated random fields at the two labeled 13C sites. In a fully-labelled system with a short 13C-13C distance of 0.153 nm, the measured rate constants are inconsistent with the uncorrelated random field model.

Carbon Isotopes↗
PubMed1999

13C cross-polarization magic angle spinning NMR and gauge-independent atomic orbital, coupled Hartree-Fock calculations of buspirone analogues. Part 2. Hydrochlorides and perchlorates of 1-arylpiperazine-4-alkylimides.

13C cross-polarization (CP) magic angle spinning (MAS) solid state NMR spectra of hydrochlorides and perchlorates of buspirone analogues (2-5) were recorded. In the spectra for each compound, one set of signals appeared, in agreement with single crystal X-ray diffraction data indicating the presence of one molecule per crystal unit. The resonances of 2-5 hydrochlorides were assigned by comparison with the solution chemical shifts. For perchlorate 2b and diperchlorate 2c, the reasonable assignment of signals was made with the aid of the theoretical studies. Ab initio calculations of the carbon shieldings were performed by means of the GIAO-CHF method for two model systems: perchlorate and diperchlorate of quinoline-(N-methyl)piperazine. As no remarkable differences between carbon chemical shifts of hydrochlorides 3-5 in solid state and in solution were observed, it was concluded that in solution these compounds adopted the same conformation as in the solid state.

Buspirone↗
PubMed2000

Spin-locking mechanism of spin I = 3/2 quadrupolar nuclei undergo magic angle spinning.

The spin-locking mechanism of the spin I = 3/2 quadrupolar nuclei under magic angle spinning (MAS) has been theoretically and experimentally investigated, and the criterion of adiabatic passage around zero-crossings of the quadrupole splitting was inferred from the time-dependent Shrödinger equation in this article. The theory, numerical simulations, and experiments conducted in this work all indicated that second-order quadrupole interaction and off-resonance play important roles in the spin-locking of the quadrupolar nuclei, and they were responsible for the great loss of the spin-locking signals. The spin-locking for a spin I = 3/2 nucleus might be achieved by minimizing the effect of the second-order quadrupole interaction by using a radio frequency (RF) offset. This offset was realized by setting the RF to the opposite position of the isotropic second-order quadrupolar shift of single quantum coherences.

Magnetic Resonance Spectroscopy↗
PubMed1998

Perceived virulence of germs from a liked versus disliked source: evidence of magical contagion.

PURPOSE: This research tested the hypothesis that adolescents perceive germs and resulting illness to be more virulent when contracted from a disliked source than from a liked source. METHODS: High school students rated their imagined illness from a disliked person and a friend. Independent judges rated students' drawings of germs from the disliked source and from the friend. RESULTS: Students imagined their illness as more serious when contracted from a disliked source, and judges rated the germs from a disliked source as angrier and more threatening. CONCLUSIONS: These results are discussed in terms of the role of "magical contagion" in reducing adolescents' perceived vulnerability to consequences of their risk-taking behavior.

Adolescent↗
PubMed2003

Multiple-quantum magic-angle spinning spectroscopy using nonlinear sampling.

NMR spectroscopy is a relatively insensitive technique and many biomolecular applications operate near the limits of sensitivity and resolution. A particularly challenging example is detection of the quadrupolar nucleus 17O, due to its low natural abundance, large quadrupole couplings, and low gyromagnetic ratio. Yet the chemical shift of 17O spans almost 1000 ppm in organic molecules and it serves as a potentially unique reporter of hydrogen bonding in peptides, nucleic acids, and water, and as a valuable complement to 13C and 15N NMR. Recent developments including the multiple-quantum magic-angle spinning (MQMAS) experiment have enabled the detection of 17O in biological solids, but very long data acquisitions are required to achieve sufficient sensitivity and resolution. Here, we perform nonlinear sampling in the indirect dimension of MQMAS experiments to substantially reduce the total acquisition time and improve sensitivity and resolution. Nonlinear sampling prevents the use of the discrete Fourier transform; instead, we employ maximum entropy (MaxEnt) reconstruction. Nonlinearly sampled MQMAS spectra are shown to provide high resolution and sensitivity in several systems, including lithium sulfate monohydrate (LiSO(4)-H(2)17O) and L-asparagine monohydrate (H(2)17O). The combination of nonlinear sampling and MaxEnt reconstruction promises to make the application of 17O MQMAS practical in a wider range of biological systems.

Anisotropy↗
PubMed2003

Measurement of 15N chemical shift anisotropy in a protein dissolved in a dilute liquid crystalline medium with the application of magic angle sample spinning.

The chemical shifts of nuclei that have chemical shielding anisotropy, such as the 15N amide in a protein, show significant changes in their chemical shifts when the sample is altered from an isotropic state to an aligned state. Such orientation-dependent chemical shift changes provide information on the magnitudes and orientation of the chemical shielding tensors relative to the molecule's alignment frame. Because of the extremely high sensitivity of the chemical shifts to the sample conditions, the changes in chemical shifts induced by adding aligned bicelles do not arise only from the protein alignment but should also include the accumulated effects of environmental changes including protein-bicelle interactions. With the aim of determining accurate 15N chemical shielding tensor values for solution proteins, here we have used magic angle sample spinning (MAS) to observe discriminately the orientation-dependent changes in the 15N chemical shift. The application of MAS to an aligned bicelle solution removes the torque that aligns the bicelles against the magnetic field. Thus, the application of MAS to a protein in a bicelle solution eliminates only the molecular alignment effect, while keeping all other sample conditions the same. The observed chemical shift differences between experiments with and without MAS therefore provide accurate values of the orientation-dependent 15N chemical shifts. From the values for ubiquitin in a 7.5% (w/v) bicelle medium, we determined the 15N chemical shielding anisotropy (CSA) tensor. For this evaluation, we considered uncertainties in measuring the 1H-15N dipolar couplings and the 15N chemical shifts and also structural noise present in the reference X-ray structure, assuming a random distribution of each NH bond vector in a cone with 5 degrees deviation from the original orientation. Taking into account these types of noise, we determined the average 15N CSA tensor for the residues in ubiquitin as Delta sigma=-162.0+/-4.3 ppm, eta=0.18+/-0.02, and beta=18.6+/-0.5 degrees, assuming a 1H-15N bond length of 1.02 A. These tensor values are consistent with those obtained from solid-state NMR experiments.

Amides↗
PubMed2003

Sensitivity-enhanced phase-corrected ultra-slow magic angle turning using multiple-echo data acquisition.

The increase in the sensitivity of the phase-corrected magic angle turning (PHORMAT) experiment at ultra-slow spinning rates by means of multiple-echo data acquisition (ME-PHORMAT) is evaluated. This is achieved by replacing the acquisition dimension in the original experiment with a train of equally spaced pi-pulses. It is shown that the echoes following the odd and even pi-pulses in the CPMG train must be processed differently in order to avoid spectral distortions. The method is illustrated for 13C CP-ME-PHORMAT on solid 1,2,3-trimethoxybenzene and for 1H ME-PHORMAT on excised rat liver tissue, both at a sample-spinning rate of 1.3 Hz. Sensitivity enhancements of a factor 4 for the solid and 2.3 for the liver were obtained. Finally, it is shown that with ME-PHORMAT one of the two RF pulse sequences, in standard PHORMAT used to obtain a pure absorption mode 2D spectrum, can be eliminated, thus reducing the usually long measuring time by a factor 2.

Algorithms↗
PubMed2003

Recoupling of residual dipolar couplings in single-domain polymer-stabilized liquid crystals undergoing magic-angle spinning.

Measurement of dipolar couplings, chemical shift anisotropies, and quadrupole couplings in oriented media such as liquid crystals are of great importance for extraction of structural parameters in biological macromolecules. Here, we introduce a new technique, SAD-REDOR, that consists of recoupling heteronuclear dipolar couplings in molecules dissolved in a single-domain liquid crystal or other oriented medium through the combined use of magic-angle spinning and rotor-synchronized radiofrequency pulses. This application of the REDOR pulse sequence to oriented media offers several advantages such as selectivity over the type of coupling recovered and tunable scaling of the interaction. The effectiveness of the technique is demonstrated both theoretically and experimentally, using the recently developed polyacrylamide-stabilized Pf1 phage medium and 15N-labeled benzamide as the aligned molecule.

Algorithms↗
PubMed2000

Hans Castorp's journey-to-knowledge of disease and health in Thomas Mann's The Magic Mountain.

The paper examines Thomas Mann's novel, The Magic Mountain, to show how imaginative literature can enhance our understanding of health in place. The story centers on the experiences of Hans Castorp, a young bourgeois German, at a tuberculosis sanatorium in the Swiss Alps. Three themes are examined: (1) how knowledge about illness and health, death and life, is gained; (2) how knowledge is arrived at through a dialectical process which reconciles seeming opposites; and(3) how new knowledge is gained through making transitions. Lessons for health geography are drawn from analysis of the three themes.

Adaptation, Psychological↗
PubMed2002

Clinical trials update from the European Society of Cardiology: CARMEN, EARTH, OPTIMAAL, ACE, TEN-HMS, MAGIC, SOLVD-X and PATH-CHF II.

This article continues a series of reports on research developments related to the field of heart failure. Reports of presentations made at the Hot Line sessions of the European Society of Cardiology XXIV Congress held in Berlin, Germany, between 31 August and 4 September 2002 are included. Summaries of the results of the following trials are presented: CARMEN, EARTH, OPTIMAAL, ACE, TEN-HMS, MAGIC, SOLVD-X and PATH-CHF II.

Cardiology↗
PubMed2005

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

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

Administration, Topical↗
PubMed2004

Probing molecular dynamics in chromatographic systems using high-resolution 1H magic-angle-spinning NMR spectroscopy: interaction between p-Xylene and C18-bonded silica.

The exact nature of the interaction between small molecules and chromatographic solid phases has been the subject of much research, but detailed understanding of the molecular dynamics in such systems remains elusive. High-resolution (1)H magic-angle-spinning (MAS) NMR spectroscopy has been applied to the investigation of C18-bonded silica material as used in chromatographic separation techniques together with an adsorbed model analyte, p-xylene. Two distinct p-xylene and water environments were identified within the C18-bonded silica through the measurement of (1)H NMR chemical shifts, T(1) and T(2) relaxation times and diffusion coefficients, including their temperature dependence. The results have been analyzed in terms of two environments, p-xylene within the C18 chains, in slow exchange on the NMR time scale with p-xylene in a more mobile state adsorbed as a layer in close proximity to the C18 particles, but which is distinct from free liquid p-xylene. The techniques used here could have more general applications, including the study of drug molecules bound into phospholipid membranes in micelles or vesicles.

Journal Article↗