Pulsed Field Gradient Spin-echo Method Research Articles

Self-diffusion of water-cyclohexane mixtures in supercritical conditions as studied by NMR and molecular dynamics simulation.

The self-diffusion coefficients of water (Dw) and cyclohexane (Dch) in their binary mixtures were determined using the proton pulsed field gradient spin-echo method from medium to low densities in subcritical and supercritical conditions. The density (ρ), temperature (T), and water mole fraction (xw) are studied in the ranges 0.62-6.35 M (M = mol dm-3), 250-400 °C, and 0.109-0.994, respectively. A polynomial fitting function was developed for a scaled value of Ξ = ρDT-1/2 with ρ, T, and xw as variables in combination with a comprehensive molecular dynamics (MD) simulation. The NMR and MD results agree within 5% for water and 6% for cyclohexane, on average. The differences between Dw and Dch in the dependence on ρ, T, and xw are characterized by the activation energy Ea and the activation volume ΔVΞ ‡ expressed by the scaled fitting function. The decrease in the ratio Dw/Dch and the increase in the Ea of water with increasing xw are related to the increase in the number of hydrogen bonds (HBs). The Dw value for a solitary water molecule at a low xw is controlled by the solvation shell, most of which is occupied by nonpolar cyclohexane molecules that provide less friction as a result of weaker interactions with water. A microscopic diffusion mechanism is discussed based on an analysis of the HB number as well as the first-peak height of the radial distribution functions that are taken as measures of the potential of the mean field controlling self-diffusion.

Effect of CO2 dissolution on electrical conductivity and self-diffusion coefficients of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid

We have determined the electrical conductivity in CO2-saturated 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) at 298.1, 313.1 and 333.1K as a function of CO2 pressure. Moreover, self-diffusion coefficients of cation and anion in CO2-saturated [C4mim][PF6] have been measured at high pressures up to ∼15MPa and at a fixed temperature of 333.2K by 1H and 19F NMR using the pulsed field gradient spin-echo method. As CO2 dissolves in [C4mim][PF6], marked increases in all the three transport quantities were observed at lower pressure, and then they showed very slight changes at higher pressure. The correlation between the conductivity and the ionic diffusion coefficients has been discussed.

In situ pulsed-field gradient NMR determination of the size of oil bodies in vegetable seeds. Analysis of the effect of the gradient pulse length.

We report a pulsed-field gradient NMR study of the size of the oil bodies in lettuce seeds. The pulsed-field gradient spin-echo method (PFGSE) was applied to measure the self-diffusion coefficient of triacylglycerol molecules (TAG) inside the oil bodies. The confined nature of TAG diffusion is used to determine the size dispersion of the oil bodies. At long diffusion time, we measure a spin-echo attenuation that is related to the form factor of the confining volumes in the reciprocal q space, where q is proportional to the product of the gradient intensity and the length of the pulse gradient. Specific care was taken in analyzing the influence of the gradient pulse length delta on the shape of the PFGSE decay in order to construct the function corresponding to the short gradient pulse approximation (SGP). The SGP model gives an analytical framework for the PFGSE signal that enables the size distribution of the oil bodies to be determined. The SGP function was unambiguously obtained by varying the gradient pulse length delta in order to linearly extrapolate at delta = 0 the SGP limit. In this work, we also consider the Gaussian phase distribution (GPD) assumption that is often used to analyze confined diffusion experiments. Although the GPD assumption is known to be inaccurate in predicting the fine structure of the PFGSE function in q space, we point out that in the present case it can be used to take into account the finite value of delta. A log-normal distribution of the radius values was assumed in simulating the PFGNMR experiments since this type of distribution is observed in vegetable seeds by transmission electronic microscopy. From a practical and experimental standpoint, the NMR measurements reported here require no specific treatment of the seeds and the size of oil bodies is determined "in situ" on seeds poured into the NMR tube.

A Pulsed Field Gradient Spin-Echo Method for Diffusion Measurements in the Presence of Internal Gradients

Over the past decade several pulsed field gradient stimulated-echo methods have been presented for diffusion measurements in heterogeneous media. These methods have reduced or eliminated the coupling between the applied magnetic field gradient and a constant internal magnetic field gradient caused by susceptibility changes throughout the sample. For many research purposes thez-storage delay between the second and third π/2 RF pulse has been included in order to increase the decay of the echo attenuation to an appropriate level and to increase the signal-to-noise ratio by avoidingT2relaxation of the magnetization in parts of the pulse sequence. For these reasons a stimulated-echo method has been applied instead of a spin-echo method. When studying systems where it is necessary to keep the duration of the pulse sequence at a minimum, and one is not dependent on usingz-storage time to increase the echo attenuation or to study diffusion as a function of observation time, a spin-echo method should be chosen. Here we propose a bipolar pulsed field gradient spin-echo method which is well suited to this purpose, and preliminary diffusion measurements are presented as illustration.

Pulsed field gradient-spin echo NMR studies of water diffusion in a phospholipid model membrane

Water diffusion in the lamellar phase of egg phosphatidylcholine (egg PC)-water was studied by 1H NMR using the pulsed field gradient-spin echo method. The curvature of diffusion plots obtained with egg PC-water mixtures indicates that water diffusion is highly anisotropic with respect to lipid lamellae. This was confirmed by measurements made on macroscopically aligned egg PC-water as a function of orientation that categorically establish DII/DI >> .1, where the respective subscripts refer to parallel and perpendicular to the lipid bilayer. A smooth, monotonic dependence on water concentration was observed for water diffusion in aligned egg PC-water, varying at 25 degrees C from DII = 1.2 x 10(-10) m2 s 1 at n = 4.9 mol water/lipid to DII = 4.0 x 10(-10) m2 s-1 at n = 18.6 mol water/lipid. The diffusion is approximately a factor of 10 slower than in pure water because of water binding and restriction to translational motion within the aqueous layer. No evidence for a sudden drop in water diffusion coefficient at a specific water content, as previously reported with egg PC-water mixtures (Lange and Gary Bobo. 1974. J. Gen. Physiol 63:690-706), was detected. A morphological reorganization of lamellar domains, which in random orientational distribution comprise lipid-water mixtures, is the likely explanation. The study of aligned lipid-water systems is manifestly preferable.

Analysis of the PFG-SE NMR Experiments in Lyotropic Mesophases: The Hexagonal Case

Abstract The NMR Pulsed Field Gradient Spin-Echo method (PFG-SE) may be conveniently applied to the study of water self-diffusion in lyotropic liquid crystals, giving insight on their molecular organization. The technique has been widely used and mathematical descriptions of the experiments have been worked out which, although simple to visualize, may involve computer calculations rather cumbersome and time consuming. Here we derive a mathematical expression giving the echo attenuation in a PFG-SE experiment which is formally compact and easy to handle by computer simulations technique. Its application to hexagonal mesophases is discussed as an example of how to handle complex situations.

Pulsed field gradient NMR for the study of the structure of membrane systems

The usefulness of the pulsed field gradient spin-echo method in determining structural parameters in heterogeneous systems has been examined. Theoretical analysis and computer simulations of a rectangular lattice with prohibited nodes have been carried out. From the time dependences of diffusion coefficients of small molecules moving in inhomogeneous systems the characteristic dimensions of the structure of the system could be obtained. The self-diffusion coefficients of water and glycerol molecules in synthetic membranes have been studied experimentally.

Measurement of self-diffusion coefficients in extractant systems using the FTNMR technique

The Fourier-transform NMR pulsed field gradient spin-echo method was applied to the measurement of the self-diffusion coefficients of the active components in the commercial extractants LIX65N, LIX63 and Cyanex 272. CCl 4 and CDCl 3 were used as solvents. The self-diffusion coefficients in 0.16 M CDC1 3 solutions are 8.2, 9.2 and 6.7 × 10 −10 m 2 s −1, respectively.