Magnetic field mapping in NMR imaging

The Hahn spin preparation sequence provides a practical means for rapid and sensitive mapping of magnetic field inhomogeneity in NMR imaging applications. Choice of the rf pulse delay times tau 1 and tau 2 as well as conditions and limitations on the proposed use of this sequence for chemical shift imaging are discussed.     

Water dynamics in ionomer membranes by field-cycling NMR relaxometry

The dynamic behavior of water within two types of ionomer membranes, Nafion and sulfonated polyimides, has been investigated by field-cycling nuclear magnetic relaxation. This technique, applied to materials prepared at different hydration levels, allows to probe the proton motion on a time scale of the microsecond. The NMR longitudinal relaxation rate R(1) measured over three decades of Larmor angular frequencies omega is particularly sensitive to the host-water interactions and thus well suited to study fluid dynamics in restricted geometries. In the polyimide membranes, we have observed a strong dispersion of R(1)(omega) following closely a 1/sqrt[omega] law in a low-frequency range (correlation times from 0.1 to 10 micros). This is indicative of a strong interaction of water with "interfacial" hydrophilic groups of the polymeric matrix (wetting situation). On the contrary, in the Nafion, we observed weak variations of R(1)(omega) at low frequency. This is typical of a nonwetting behavior. At early hydration stages, the proton-proton inter-dipolar contribution to R(1)(omega) evolves logarithmically, suggesting a confined bidimensional diffusion of protons in the microsecond time range. Such an evolution is lost at higher swelling where a plateau related to 3D diffusion is observed.     

Magnetic studies with zero field NMR

A review is given of the information about a ferromagnetic system obtainable from swept frequency NMR. The distinction between signals from nuclei in domains and domain walls is stressed and recent advances in instrumentation described.     

Magnetic Properties of Nanoparticles Useful for SQUID Relaxometry in Biomedical Applications

We use dynamic susceptometry measurements to extract semiempirical temperature-dependent, 255-400 K, magnetic parameters that determine the behavior of single-core nanoparticles useful for SQUID relaxometry in biomedical applications. Volume susceptibility measurements were made in 5 K degree steps at nine frequencies in the 0.1-1000 Hz range, with a 0.2 mT amplitude probe field. The saturation magnetization (M_s) and anisotropy energy density (K) derived from the fitting of theoretical susceptibility to the measurements both increase with decreasing temperature; good agreement between the parameter values derived separately from the real and imaginary components is obtained. Characterization of the Néel relaxation time indicates that the conventional prefactor, 0.1 ns, is an upper limit, strongly correlated with the anisotropy energy density. This prefactor decreases substantially for lower temperatures as K increases. We find, using the values of the parameters determined from the real part of the susceptibility measurements at 300 K, that SQUID relaxometry measurements of relaxation and excitation curves on the same sample are well described.     

Proton tunneling in a hydrogen bond measured by cross-relaxation field-cycling NMR

A field-cycling NMR pulse sequence is described for studying cross-relaxation between unlike nuclear spins in the solid state. The technique has been applied to study proton tunneling in the hydrogen bonds of a carboxylic acid containing 19F and 1H spins. By studying the B-field dependence of the off-diagonal element of the relaxation matrix that characterizes the longitudinal polarizations, an accurate measure of the proton transfer rate is obtained.     

Efficient compensation of low-frequency magnetic field disturbances in NMR with fluxgate sensors

A simple stabilization scheme of B(0) magnetic field fluctuations is described. The method is based on external measurements of time dependent magnetic field fluctuations by fluxgate sensors and generation of a compensating correction current in a coil mounted directly on an NMR magnet. It is shown that such an approach efficiently eliminates relatively slow magnetic field variations with frequency up to approximately 100 Hz. In combination with a standard (2)H field-frequency lock system, the method enables acquisition of reproducible lineshapes and dramatically improves overall performance of a high resolution NMR spectrometer. The presented solution might substitute for the internal lock system in these case where deuterium lock is not available.     

Magnetic band structure in the valence band of CdSb

Starting from the band structure calculations of Yamada, we have undertaken to calculate in analytic form the Landau levels, de Haas-Shubnikov oscillation periods and effective masses in the valence band of CdSb. Because of the anomalous character of the E — k relation in the x-direction, it is necessaryto use different approximation methods for low and high hole energies; between the two is a region for which calculation is very difficult. Analytic forms have been obtained in both regimes, which should facilitate the calculation of magneto-transport properties and thus the determination of band parameters.     

Chain dynamics in mesoscopically confined polymer melts. A field-cycling NMR relaxometry study

Polymer chain dynamics were studied with the aid of field-cycling NMR relaxometry (time scale: 10^-9s... 10^-4s) supplemented by field gradient NMR diffusometry (time scale: 10^-4s...10⁰s). Three sorts of samples of mesoscopically confined polymer melts were examined. In the first sample series, linear poly(ethylene oxide) was incorporated in strands embedded in a quasi-solid and impenetrable methacrylate matrix. The strand diameters ranged from 10 to 60 nm. It was shown that chain dynamics becomes dramatically different from bulk behavior. This so-called “corset effect” occurs both above and below the critical molecular mass and reveals dynamic features predicted for reptation. On the time scale of spin-lattice relaxation, the frequency and molecular weight, signature of reptation, T₁ ∼M⁰ ν^3/4, that is limit II of the Doi/Edwards formalism corresponding to the mean squared segment displacement law 〈r² 〉∼M⁰ t^1/4, showed up. A “tube” diameter of only 0.6 nm was concluded to be effective on this time scale even when the strand diameter was larger than the radius of gyration of the PEO random coils. The corset effect is traced back to the lack of the local fluctuation capacity of the free volume under nanoscopic confinements. The confinement dimension at which the cross-over from confined to bulk chain dynamics is expected was estimated to be micrometers. Using the so-called roll-coating technique, micrometer thick polymer melt layers between Kapton foils were prepared. Perceptible differences from the bulk materials were found. The polymer species studied in this case was perfluoropolyether with Flory radii in the order of 7 nm. Remarkably, the confinement effect was shown to reach polymer-wall distances of the order 100 Flory radii. As a third confinement system, melts of perfluoropolyether were filled into a porous silica glass (Vycor; 4 nm nominal pore size). In this case, a crossover from Rouse dynamics in the bulk to reptation in the Doi/Edwards limit III (T₁∼M^-1/2 ν^1/2 corresponding to 〈r² 〉∼M^-1/2 t^1/2) was observed.     

Characterisation of Ripening and Pressure-Induced Changes in Tomato Pericarp Using NMR Relaxometry

A combination of two-dimensional nuclear magnetic resonance (NMR) relaxometry and optical microscopy is used to investigate the effects of ripening and high-pressure treatment on tomato pericarp tissue. It is shown that the relaxation times of the vacuolar water increase during the early stages of ripening even when there is no visible change and that this could be the basis of a useful on-line sensor for sorting tomatoes. The membrane rupturing and biopolymer denaturation associated with high-pressure treatments are also reflected in the NMR relaxation spectra.     

Magnetic field gradients in solid state magic angle spinning NMR.

Magnetic field gradients have proven useful in NMR for coherence pathway selection, diffusion studies, and imaging. Recently they have been combined with magic angle spinning to permit high-resolution measurements of semi-solids, where magic angle spinning averages any residual dipolar couplings and local variations in the bulk magnetic susceptibility. Here we show the first examples of coherence pathway selection by gradients in dipolar coupled solids. When the gradient evolution competes with dipolar evolution the experiment design must take into account both the strength of the dipolar couplings and the means to refocus it. Examples of both homonuclear and heteronuclear experiments are shown in which gradients have been used to eliminate the need for phase cycling.     

Detection of anisotropic hyperfine transitions in zero magnetic field using field-cycling techniques

For the first time, we describe the detection of hyperfine transitions in zero magnetic field using field-cycling techniques and pulsed EPR spectroscopy. The sample investigated was coal, which shows an anisotropic electron spin-(13)C hyperfine interaction.     

Flow-enhanced molecular reorientations and interfacial slip probed by field-cycling NMR relaxometry in microscopic pores

It is shown that hydrodynamic flow has an effect on spin-lattice relaxation in water filled into a porous monolithic silica material. This is a rotational analogue of translational hydrodynamic (or Taylor-Aris) dispersion arising from incoherent Brownian motion in combination with coherent flow. The effect is demonstrated with the aid of field-cycling NMR relaxometry and confirmed by theoretical considerations. The results directly verify bulk mediated surface diffusion and reveal interfacial slip at fluid-solid interfaces.     

A field-cycling NMR study of nematic 4-pentyl-4′-cyanobiphenyl confined in porous glasses

The proton spin-lattice relaxation time T₁, in the nematic liquid crystal 4-pentyl-4′-cyanobiphenyl confined in a glassy porous matrix has been measured in a wide Larmor frequency range of 1 · 10²?2 · 10⁷ Hz employing the fast field-cycling NMR technique. A strong influence of the restricted geometry on the character of the T₁ dispersion was found. Our investigation clearly demonstrates the importance of the translationally induced molecular reorientations in inhomogeneous director field for the relaxation in the samples with 200 and 80 nm mean pore size. The experimental results are in a good agreement with the theoretical predictions. In the sample with 7 nm pore size the main contribution to the relaxation is ascribed to the slowing down of the molecular motion in the near-surface layer. Zero-field 1H NMR spectra of a microconfined liquid crystal are reported for the first time.     

Nuclear (Proton) Magnetic Resonance Relaxometry Study of the Effect of Rotating Magnetic Field on the Emulsion Structure

Concentrated oil-in-water emulsions have been studied using nuclear magnetic resonance relaxometry (NMRR). To characterize the size distribution of water droplets, correlations between NMRR data and integral droplets diameters have been established and used for data interpretation. The dependences of parameters of emulsion components have been obtained from proton relaxation data after rotating magnetic field application and sedimentation.     

Inter- and Intramolecular Relaxation in Molecular Liquids by Field Cycling 1H NMR Relaxometry

Field cycling ¹H nuclear magnetic resonance (NMR) relaxometry is applied to study rotational as well as translational dynamics in molecular liquids. The measured relaxation rates, $ T_{1}^{ - 1} \left( \omega \right) \equiv R_{1} \left( \omega \right) $ , contain intra- and intermolecular contributions, $ R_{{1,{\text{intra}}}}^{{}} \left( \omega \right) $ and $ R_{{ 1 , {\text{inter}}}}^{{}} \left( \omega \right) $ . The intramolecular part is mediated by rotational dynamics, the intermolecular part by translation as well as rotation. The rotational impact on the intermolecular relaxation (eccentricity effect) is due to the spins not located in the molecule’s center. The overall relaxation rate is decomposed into $ R_{{1,{\text{intra}}}}^{{}} \left( \omega \right) $ and $ R_{{ 1 , {\text{inter}}}}^{{}} \left( \omega \right) $ by isotope dilution experiments. It is shown that the eccentricity model (Ayant et al. in J. Phys. (Paris) 38:325, 1977) reproduces fairly well the bimodal shape of $ R_{{ 1 , {\text{inter}}}}^{{}} \left( \omega \right) $ for o-terphenyl and glycerol. As the relaxation contribution associated with translational dynamics dominates at lower frequencies, the overall relaxation rate shows a universal linear behavior when plotted versus square root of frequency. This allows determining the self-diffusion coefficient, D, in a model-independent way. It is demonstrated that the shape of NMR master curves comprising relaxation data for different temperatures, linked by frequency–temperature superposition, reflects the relative strength of translational and rotational contributions.     

Magnetic hyperfine field of arsenic in nickel by NMR/ON of71,72As

The magnetic hyperfine splitting frequencies of⁷¹AsNi and⁷²AsNi in a 0.11 Tesla external magnetic field have been determined by NMR/ON method as 66.00(6) MHz and 106.17(13) MHz respectively. Using the known magnetic moments of μ(⁷¹As)=1.6735(18) and μ(⁷²As)=−2.1566(3), the hyperfine fields were deduced asB _hf(⁷¹AsNi)=12.824(19) Tesla andB _hf(⁷²AsNi)=12.807(16) Tesla.     

Application of field-cycling NMR relaxometry to the study of ultrasound-induced effects in the molecular dynamics and order of mesomorphic materials

A salient characteristic of nuclear magnetic resonance (NMR) techniques is the possibility to scan nuclear spin evolutions within a broad Larmor frequency range. Special instrumentation was developed to extend nuclear spin relaxation studies up to proton Larmor frequencies in the sub-kilohertz regime, a technique known as field-cycling NMR relaxometry. This article refers to an experimental version where the sample under study is selectively subjected to ultrasonic irradiation. The fact that ultrasound couples selectively to the collective dynamics of liquid crystals, offers new insights for the study of the molecular dynamics in these materials using NMR relaxation.