Radiofrequency magnetic field gradient echoes have reduced sensitivity to susceptibility gradients

The amplitudes of gradient-echoes produced using static field gradients are sensitive to diffusion of tissue water during the echo evolution time. Gradient-echoes have been used to produce MR images in which image intensity is proportional to the self-diffusion coefficient of water. However, such measurements are subject to error due to the presence of background magnetic field gradients caused by variations in local magnetic susceptibility. These local gradients add to the applied gradients. The use of radiofrequency (RF) gradients to produce gradient-echoes may avoid this problem. The RF magnetic field is orthogonal to the offset field produced by local magnetic susceptibility gradients. Thus, the effect of the local gradients on RF gradient-echo amplitude is small if the RF field is strong enough to minimize resonance offset effects. The effects of susceptibility gradients can be further reduced by storing magnetization longitudinally during the echo evolution period. A water phantom was used to evaluate the effects of background gradients on the amplitudes of RF gradient-echoes. A surface coil was used to produce an RF gradient of between 1.3 and 1.6 gauss/cm. Gradient-echoes were detected with and without a 0.16 gauss/cm static magnetic field gradient applied along the same direction as the RF gradient. The background static field gradient had no significant effect on the decay of RF gradient-echo amplitude as a function of echo evolution time. In contrast, the effect of the background gradient on echoes produced using a 1.6 gauss/cm static field gradient is calculated to be significant. This analysis suggests that RF gradient-echoes can produce MR images in which signal intensity is a function of the self-diffusion coefficient of water, but is not significantly affected by background gradients.     

Self-diffusion of water and benzene molecules adsorbed in synthetic opal samples

The self-diffusion of adsorbed molecules of water and benzene in porous synthetic opals has been studied by pulsed field gradient nuclear magnetic resonance. The study indicates two “phases” of water molecules differing by the self-diffusion coefficients, indicating two types of porosities existing in the synthetic opals. The smallest self-diffusion coefficient characterizes water in ultramicropores found on the surface of nanospheres. The form of the diffusion decay depends on temperature in the region of high temperatures as a result of exchange between pores of different sizes. The ultramicropores are inaccessible for the largest benzene molecules. Water adsorption and self-diffusion data confirm that annealing of the opal samples at 1293 K caused the collapse of ultramicropores.     

Peculiarities of self-diffusion of alkane molecules in kaolinite

Self-diffusion of alkanes in kaolinite has been explored by pulsed field gradient nuclear magnetic resonance. The concentration dependences of average self-diffusion coefficient (SDC) of liquid have been studied in the wide temperature interval (T=253?383 K). The translational mobility of alkane molecules in kaolinite was shown to have some specific peculiarities. An anomalous rise was found in the average self-diffusion coefficient of the liquid as its content in kaolinite decreased. To explain this we should introduce a new “gas-like” state for the diffusant, whose mobility exceeds that of pure liquid. The possibility of the existence of such a state is explained by kaolinite’s ability to increase the specific surface area of the induced liquid. Analysis of a shape of the spin-echo diffusion attenuation leads one to suppose that there are heterogeneities in the medium’s porous space.     

NMR studies of water diffusion and relaxation in hydrating slag-based construction materials.

The NMR relaxation properties of hydrating blast-furnace slag cements have recently been shown to be dominated by the effect of water self-diffusion in internal magnetic field gradients in the pastes. While this was suggested on the basis of NMR relaxometry and magnetic susceptibility data, we report here the results from first direct studies of the water self-diffusion in the hydrating paste using a specialized PFG sequence and very intensive magnetic field gradient pulses.     

核磁共振中多量子相干扩散行为的理论表述和计算机模拟

改进了Warren所提出的CRAZED脉冲序列以研究分子间多量子相干的扩散过程 ,讨论了利用核磁共振测量分子内和分子间多量子相干表观自扩散系数的理论表述 ,采用粒子的随机行走模型模拟其扩散行为 .在短脉冲近似和长脉冲梯度场两种实验条件下 ,分别获得了因扩散引起的不同相干阶数的相对信号衰减强度随梯度场脉冲间隔时间的变化曲线 ,由此得到分子内多量子相干和分子间多量子相干的表观扩散率与溶液分子扩散系数的关系 .还将计算机模拟结果与理论预测进行分析和比较 ,发现二者能很好地吻合 .研究结果表明 ,分子间多量子相干的表观扩散率与常规的分子内多量子相干的表观扩散率明显不同 ,因此 ,分子间多量子相干的表观扩散率可能提供一种新的核磁共振成像的对比度机理     

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.     

Determination of water self-diffusion coefficient in complex food products by low field 1H PFG-NMR: comparison between the standard spin-echo sequence and the T1-weighted spin-echo sequence

In 1990, Van Den Enden et al. proposed a method for the determination of water droplet size distributions in emulsions using a pulsed-field-gradient nuclear magnetic resonance (PFG-NMR) T1-weighted stimulated-echo technique. This paper describes both the T1-weighted spin-echo sequence, an improved method based on this earlier work, and, the standard PFG spin-echo sequence. These two methods were compared for water self-diffusion coefficient measurement in the fatty protein concentrate sample used as a 'cheese model.' The transversal and longitudinal relaxation parameters T1 and T2 were determined according to the temperature and investigated for each sample; fat-free protein concentrate sample, pure anhydrous milk fat, and fatty protein concentrate sample. The water self-diffusion in fat-free protein concentrate samples followed a linear behavior. Consequently, the water self-diffusion coefficient could be easily characterized for fat-free protein concentrate samples. However, it seemed more complicated to obtain accurate water self-diffusion in fatty protein concentrate samples since the diffusion-attenuation data were fitted by a bi-exponential function. This paper demonstrates that the implementation of the T1-weighted spin-echo sequence, using the different T1 properties of water and fat phases, allows the accurate determination of water self-diffusion coefficient in a food product. To minimize the contribution of the 1H nuclei in the fat phase on the NMR echo signal, the fat protons were selectively eliminated by an additional 180 degrees pulse. This new method reduces the standard errors of diffusion data obtained with a basic spin-echo technique, by a factor of 10. The effectiveness of the use of the T1-weighted spin-echo sequence to perform accurate water self-diffusion coefficients measurement in fatty products is thus demonstrated.     

Molecular collisions and self-diffusion in liquids

The velocity autocorrelation function and coefficient of self-diffusion are derived for a hard-sphere fluid. An earlier quasi-lattice model of self-diffusion in liquids is re-examined and a less restrictive expression for the self-diffusion coefficient is derived. The coefficient of self-diffusion of a light or heavy isotope in the normal liquid is considered both for hard spheres and in the quasi-lattice approximation. An experiment is proposed to clarify the nature of the isotope effect in self-diffusion.     

Concentration dependences of solvent self-diffusion coefficients in solutions and heterogeneous systems

On the basis of the concepts of exchange processes the problem to interpret solvent self-diffusion coefficients measured by pulsed field gradient nuclear magnetic resonance in solutions of various nature and heterogeneous systems is discussed. The problem to choose the concentration scale for the interpretation of the concentration dependences of self-diffusion coefficients in such systems is discussed as well.     

A statistical-mechanical theory of self-diffusion in colloidal suspensions — application to colloidal glass transitions

A statistical-mechanical theory of self-diffusion in colloidal suspensions is presented. A renormalized linear Langevin equation is derived from a nonlinear Langevin equation by employing the Tokuyama–Mori projection operator method. The friction constant is thus shown to be renormalized by the many-body correlation effects due to not only the direct interactions between particles, but also due to the hydrodynamic interactions between particles. The equations for the mean-square displacement and the non-Gaussian parameter are then derived. The present theory is applied to colloidal glass transitions to discuss the crossover phenomena in the dynamics of a single particle from a short-time self-diffusion process to a long-time self-diffusion process via a β (caging) stage. The effects of the renormalized friction coefficient on self-diffusion are thus explored with the aid of the analyses of the experimental data and the simulation results by the mean-field theory proposed by the present author. It is thus shown that the relaxation time of the renormalized memory function is given by the β-relaxation time. It is also shown that the non-Gaussian parameter is very small, even near the glass transition, because of the existence of the short-time self-diffusion coefficient caused by the hydrodynamic interactions.     

In vivo magnetic resonance diffusion measurement in the brain of patients with multiple sclerosis.

Measurement of water self-diffusion in the brain in 25 patients with multiple sclerosis was performed by magnetic resonance imaging. Quantitative diffusion measurements were obtained using single spin-echo pulse sequences with pulsed magnetic field gradients of different magnitude. Twenty-two of these patients also underwent measurement of the transverse relaxation time (T2). Only one plaque was evaluated in each patient. Based on prior knowledge, 12 plaques were classified as being 3 mo or less in age, and 7 plaques were classified as being more than 3 mo old. In all 25 plaques, water self-diffusion was found to be higher than in apparently normal white matter. Furthermore, water self-diffusion was found to be higher in acute plaques compared with chronic plaques. Finally, a slight tendency toward a relationship between the diffusion capability and T2 was found. We believe that an increased diffusion capability signifies an increase of the extracellular water space, which probably is related to the degree of demyelination. Thus, measurement of water self-diffusion in multiple sclerosis plaques may contribute to the study of pathogenesis of demyelination.     

Determination of genuine diffusivities in heterogeneous media using stimulated echo pulsed field gradient NMR

Pulsed field gradient (PFG) NMR diffusion measurements in heterogeneous media may lead to erroneous results due to the disturbing influence of internal magnetic field gradients. Here, we present a simple theoretical model which allows one to interpret data obtained by stimulated spin echo PFG NMR in the presence of spatially varying internal field gradients. Using the results of this theory, the genuine self-diffusion coefficients in heterogeneous media may be extrapolated from the dependence of the apparent diffusivities on the dephasing time of the simulated echo PFG NMR sequence. Experimental evidence that such extrapolation yields satisfactory results for self-diffusion of hexadecane in natural sediments (sand) and of n-octanol in doped MgO pastes is provided.     

Ionic and molecular Self-Diffusion in Ion-Exchange materials for fuel energetics studied by pulsed field gradient NMR

Pulsed field gradient nuclear magnetic resonance technique was applied to investigate the self-diffusion mechanism of water, alcohol molecules and Li⁻ counterions in sulfocation exchangers with different structures of the polymeric matrix. It was shown that in the homogeneous perfluorinated sulfocation exchange membranes the ionic and water translation motions are controled by the hydrogen bond network forming in ionogenic channels at the high water content. At the low solvent content, the self-diffusion coefficients of methanol and ethanol are higher than the water self-diffusion coefficients. The influence of non-ion-exchange sorbed electrolyte on Li⁺ self-diffusion coefficients was observed in the heterogeneous sulfocation exchanger KU-23.     

Self-diffusion of aluminium in the intermetallic compound Fe-48 at.% Al

The self-diffusion coefficient of Al in the B2-type intermetallic compound Fe-48 at.% Al has been determined using the intrinsic diffusion coefficients of Fe and Al and the self-diffusion coefficient of Fe with the help of the Darken-Manning relation. The self-diffusion coefficient of Al in Fe-48 at.% Al is estimated to be a factor of about 0.6 smaller than that of Fe, and the activation energy for the self-diffusion of Al is obtained to be 280 kJ mol^?1 which is a little larger than the value of 262 kJ mol^?1 for the self-diffusion of Fe, indicating that the diffusion mechanisms for both components are nearly equal.     

1H NMR study of water relaxation and self-diffusion in human serum albumin aqueous solutions

Summary Water proton spin-lattice relaxation and self-diffusion in aqueous solutions of human serum albumin have been studied by¹H NMR as a function of the protein concentration. Spin-lattice relaxation data, which display a nonlinear behaviour with the protein concentration, could be fitted with a two-phase model taking into account the experimentally determined hydration (?bound?) water values. Despite a similar trend is registered for the water self-diffusion coefficient, such a model has been found unable to explain the related experimental data taken as a function of the biomolecule concentration. On the other hand, the solute-induced proton self-diffusion decrease could be satisfactorily interpreted by postulating an enhanced probability of hydrogen-bond formation occurring within the ?vicinal? water surrounding the biomolecules for several hydration shells. The consistency within the two models is discussed in connection with the magnetic interactions occurring within the solute-solvent systems.     

Molecular dynamics study on water self-diffusion in aqueous mixtures of methanol,ethylene glycol and glycerol: investigations from the point of view of hydrogen bonding

Molecular dynamics simulations have been performed to investigate the aqueous binary mixtures of alcohols, including methanol, ethylene glycol (EG) and glycerol of molalities ranging from 1 to 5 m at the temperatures of 273, 288 and 298 K, respectively. The primary purpose of this paper is to investigate the mechanism of water self-diffusion in water-alcohol mixtures from the point of view of hydrogen bonding. The effects of temperature and concentration on water self-diffusion coefficient are evaluated quantitatively in this work. Temperature and concentration to some extent affect the hydrogen bonding statistics and dynamics of the binary mixtures. It is shown that the self-diffusion coefficient of water molecules decreases as the concentration increases or the temperature decreases. Moreover, calculations of mean square displacements of water molecules initially with different number n of H-bonds indicate that the water self-diffusion coefficient decreases as n increases. We also studied the aggregation of alcohol molecules by the hydrophobic alkyl groups. The largest cluster size of the alkyl groups clearly increases as the concentration increases, implying the emergence of a closely connected network of water and alcohols. The clusters of water and alcohol that interacted could block the movement of water molecules in binary mixtures. These findings provide insight into the mechanisms of water self-diffusion in aqueous binary mixtures of methanol, EG and glycerol.     

高分子溶液体系的自扩散系数的NMR测量

用核磁共振方法测量高聚物体系的自扩散系数是一种有效而直接的方法。本文报告了用核磁共振方法测量高分子在溶液中自扩散系数实验方法的研究结果,并对聚苯乙烯良溶液体系和θ溶液体系的自扩散现象进行了研究和比较,为半浓溶液范围的de-Gennes的"蠕动"理论提供了实验验证。