Diffusion exchange NMR spectroscopy in inhomogeneous magnetic fields

Two-dimensional diffusion exchange experiments in the presence of a strong, static magnetic field gradient are presented. The experiments are performed in the stray field of a single sided NMR sensor with a proton Larmor frequency of 11.7 MHz. As a consequence of the strong and static magnetic field gradient the magnetization has contributions from different coherence pathways. In order to select the desired coherence pathways, a suitable phase cycling scheme is introduced. The pulse sequence is applied to study diffusion as well as the molecular exchange properties of organic solvents embedded in a mesoporous matrix consisting of a sieve of zeolites with a pore size of 0.8 nm and grain size of 2 μm. This pulse sequence extends the possibilities of the study of transport properties in porous media, with satisfying sensitivity in measurement times of a few hours, in a new generation of relatively inexpensive low-field NMR mobile devices.     

Influential Factors of Internal Magnetic Field Gradient in Reservoir Rock and Its Effects on NMR Response

Nuclear magnetic resonance (NMR) plays a significant role in porous media analysis and petroleum exploration, but its response is significantly influenced by the internal magnetic field gradient in fluid saturated porous medium, which obviously limits the accuracy of rock core analysis and logging interpretation. The influential factors of the internal magnetic field gradient in formation and its influences on NMR response are studied in this paper, based on NMR mechanism through one- and two-dimensional core NMR experiments. The results indicate that the internal magnetic field gradient is positively correlated with the static magnetic field strength and the magnetic susceptibility difference between pore fluid and solid grains, while it presents negative correlation with pore radius. The internal magnetic field gradient produces an additional diffusion relaxation in hydrogen relaxation system and accelerates the attenuation of magnetization vector. As a result, T₂ spectrum shifts to the left and NMR porosity and diffusion coefficient of the fluid could be inaccurate. This research sets a foundation for the NMR porosity correction and fluid distribution on T₂-G maps based on the internal magnetic field gradient correction.     

Electrically induced Raman emission from planar spin oscillator

We predict that two-dimensional electrons confined by a magnetic field gradient resonantly transfer energy to the electromagnetic field by a process of inverse electron spin resonance that is realized when the frequency of an open orbit equals the Larmor frequency. The calculated emission spectra show multiple peaks modulated by strong optical nonlinearities whose frequencies may be tuned by the magnetic field gradient and the electron concentration.     

Magnetization-Grid Rotating-Frame Imaging Technique for Diffusion and Flow Measurements

A method for NMR imaging of magnetization patterns generated by a preparation radiofrequency pulse is reported. The technique is suitable for the simultaneous spatially and spectroscopically resolved acquisition of diffusion, flow, and spin-lattice relaxation data. The procedure is based on gradients of the RF amplitude B₁. A first preparation RF pulse produces a z-magnetization grid. After a certain evolution interval, the grid is imaged by a rotating-frame imaging technique using the same RF coil. Neither rotary nor Hahn echoes are intrinsic to the method. Transverse relaxation in the free-evolution intervals is irrelevant. High-power transmitters in combination with suitable probeheads normally produce RF pulses which are short relative to transverse relaxation in the presence of RF, so that spin-lattice relaxation is the only time-limiting factor. Gradients of the main magnetic field induced by variations of the magnetic susceptibility are uncritical. The proposed "real-space detection" method is compared with stimulated or rotary-echo "wave number encoding" procedures for diffusion experiments. It is shown that the imaging procedure presented not only makes visible the spatial (apart from the spectral) distribution of transport properties which otherwise are concealed in the wave-number encoded signal, but also renders the measuring procedure insensitive to inhomogeneities of the B₁ gradient, which needs neither to be constant nor to be uniformly oriented. Extremely inhomogeneous B₁ gradient distributions should even make single-scan diffusion experiments feasible. The magnetization-grid rotating-frame imaging procedure can be employed for the two-dimensional measurement and representation of the probability P(z₁, 0|z₂, t) that a particle is at a position z₁ at a time 0 and at a position z₂ at a time t.     

Sizeable pure tensor polarization of deuterons in a solid

A new effect of dynamic nuclear orientation has been observed in deuterated 1, 2-ethanediol, (CD₂OH)₂, at 0.12 K in a magnetic field of 25 kG: a strong RF field applied at a frequency slightly different from the proton Larmor frequency changes the deuteron tensor polarization. Mechanisms for this effect are proposed.     

Production of Fe clusters by collisions of metal vapour with supersonic argon beams

For a spin-polarized plane wave passing through a spin-rotator containing uniform magnetic field, we provide a detailed analysis for solving the appropriate Schrödinger equation. A modified expression for spin precession is obtained which reduces to the standard Larmor precession relation when kinetic energy is very large compared to the spin-magnetic field interaction. We show that there are experimentally verifiable regimes of departure from the standard Larmor precession formula. The treatment is then extended to the case of a spin-polarized wave packet passing through a uniform magnetic field. The results based on the standard expression for Larmor precession and that obtained from the modified formula are compared in various regimes of the experimental parameters.     

One-dimensional DOSY.

A new NMR experiment for correlating diffusion coefficients and chemical shifts is presented. This experiment provides the same information as the conventional DOSY experiment, but only requires a single dimension because a nonuniform magnetic field gradient is used to encode the diffusion information into the lineshapes of the peaks in the chemical shift dimension. By fitting the resulting lineshapes, the diffusion coefficient for each peak in the spectrum can be extracted. Using this experiment, a qualitative DOSY spectrum can be generated using the results from a single one-dimensional experiment. Quantitative results can be determined with the use of reference experiments.     

Anisotropic water diffusion in macroscopically oriented lipid bilayers studied by pulsed magnetic field gradient NMR

The anisotropy, D(parallel)/D( perpendicular ), of water diffusion in fully hydrated bilayers of dimyristoylphosphatidylcholine at 29 degrees C has been measured by pulsed magnetic field gradient (pfg) NMR. By using NMR imaging hardware to produce magnetic field gradients in an arbitrary direction with respect to a stack of macroscopically aligned lipid bilayers, translational diffusion of water was measured as a function of the angle between the direction of the magnetic field gradient and the normal of the lipid membrane. The observed diffusion coefficient is found to depend strongly on this angle. The anisotropy cannot be accurately determined due to the very small value of D( perpendicular ), but a lower limit of about 70 can be estimated from the observed diffusion coefficients. The results are discussed in terms of the relatively low permeability of water across the lipid bilayer, instrumental limitations, and/or possible defects in the lamellae.     

Measuring small compartments with relatively weak gradients by angular double-pulsed-field-gradient NMR

NMR diffusion–diffraction patterns observed in compartments in which restricted diffusion occurs are a useful tool for direct extraction of compartment sizes. Such diffusion–diffraction patterns may be observed when the signal intensity E_(q,?) is plotted against the wave-vector q (when q = (2π)^− 1γδG). However, the smaller the compartment sizes are, the higher are the q-values needed to observe such diffractions. Moreover, these q-values should be achieved using short gradient pulses requiring extremely strong gradient systems. The angular double-pulsed-field gradient (d-PFG) NMR methodology has been proposed as a tool to extract compartment sizes using relatively low q-values. In this study, we have used single-PFG (s-PFG) NMR and angular d-PFG NMR to characterize the size of microcapillaries of about 2 ± 1 μm in diameter. We found that these microcapillaries are characterized by relatively strong background gradients that completely masked the effects of the microscopic anisotropy (μA) of the sample, resulting in a completely unexpected E(φ) profile in the angular d-PFG NMR experiments. We also show that bipolar angular d-PFG NMR experiments can largely suppress the effect of these background gradients resulting in the expected E(φ) profile from which the compartment dimensions could be obtained with relatively weak gradient pulses. These results demonstrate that the above methodology provides a quick, reliable, non-invasive means for estimating small pore sizes with relatively weak gradients in the presence of large magnetic susceptibility.     

A practical and flexible implementation of 3D MRI in the Earth's magnetic field

The Earth's magnetic field, though weak, is appealing for NMR applications because it is highly homogeneous, globally available and free. However, the practicality of Earth's field NMR (EFNMR) has long been limited by the need to perform experiments in outdoor locations where the local field homogeneity is not disrupted by ferrous or magnetic objects and where ultra-low frequency (ULF) noise sources are at a minimum. Herein we present a flexible and practical implementation of MRI in the Earth's magnetic field that demonstrates that EFNMR is not as difficult as it was previously thought to be. In this implementation, pre-polarization and ULF noise shielding, achieved using a crude electromagnet, are used to significantly improve signal-to-noise ratio (SNR) even in relatively noisy environments. A three axis gradient coil set, in addition to providing imaging gradients, is used to provide first-order shims such that sub-hertz linewidths can routinely be achieved, even in locations of significant local field inhomogeneity such as indoor scientific laboratories. Temporal fluctuations in the magnitude of the Earth's magnetic field are measured and a regime found within which these variations in Larmor frequency produce no observable artefacts in reconstructed images.     

Self-diffusion measurements by a mobile single-sided NMR sensor with improved magnetic field gradient

A simple and fast method of measuring self-diffusion coefficients of protonated systems with a mobile single-sided NMR sensor is discussed. The NMR sensor uses a magnet geometry that generates a highly flat sensitive volume where a strong and highly uniform static magnetic field gradient is defined. Self-diffusion coefficients were measured by Hahn- and stimulated echoes detected in the presence of the uniform magnetic field gradient of the static field. To improve the sensitivity of these experiments, a Carr-Purcell-Meiboom-Gill pulse sequence was applied after the main diffusion-encoding period. By adding the echo train the experimental time was strongly shortened, allowing the measurement of complete diffusion curves in less than 1min. This method has been tested by measuring the self-diffusion coefficients D of various organic solvents and poly(dimethylsiloxane) samples with different molar masses. Diffusion coefficients were also measured for n-hexane absorbed at saturation in natural rubber with different cross-link densities. The results show a dependence on the concentration that is in good agreement with the theoretical prediction. Moreover, the stimulated-echo sequence was successfully used to measure the diffusion coefficient as a function of the evolution time in systems with restricted diffusion. This type of experiment proves the pore geometry and gives access to the surface-to-volume ratio. It was applied to measure the diffusion of water in sandstones and sheep Achilles tendon. Thanks to the strong static gradient G(0), all diffusion coefficients could be measured without having to account for relaxation during the pulse sequence.     

Effect of a magnetic field on the rate of etching of silicon dioxide in a CF4 + O2 plasma

A near-electrode nonuniform magnetic field crossed with an electric field is found to strongly affect the rate of etching of silicon dioxide on glass substrates in a CF₄ + O₂ plasma when the Larmor frequency (≈10⁹ s⁻¹) is much higher than the frequency of collisions of an electron with surrounding plasma particles (≈10⁶ s⁻¹) and the frequency of the applied rf electric field (≈10⁷ s⁻¹). The confinement of electrons by the magnetic field in the immediate vicinity of the substrate surface to be treated increases the rate of generation of chemically active particles, which increases the etching rate of silicon dioxide.     

磁场梯度对Hall推力器放电特性影响的实验研究

为进一步探索Hall推力器通道内磁场优化设计理论,通过实验分析了强场区磁场梯度对推进剂的电离与加速等放电过程的影响. 研究发现,在本实验设计的磁场梯度范围内,磁场梯度大小对推进剂的电离过程影响较小,但是对离子流的加速特性会产生较为明显的影响.随着磁场梯度的增加,离子束的能量分布会趋于集中,推力器效率提高. 最后,对磁场轴向梯度进一步变大可能会引起的一系列物理问题如有限Larmor半径效应、电子传导机理转变规律和梯度漂移效应等进行了分析和思考.     

固态样品中扩散的核磁共振测量

用脉冲梯度切核磁共振测量固态样品中的扩散遇到很多困难,对于一个不用内锁的电磁体系统,观测到脉冲场梯度过后涡流造成样品处的磁场强度的强烈振荡.提出了一个用该系统测量凝胶聚合物中锂离子扩散可获得较好结果的脉冲序列.     

Magnetic resonance imaging at frequencies below 1 kHz

Within the magnetic resonance imaging (MRI) community the trend is going to higher and higher magnetic fields, ranging from 1.5 T to 7 T, corresponding to Larmor frequencies of 63.8–298 MHz. Since for high-field MRI the magnetization increases with the applied magnetic field, the signal-to-noise-ratio increases as well, thus enabling higher image resolutions. On the other hand, MRI is possible also at ultra-low magnetic fields, as was shown by different groups. The goal of our development was to reach a Larmor frequency range of the low-field MRI system corresponding to the frequency range of human brain activities ranging from near zero-frequency (near-DC) to over 1 kHz. Here, first 2D MRI images of phantoms taken at Larmor frequencies of 100 Hz and 731 Hz will be shown and discussed. These frequencies are examples of brain activity triggered by electrostimulation of the median nerve. The method will allow the magnetic fields of the brain currents to influence the magnetic resonance image, and thus lead to a direct functional imaging modality of neuronal currents.     

Phase gradient imaging for positive contrast generation to superparamagnetic iron oxide nanoparticle-labeled targets in magnetic resonance imaging

Positive contrast imaging methods produce enhanced signal at large magnetic field gradient in magnetic resonance imaging. Several postprocessing algorithms, such as susceptibility gradient mapping and phase gradient mapping methods, have been applied for positive contrast generation to detect the cells targeted by superparamagnetic iron oxide nanoparticles. In the phase gradient mapping methods, smoothness condition has to be satisfied to keep the phase gradient unwrapped. Moreover, there has been no discussion about the truncation artifact associated with the algorithm of differentiation that is performed in k-space by the multiplication with frequency value. In this work, phase gradient methods are discussed by considering the wrapping problem when the smoothness condition is not satisfied. A region-growing unwrapping algorithm is used in the phase gradient image to solve the problem. In order to reduce the truncation artifact, a cosine function is multiplied in the k-space to eliminate the abrupt change at the boundaries. Simulation, phantom and in vivo experimental results demonstrate that the modified phase gradient mapping methods may produce improved positive contrast effects by reducing truncation or wrapping artifacts.     

The Evaluation of Dielectric Resonators Containing H2O or D2O as RF Coils for High-Field MR Imaging and Spectroscopy

Electromagnetic resonators consisting of low-loss dielectric material and/or metallic boundaries are widely used in microwave technologies. These dielectric resonators usually have high Q factors and well-defined field distributions. Magnetic resonance imaging was shown as a way of visualizing the magnetic field distribution of the resonant modes of these resonators, if the dielectric body contains NMR sensitive nuclei. Dielectric resonators have also been proposed as RF coils for magnetic resonance experiments. The feasibility of this idea in high-field MR is discussed here. Specifically, the dielectric resonances of cylindrical water columns were characterized at 170.7 MHz (4 T¹H Larmor frequency), and evaluated as NMR transmit and receive coils. The dielectric resonance of a cylindrical volume of D₂O was used to image a hand at 170.7 MHz. This study demonstrated that MRI is an effective way of visualizing the magnetic field in dielectric structures such as a water cylinder, and can potentially be generalized to solid-state dielectric devices. The possible applications of dielectric resonators other than simple cylindrical volumes in MRI and MR solution spectroscopy at high field strengths are also discussed.     

Periodic structure of acicular magnetic clusters in a magnetic liquid

The behavior of magnetic clusters in a magnetic liquid placed in a circular capillary is considered. When a uniform magnetic field is applied to the system, acicular clusters grow from the sediment, being aligned with the field. The interaction of the clusters as magnetic dipoles with one another and with an external gradient magnetic field is considered theoretically. In a nonuniform symmetric magnetic field with a peak, the cluster distribution is uniform near the peak. Such a distribution is fairly stable when the magnetic field gradient is varied over certain limits. The ordered (periodic) cluster configuration is realized experimentally, and it is shown that its period can be controlled. As the magnetic field gradient exceeds a certain threshold, the clusters are redistributed, forming a multirow hexagonal array.     

Effective Gradients in Porous Media Due to Susceptibility Differences

In porous media, magnetic susceptibility differences between the solid phase and the fluid filling the pore space lead to field inhomogeneities inside the pore space. In many cases, diffusion of the spins in the fluid phase through these internal inhomogeneities controls the transverse decay rate of the NMR signal. In disordered porous media such as sedimentary rocks, a detailed evaluation of this process is in practice not possible because the field inhomogeneities depend not only on the susceptibility difference but also on the details of the pore geometry. In this report, the major features of diffusion in internal gradients are analyzed with the concept of effective gradients. Effective gradients are related to the field inhomogeneities over the dephasing length, the typical length over which the spins diffuse before they dephase. For the CPMG sequence, the dependence of relaxation rate on echo spacing can be described to first order by a distribution of effective gradients. It is argued that for a given susceptibility difference, there is a maximum value for these effective gradients,g_max, that depends on only the diffusion coefficient, the Larmor frequency, and the susceptibility difference. This analysis is applied to the case of water-saturated sedimentary rocks. From a set of NMR measurements and a compilation of a large number of susceptibility measurements, we conclude that the effective gradients in carbonates are typically smaller than gradients of current NMR well logging tools, whereas in many sandstones, internal gradients can be comparable to or larger than tool gradients.     

NMR Relaxation and Diffusion Measurements on Iron(III)-Doped Kaolin Clay

Kaolin clay samples were mixed with various amounts of Fe₂O₃ powder. The influence of this magnetic impurity on NMR relaxation and diffusion measurements on the water in this porous material was investigated. The NMR relaxation measurements showed a nearly mono-exponential decay, leading to the conclusion that the pore size distribution of the clay samples is either narrow and/or that the pores are interconnected very well. Both the longitudinal and the transverse relaxation rate depend linearly on the concentration of the Fe₂O₃ impurity. The NMR diffusion measurements revealed that the Fe₂O₃ causes internal magnetic field gradients that largely exceed the maximum external gradient that could be applied by our NMR apparatus (0.3 T/m). Additional SQUID measurements yielded the magnetization and magnetic susceptibility of the samples at the magnetic field strength used in the NMR measurements (0.8 T). A theoretical estimate of the internal magnetic field gradients leads to the conclusion that the water in the porous clay samples cannot be described by the commonly observed motional averaging regime. Probably an intermediate or a localization regime is induced by the large internal gradients, which are estimated to be on the order of 1 to 10 T/m in the pore volume and may exceed 1000 T/m at the pore surface.