The coordination of boron in aSi: (B,H)

Pulsed ¹¹B NMR measurements performed on an aSi: (B,H) film containing ～10 atomic % B reveal the presence of two distinct boron sites. The spin-spin relaxation time T₂ is frequency independent and of a magnitude which indicates that the boron is clustered rather than uniformly distributed. The large quadrupolar coupling inferred from the NMR linewidth strongly suggests that most of the boron in aSi: (B,H) does not exist in tetrahedral sites but is threefold coordinated.     

14N NMR relaxation times of several protein amino acids in aqueous solution--comparison with 17O NMR data and estimation of the relative hydration numbers in the cationic and zwitterionic forms

The 14N nuclear magnetic resonance (NMR) linewidths of the alpha-amino groups of several protein amino acids were measured in aqueous solution, with and without composite proton decoupling, to estimate the effect of proton exchange and molecular weight on the linewidths. It is shown that, contrary to earlier claims, the increase in the linewidth at low pH is not exclusively due to the effect of proton exchange broadening. The 14N linewidths, under composite proton decoupling, increase with the bulk of the amino acid, and increase at low pH. Statistical treatment of the experimental 14N and literature 17O NMR data was performed assuming two models: (i) an isotropic molecular reorientation of a rigid sphere in a medium of viscosity eta, (ii) a stochastic diffusion of the amino and carboxyl groups comprising contributions from internal (tauint) and overall (taumol) motions. Assuming a single correlation time from overall molecular reorientation (taumol), then, a linear correlation was found between the linewidths and the molecular weights of the protein amino acids at the pH values 0.5 and 6.0, which are characteristic of the cationic and zwitterionic forms, respectively. The slopes of the straight-lines were found to be dependent of pH for 14N, contrary to the 17O linear correlations whose slopes were found to be independent of pH. Assuming effective correlation times of the amino and carboxyl groups, which comprise contributions from the internal (tauint) and overall (taumol) motions, then, a significant improvement of the statistics of the regression analysis was observed. The 14N relaxation data, in conjunction with 17O NMR linewidths, can be interpreted by assuming that the 14N quadrupole coupling constants (NQCCs) are influenced by the protonation state of the carboxyl group, the 17O NQCCs remain constant, and the cationic form of the amino acids is hydrated by an excess of 1-3 molecules of water relative to the zwitterionic state.     

Correlations in 11B NMR spectra of dihalo derivatives of bis(1,2-dicarbollyl)cobalt(III)

In the ¹¹B NMR spectra of dihalo derivatives of bis(dicarbollyl)cobalt(III), we have identified a correlation between the ¹¹B NMR chemical shifts of substituted boron atoms and boron atoms found in other positions on the carborane skeleton. We have observed an increased shielding effect for fluorine atoms (compared with other halogens), manifested in an upfield shift of the ¹¹B NMR signals for antipodal and trans boron atoms. For the fluorine-containing compound Bu₄N⁺ [8,8′-F₂-3,3′-Co(1,2-C₂B₉H₁₀)₂]⁻, we propose the following sequence of electron density transfer: B(8) → {B(6) and B(10)} → B(4, 7). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 547–549 (cont.), July–August, 2006.     

Transverse relaxation mechanisms in articular cartilage

Relaxation rates in the rotating frame (R1rho) and spin-spin relaxation rates (R2) were measured in articular cartilage at various orientations of cartilage layer to the static magnetic field (B0), at various spin locking field strengths and at two different static magnetic field strengths. It was found that R1rho in the deep radial zone depended on the orientation of specimens in the magnet and decreased with increasing the spin locking field strength. In contrast, R1rho values in the transitional zone were nearly independent of the specimen orientation and the spin locking field strength. Measurements of the same specimens at 2.95 and 7.05 T showed an increase of R1rho and most R2 values with increasing B0. The inverse B0 dependence of some R2 values was probably due to a multicomponent character of the transverse magnetization decay. The experiments revealed that the dominant T1rho and T2 relaxation mechanism at B0 < or = 3 T is a dipolar interaction due to slow anisotropic motion of water molecules in the collagen matrix. On average, the contribution of scalar relaxation due to rapid proton exchange in femoral head cartilage at 2.95 T is about 6% or less of the total R1rho at the spin locking field of 1000 Hz.     

Effects of T2-relaxation in MAS NMR spectra of the satellite transitions for quadrupolar nuclei: a 27Al MAS and single-crystal NMR study of alum KAl(SO4)2.12H2O

Asymmetries in the manifold of spinning sidebands (ssbs) from the satellite transitions have been observed in variable-temperature 27Al MAS NMR spectra of alum (KAl(SO4)2.12H2O), recorded in the temperature range from -76 to 92 degrees C. The asymmetries decrease with increasing temperature and reflect the fact that the ssbs exhibit systematically different linewidths for different spectral regions of the manifold. From spin-echo 27Al NMR experiments on a single-crystal of alum, it is demonstrated that these variations in linewidth originate from differences in transverse (T2) relaxation times for the two inner (m=1/2<-->m=3/2 and m=-1/2<-->m=-3/2) and correspondingly for the two outer (m=3/2<-->m=5/2 and m=-3/2<-->m=-5/2) satellite transitions. T2 relaxation times in the range 0.5-3.5 ms are observed for the individual satellite transitions at -50 degrees C and 7.05 T, whereas the corresponding T1 relaxation times, determined from similar saturation-recovery 27Al NMR experiments, are almost constant (T1=0.07-0.10 s) for the individual satellite transitions. The variation in T2 values for the individual 27Al satellite transitions for alum is justified by a simple theoretical approach which considers the cross-correlation of the local fluctuating fields from the quadrupolar coupling and the heteronuclear (27Al-1H) dipolar interaction on the T2 relaxation times for the individual transitions. This approach and the observed differences in T2 values indicate that a single random motional process modulates both the quadrupolar and heteronuclear dipolar interactions for 27Al in alum at low temperatures.     

Power dependence of Brillouin linewidths in a silica fiber

We report the dependence of Brillouin linewidths on the pump power below the threshold of Brillouin lasing in a silica fiber. The Stokes Brillouin shift in a silica fiber is nearly unchanged, and its linewidth decreases with increasing pump power. However, the anti-Stokes Brillouin shift becomes smaller and its linewidth larger with increasing pump power. We explain these experimental results by the distributed fluctuating source model.     

A high-resolution 19F NMR spectroscopic study of barium fluorozirconate glasses and related crystals

Fluorozirconate glasses have attracted considerable attention not only for their transparency in the infrared, but also due to their high fluorine ion conductivities and extreme fragility in the viscosity-temperature relationship. We report on structural studies of binary BaF2-ZrF4 glasses with 58-78 mol% ZrF4 using high-resolution magic-angle-spinning 19F NMR. High-speed 19F MAS NMR allows us to resolve at least three unique fluorine environments in these binary glasses. These fluorine environments are attributed to one type of bridging fluorine, between corner-sharing Zr-F coordination polyhedra, and two types of non-bridging fluorine (NBF), one of which is bonded to one Zr and one Ba atom while the other is bonded to one Zr and two Ba atoms. The concentration of the first type of NBF increases with decreasing ZrF4 concentration, while that of the second type is essentially independent of glass composition. These assignments have been made on the basis of detailed 19F NMR studies of a wide variety of crystalline fluorozirconates with known crystal structures. A comparison between the glass and crystal 19F NMR spectra rules out any significant concentration of edge-shared Zr-F polyhedra in these binary glasses. The Zr atoms in all glasses are found to be coordinated to approximately 7.8+/-0.2F atoms.     

Fast nuclear spin relaxation in hyperpolarized solid 129Xe

We report extensive new measurements of the longitudinal relaxation time T1 of 129Xe nuclear spins in solid xenon. For temperatures T<120 K and magnetic fields B>0.05 T, we found T1 on the order of hours, in good agreement with previous measurements and with the predicted phonon-scattering limit for the spin-rotation interaction. For T>120 K, our new data show that T1 can be much shorter than the phonon scattering limit. For B = 0.06 T, a field often used to accumulate hyperpolarized xenon, T1 is approximately 6 s near the Xe melting point T(m) = 161.4 K. From T = 50 K to T(m), the new data are in excellent agreement with the theoretical prediction that the relaxation is due to (i) modulation of the spin-rotation interaction by phonons, and (ii) modulation of the dipole-dipole interaction by vacancy diffusion.     

A simple, small and low cost permanent magnet design to produce homogeneous magnetic fields

A new portable, pocket-size NMR probe based on a novel permanent magnet arrangement is presented. It is based on a Halbach-type magnet design which mimics the field of a spherical dipole by using cylindrical bar and ring magnets. The magnet system is made up of only three individual magnets, and most field calculations and optimisations can be performed analytically. A prototype system has been built using a set of small, off the shelf commercially available permanent magnets. Proton linewidths of 50 ppm FWHM could be achieved at a field strength of 1T. Calculations show that with custom-sized permanent magnets, linewidths of less than 1 ppm can be achieved over sample volumes of up to 1 mm3, which would in theory enable chemical shift resolved proton spectroscopy on mass-limited samples. But even with the achieved linewidth of 50 ppm, this can be a useful portable sensor for small amounts of liquid samples with restricted molecular mobility, like gels, polymers or high viscosity liquids.     

High resolution XPS study of the large-band-gap semiconductor stibnite (Sb2S3): Structural contributions and surface reconstruction

Conventional X-ray photoelectron spectroscopy (XPS) and synchrotron radiation XPS (SRXPS) were used to probe the chemical state properties of stibnite (Sb₂S₃), a large-band-gap semiconductor of complex structure. The conventional spectra were obtained with a Kratos Axis Ultra XPS with magnetic confinement charge neutralization, which is very effective in minimizing both uniform charging and differential charging on this large-band-gap semiconductor. The narrow linewidths (much narrower than previously obtained) for single doublet fits (e.g. Sb 4d_5/2 of 0.57 eV and S 2p_3/2 of 0.63 eV) enabled the observation of a small peak on the low binding energy side of the Sb 3d and Sb 4d lines. With the aid of the very surface-sensitive Sb 4d SRXPS spectra, these low energy peaks are assigned to small Sb metal clusters at the surface after cleavage; the signal for these clusters increases with X-ray dose on the sample.A detailed analysis of the Sb 4d and S 2p linewidths concludes that the Sb 4d_5/2 linewidth is larger than expected based on the inherent linewidth of the instrument and the Sb 4d lifetime width, and on comparison with the As 3d linewidth (0.52 eV) for the analogous As₂S₃. Also, the S 2p_3/2 linewidth is substantially broader than the Sb 4d_5/2 linewidth. These larger than expected linewidths are due to two structurally distinct Sb atoms and three structurally distinct S atoms in the Sb₂S₃ crystal structure. Accordingly, the Sb 4d and S 2p spectra have been fitted to two and three doublets respectively, and the linewidth for all peaks is 0.53 eV. Using recent molecular orbital calculations, the doublets have been assigned to the different structural Sb and S sites.     

Magic-angle-spinning NMR on solid biological systems. Analysis Of the origin of the spectral linewidths

Magic-angle-spinning (MAS) high-power ¹H-decoupled ¹³C and ³¹P NMR has been applied to solid biological materials to obtain information about the mechanisms that determine the spectral linewidths. The line broadening in MAS ³¹P NMR spectra of solid tobacco mosaic virus (TMV) has been investigated by selective saturation and T₂ measurements. About 90 Hz stems from homogeneous effects, whereas the inhomogeneous contribution is approximately 100 Hz. The inhomogeneous line broadening is assigned to macroscopic inhomogeneities in the sample and not to variations in the nucleotide bases along the RNA strand in TMV. It is concluded that sample preparation is of vital importance for obtaining well-resolved spectra. Under optimal preparation techniques the isotropic values of the chemical shift of the different ³¹P sites have been determined to obtain information about the secondary structure of the viral RNA. The chemical shift anisotropy has been determined from the relative intensities of the spinning side bands in the spectra. The chemical shift information is used to make a tentative assignment of the resonance in terms of the three structurally distinguishable phosphate groups in TMV. The origin of the linewidths in MAS NMR has been examined further by ¹³C NMR of approximately 10% ¹³C-enriched coat protein of cowpea chlorotic mottle virus, using selective excitation and saturation techniques, as well as measurements of the relaxation times T_1γ and T₂. The CO resonance in the spectrum is composed of an inhomogeneous and homogeneous part with a total linewidth of 700 Hz. The homogeneous linewidth, contributing with 200 Hz, is found to arise from slow molecular motions in the solid on a millisecond timescale.     

Cross-correlated (19)F relaxation measurements for the study of fluorinated ligand-receptor interactions.

Fluorine is often used in drug-design efforts to enhance the pharmacokinetic properties of biologically active compounds. Additionally fluorine nuclei ((19)F) have properties that are well suited to current pharmaceutical NMR screening programs. Together, these considerations have motivated our interest in the utility of fluorine relaxation parameters to study ligand-receptor interactions. Here, we investigate the potential for cross-correlated relaxation effects between the (19)F anisotropic chemical-shift and (19)F-(1)H dipole-dipole relaxation mechanisms to help pinpoint and quantify exchange processes. Methods are proposed and demonstrated in which the magnitude ratio of the transverse cross-correlation rate constant eta(xy) and the fluorine transverse relaxation rate constant, R(2), help estimate the exchange rate constant for ligand-binding equilibria. These exchange rate constants provide estimates of the ligand dissociation rate constants k(off) and can thus provide a means for rank-ordering the binding affinities of ligands identified in pharmaceutical screens.     

Study of molecular dynamics and cross relaxation in tetramethylammonium hexafluorophosphate (CH(3))(4)NPF(6) by (1)H and (19)F NMR

(CH(3))(4)NPF(6) is studied by NMR measurements to understand the internal motions and cross relaxation mechanism between the heterogeneous nuclei. The spin lattice relaxation times (T(1)) are measured for (1)H and (19)F nuclei, at three (11.4, 16.1 and 21.34 MHz) Larmor frequencies in the temperature range 350-50K and (1)H NMR second moment measurements at 7 MHz in the temperature range 300-100K employing home made pulsed and wide-line NMR spectrometers. (1)H NMR results are attributed to the simultaneous reorientations of both methyl and tetramethylammonium groups and motional parameters are evaluated. (19)F NMR results are attributed to cross relaxation between proton and fluorine and motional parameters for the PF(6) group reorientation are evaluated.     

Suppression of diagonal peaks in TROSY-type 1H NMR NOESY spectra of 15N-labeled proteins.

A novel method for suppression of diagonal peaks in the amide region of NOESY NMR spectra of 15N-labeled proteins is presented. The method is particularly useful for larger proteins at high magnetic fields where interference between dipolar and chemical shift anisotropy relaxation mechanisms results in large TROSY effects, i.e. , large differences in 1HN linewidths depending on the spin state of attached 15N nuclei. In this limit the new TROSY NOESY method does not compromise sensitivity. It is demonstrated using a perdeuterated 15N-labeled protein sample, Neural Cell Adhesion Molecule 213-308 (NCAM) from rat, in H2O at 800 MHz.     

Carbon dioxide detection by boron nitride nanotubes

The effect of gas molecule adsorption is investigated on the density of states of (9,0) zigzag boron nitride nanotube within a random tight-binding Hamiltonian model. The Green function approach and coherent potential approximation have been implemented. The results show that the adsorption of carbon dioxide gas molecules by boron atoms only leads to a donor type semiconductor while the adsorption by nitrogen atoms only leads to an acceptor. Since the gas molecules are adsorbed by both boron and nitrogen atoms, a reduction of the band gap is found. In all cases, increasing the gas concentration causes an increase in the height of the peaks in the band gap. This is due to an increasing charge carrier concentration induced by adsorbed gas molecules.     

NMR study of fluorine and proton motion in the ionic conductor NH4Sn2F5

The nuclear spin relaxation times of protons and fluorine atoms in the ionic conductor NH₄ Sn₂ F₅ show a particular temperature behaviour: they decrease as the temperature decreases below 200 K and have the same temperature and frequency dependences.Cross relaxation experiments show an important coupling between fluorine atoms and protons. NMR results as well as crystallographic and conductivity data on hydrogenated and deuterated compounds, allow to determine two dominant kinds of motion: at low temperature the reorientation of the ammonium ion is observed and above 250 K the diffusion of the fluorine atoms is responsible for the relaxation. In the high temperature range, the activation energies of the motion deduced from conductivity and NMR measurements are in good agreement.     

Proton dynamics in antiferroelectric CsH3(SeO3)2 single crystal investigated by 1H NMR measurements

¹H nuclear magnetic resonance (NMR) measurements have been performed to study the proton dynamics associated with the antiferroelectric transition of a hydrogen-bonded single crystal of CsH₃(SeO₃)₂. Herein, ¹H NMR spectrum, shift, linewidth, and spin-lattice relaxation rate 1/T₁ are measured in the temperature range of 80–296 K with the c-axis parallel to a magnetic field of ~4.85 T. The spectrum exhibits a composite structure with two narrow peaks at 296 K; at a low temperature, this structure evolves into a single broad shape with three humps. This complex shape and evolution are deconvoluted into five or six components based on the number of inequivalent and disordered hydrogen sites. By estimating the chemical shift and linewidth for each proton site, we identify all peaks. The spin-lattice relaxation recovery exhibits a double-exponential behavior with two relaxation times, short T_1S and extremely large T_1L. Both T_1S and T_1L follow Arrhenius behavior. From the respective 1/T₁(T), the activation energies for proton motion are measured to be small: 1.16 ± 0.1 and 0.83 ± 0.06 kJ/mol for T_1S and T_1L, respectively. While the static NMR data, chemical shift and linewidth, show no evidence for the transition, the dynamic data 1/T_1L highlights a clear increase across T_N = 145 K, which is possibly a signature of the transition.     

Solid-state S MAS NMR of inorganic sulfates

Solid-state (33)S MAS NMR spectra of a variety of inorganic sulfates have been obtained at magnetic field strengths of 4.7, 14.1, 17.6, and 18.8 T. Some of the difficulties associated with obtaining natural abundance (33)S NMR spectra have been overcome by using a high magnetic field strength and magic angle spinning (MAS). Multiple factors were considered when analyzing the spectral linewidths, including magnetic field inhomogeneity, dipolar coupling, chemical shift anisotropy, chemical shift dispersion, and quadrupolar coupling. In most of these sulfate samples, quadrupolar coupling was the dominant line broadening mechanism. Nuclear electric quadrupolar coupling constants (C(q)) as large as 2.05 MHz were calculated using spectral simulation software. Spectral information from these new data are compared with X-ray measurements and GAUSSIAN 98W calculations. A general correlation was observed between the magnitude of the C(q) and the increasing difference between S-O bond distances within the sulfate groups. Solid-state (33)S spin-lattice (T(1)) relaxation times were measured and show a significant reduction in T(1) for the hydrated sulfates. This is most likely the result of the modulation of the time-dependent electric field gradient at the nuclear site by motion of water molecules. This information will be useful in future efforts to use (33)S NMR in the compositional and structural analysis of sulfur containing materials.     

Solid-state 33S MAS NMR of inorganic sulfates

Solid-state (33)S MAS NMR spectra of a variety of inorganic sulfates have been obtained at magnetic field strengths of 4.7, 14.1, 17.6, and 18.8 T. Some of the difficulties associated with obtaining natural abundance (33)S NMR spectra have been overcome by using a high magnetic field strength and magic angle spinning (MAS). Multiple factors were considered when analyzing the spectral linewidths, including magnetic field inhomogeneity, dipolar coupling, chemical shift anisotropy, chemical shift dispersion, and quadrupolar coupling. In most of these sulfate samples, quadrupolar coupling was the dominant line broadening mechanism. Nuclear electric quadrupolar coupling constants (C(q)) as large as 2.05 MHz were calculated using spectral simulation software. Spectral information from these new data are compared with X-ray measurements and GAUSSIAN 98W calculations. A general correlation was observed between the magnitude of the C(q) and the increasing difference between S-O bond distances within the sulfate groups. Solid-state (33)S spin-lattice (T(1)) relaxation times were measured and show a significant reduction in T(1) for the hydrated sulfates. This is most likely the result of the modulation of the time-dependent electric field gradient at the nuclear site by motion of water molecules. This information will be useful in future efforts to use (33)S NMR in the compositional and structural analysis of sulfur containing materials.     

Oxygen-sensitive 19F NMR imaging of the vascular system in vivo

The fluorine nuclear magnetic resonance spin-lattice relaxation rate (1/T1) of the perfluorochemical blood substitute perfluorotripropylamine (FTPA) is very sensitive to oxygen tension. This presents the possibility of measuring blood oxygen tension by 19F MR imaging. We obtained oxygen-sensitive 19F NMR images of the circulatory system of rats infused with emulsified FTPA. Blood oxygenation was assessed under conditions of both air- and 100% O2-breathing. T1 relaxation times were derived from MR images using a partial saturation pulse sequence. The T1 times were compared with a phantom calibration curve to calculate average blood pO2 values in the lung, liver, and spleen. The results showed marked, organ-specific increases in blood oxygen tension when the rat breathed 100% O2 instead of air.