Modelling of self-diffusion and relaxation time NMR in multicompartment systems with cylindrical geometry

Multicompartment characteristics of relaxation and diffusion in a model for (plant) cells and tissues have been simulated as a means to test separating the signal into a set of these compartments. A numerical model of restricted diffusion and magnetization relaxation behavior in PFG-CPMG NMR experiments, based on Fick's second law of diffusion, has been extended for two-dimensional diffusion in systems with concentric cylindrical compartments separated by permeable walls. This model is applicable to a wide range of (cellular) systems and allows the exploration of temporal and spatial behavior of the magnetization with and without the influence of gradient pulses. Numerical simulations have been performed to show the correspondence between the obtained results and previously reported studies and to investigate the behavior of the apparent diffusion coefficients for the multicompartment systems with planar and cylindrical geometry. The results clearly demonstrate the importance of modelling two-dimensional diffusion in relation to the effect of restrictions, permeability of the membranes, and the bulk relaxation within the compartments. In addition, the consequences of analysis by multiexponential curve fitting are investigated.     

Modeling of Self-Diffusion and Relaxation Time NMR in Multi-Compartment Systems

The theory of pulsed field gradient (pfg) NMR applied to molecules in cellular systems which contain different subcellular compartments separated by permeable membranes, acting as diffusion barriers, has been extended. A numerical model of restricted diffusion and magnetization relaxation behavior in pfg-CPMG NMR experiments, based on the Fick's second law of diffusion, is presented. This model is applicable to a wide range of systems and allows the exploration of temporal and spatial behavior of the magnetization with and without the influence of gradient pulses. Results of the numerical experiments show their correspondence to the previously observed ones and demonstrate the importance of the inclusion of the time domain data in analyzing diffusion measurements.     

CPMG relaxation by diffusion with constant magnetic field gradient in a restricted geometry: numerical simulation and application

Carr-Purcell-Meiboom-Gill (CPMG) measurements are the primary nuclear magnetic resonance (NMR) technique used for evaluating formation properties and reservoir fluid properties in the well logging industry and laboratory sample analysis. The estimation of bulk volume irreducible (BVI), permeability, and fluid type relies on the accurate interpretation of the spin-spin relaxation time (T(2)) distribution. The interpretation is complicated when spin's self-diffusion in an inhomogeneous field and restricted geometry becomes dominant. The combined effects of field gradient, diffusion, and a restricted geometry are not easily evaluated analytically. We used a numerical method to evaluate the dependence of the free and restricted diffusion on the system parameters in the absence of surface relaxation, which usually can be neglected for the non-wetting fluids (e.g., oil or gas). The parameter space that defines the relaxation process is reduced to two dimensionless groups: D* and tau*. Three relaxation regimes: free diffusion, localization, and motionally averaging regimes are identified in the (log(10)D*, log(10)tau*) domain. The hypothesis that the normalized magnetization, M*, relaxes as a single exponential with a constant dimensionless relaxation time T*(2) is justified for most regions of the parameter space. The numerical simulation results are compared with the analytical solutions from the contour plots of T*(2). The locations of the boundaries between different relaxation regimes, derived from equalizing length scales, are challenged by observed discrepancies between numerical and analytical solutions. After adjustment of boundaries by equalizing T*(2), numerical simulation result and analytical solution match each other for every relaxation regime. The parameters, fluid diffusivity and pore length, can be estimated from analytical solutions in the free diffusion and motionally averaging regimes, respectively. Estimation of the parameters near the boundaries of the regimes may require numerical simulation.     

Relaxation of nuclear magnetization in a nonuniform magnetic field gradient and in a restricted geometry

We study the influence of restriction on Carr-Purcell-Meiboom-Gill spin echo response of magnetization of spins diffusing in a bounded region in the presence of a nonuniform magnetic field gradient. We consider two fields in detail-a parabolic field which, like the uniform-gradient field, scales with the system size, and a cosine field which remains bounded. Corresponding to three main length scales, the pore size, L(S), the dephasing length, L(G), and the diffusion length during half-echo time, L(D), we identify three main regimes of decay of the total magnetization: motionally averaged, localization, and short-time. In the short-time regime (L(D) < L(S), L(G)), we confirm that the leading order behavior is controlled by the average of the square of the gradient, (nablaB(z))(2), and in the motionally averaged regime (MAv), where L(S) < L(D), L(G), by (integral dxB(z))(2). We verify numerically that two different fields for which those two averages are identical result in very similar decay profiles not only in the limits of short and long times but also in the intermediate times, with important practical implications. In the motionally averaged regime we found that previous estimates of the decay exponent for the parabolic field, based on a soft-boundary condition, are significantly altered in the presence of a more realistic, hard wall. We find the scaling of the decay exponent in the MAv regime with pore size to be L(2)(S) for the cosine field and L(6)(S) for the parabolic field, as contrasted with the linear gradient scaling of L(4)(S). In the localization regime, for both the cosine and the parabolic fields, the decay exponent depends on a fractional power of the gradient, implying a breakdown of the second cumulant or the Gaussian phase approximation. We also examined the validity of time-evolving the total magnetization according to a distribution of effective local gradients and found that such approximation works well only in the short-time regime and breaks down strongly for long times. Copyright 2000 Academic Press.     

Measurements of restricted diffusion using an oscillating gradient spin-echo sequence

An oscillating gradient spin-echo (OGSE) pulse sequence was used to measure the apparent diffusion coefficient (D(app)) of water in the short diffusion time regime in the presence of restrictions. The diffusion coefficients of water in a simple water sample and a water and oil mixture were measured to be the same for different periods of the gradient oscillation, as expected when there are no restriction effects. The D(app) of water in the spaces between closely packed beads was also measured as a function of the gradient oscillation periods in the range 11 to 80 ms. The D(app) of water in restricted systems varies with the period of the gradient oscillation and the dispersion depends on the scale of the restriction. For a sample of packed beads of diameter 9.1 +/- 0.7 microm, the pore surface-to-volume ratio was estimated experimentally by this method to be 1.3 +/- 0.1 microm(-1), corresponding to a mean pore diameter of 6.4 +/- 0.7 microm. A Monte Carlo computer simulation of the NMR OGSE signal from the spins diffusing in a system of compartments was also implemented and the D(app) demonstrated similar behavior with gradient oscillation periods.     

Investigation of multicomponent diffusion in cat brain using a combined MTC-DWI approach

In this study, multiple-component water diffusion in the cat brain is investigated using an approach that combines diffusion-weighted images using multiple b values with magnetization transfer contrast (MTC). The MTC allows filter of signal originating from water molecules that rapidly exchange with binding sites on large macromolecular structures, and in brain white matter, it is assumed that a significant portion of the MTC is due to the interaction of water with the extraaxonal myelin sheath. Henceforth, multicomponent analysis of diffusion curves with and without MTC may shed light on the contribution of the extraaxonal water to the diffusion signal and on the relationship between diffusion components and tissue compartments in the brain. When a biexponential model was applied to the data, the volume fractions of the two diffusion components changed significantly in white matter with the application of the MTC. These changes are then discussed in the frame of tissue components and the possible interaction with the myelin sheath.     

Self-Diffusion in Cell Membranes in the Long Time Regime

We consider the process of self-diffusion in the cellular structure in the presence of permeable barriers in long time regime. Based on the most general concepts of the translation mobility and geometry of a heterogeneous system, an expression for the self-diffusion coefficient of liquid molecules in such a medium in a long time regime was derived. We have shown that the value of the self-diffusion coefficient in the long-time limit is determined by the probability of interaction of the diffusant molecule with an obstacle. We obtained an expression for the probability of such interaction as a function of the surface-to-volume ratio (S/V). Comparing the obtained analytical expression with the results of computer simulation was performed. Shown the exponential dependence of the self-diffusion coefficient on the barrier pinning density.     

High-resolution DOSY NMR with spins in different chemical surroundings: influence of particle exchange

The effect of chemical exchange in the diffusion-ordered (DOSY) spectra of a two-site system in the slow-exchange limit with respect to the chemical shift is studied. The problem is addressed both theoretically and experimentally. The relationship between diffusion time (t) and mean lifetimes (tau) is studied by the simulation of the magnetization attenuations as a function of the gradient strength, under PFG conditions. The influence of the difference in populations and diffusion coefficients of the two sites is also considered. In analogy to the limiting cases of fast- and slow-exchange with respect to the chemical shift, limiting cases with respect to the diffusion dimension are defined. The slow-exchange limit in diffusion corresponds to the relation of t and tau that allows us to observe the two spins in exchange associated with the individual diffusion coefficients of the two sites when no exchange is present. The fast-exchange limit in diffusion is reached when the relation of t and tau is such that the two spins present the same apparent diffusion coefficient. By using a model system consisting of water/t-butanol it is shown that by recording several DOSY experiments with increasing diffusion times it is possible to estimate the value of the exchange rate.     

Ferromagnetic resonance of horse spleen ferritin: core blocking and surface ordering temperatures.

In nature, ferritin, an iron-storage molecule, is found in species ranging from bacteria to man. In the past 50 years its chemical, physical, and magnetic properties have been studied, searching to relate function and structure. Horse spleen ferritin has been investigated by EPR at temperatures between 7 and 290 K. These spectra change from an isotropic line at 290 K to an anisotropic one at 19 K, with a behavior consistent with a system of particles that undergoes superparamagnetic relaxation. A blocking temperature of (116+/-9) K is obtained. A new temperature-dependent signal is observed in the low field region at temperatures higher than 80 K. At 7 K no EPR signal appears, suggesting (14+/-5) K as the Néel temperature of surface spins. Analysis of the temperature dependence of the distance between EPR lines extrema, under the view of two theoretical models, allowed the evaluation of magnetic parameters. These parameters are 2K/M=2.7 x 10(3) Oe and MV=1.9 x 10(-17) emu or K/M=1.3 x 10(3) Oe and MV=2.0 x 10(-17) emu, where K is the anisotropy energy per unit volume, M is the sample magnetization, and V is the superparamagnetic core volume. The results are also discussed, and some structural models in the literature are considered.     

Spin-lattice relaxation and a fast T1-map acquisition method in MRI with transient-state magnetization

The magnetization under the spin-lattice relaxation and the nuclear magnetic resonance radiofrequency (RF) pulses is calculated for a signal RF pulse train and for a sequence of multiple RF pulse-trains. It is assumed that the transverse magnetization is zero when each RF pulse is applied. The result expressions can be grouped into two terms: a decay term, which is proportional to the initial magnetization M0, and a recovery term, which has no M0 dependence but strongly depends on the spin-lattice relaxation and the equilibrium magnetization Meq. In magnetic resonance pulse sequences using magnetization in transient state, the recovery term produces artifacts and can seriously degrade the function of the preparation sequence for slice selection, contrast weighting, phase encoding, etc. This work shows that the detrimental effect can be removed by signal averaging in an eliminative fashion. A novel fast data acquisition method for constructing the spin-lattice relaxation (T1) map is introduced. The method has two features: (i) By using eliminative averaging, the curve to fit the T1 value is a decay exponential function rather than a recovery one as in conventional techniques; therefore, the measurement of Meq is not required and the result is less susceptible to the accuracy of the inversion RF pulse. (ii) The decay exponential curve is sampled by using a sequence of multiple pulse-trains. An image is reconstructed from each train and represents a sample point of the curve. Hence a single imaging sequence can yield multiple sample points needed for fitting the T1 value in contrast to conventional techniques that require repeating the imaging sequence for various delay values but obtain only one sample point from each repetition.     

Gaussian approximation in the theory of MR signal formation in the presence of structure-specific magnetic field inhomogeneities

A detailed theoretical analysis of the free induction decay (FID) and spin echo (SE) MR signal formation in the presence of mesoscopic structure-specific magnetic field inhomogeneities is developed in the framework of the Gaussian phase distribution approximation. The theory takes into account diffusion of nuclear spins in inhomogeneous magnetic fields created by arbitrarily shaped magnetized objects with permeable boundaries. In the short-time limit the FID signal decays quadratically with time and depends on the objects' geometry only through the volume fraction, whereas the SE signal decays as 5/2 power of time with the coefficient depending on both the volume fraction of the magnetized objects and their surface-to-volume ratio. In the motional narrowing regime, the FID and SE signals for objects of finite size decay mono-exponentially; a simple general expression is obtained for the relaxation rate constant deltaR2. In the case of infinitely long cylinders in the motional narrowing regime the theory predicts non-exponential signal decay lnS approximately -tlnt in accordance with previous results. For specific geometries of the objects (spheres and infinitely long cylinders) exact analytical expressions for the FID and SE signals are given. The theory can be applied, for instance, to biological systems where mesoscopic magnetic field inhomogeneities are induced by deoxygenated red blood cells, capillary network, contrast agents, etc.     

Persistence of manifolds in nonequilibrium critical dynamics

We study the persistence probability P(t) that, starting from a random initial condition, the magnetization of a d'-dimensional manifold of a d-dimensional spin system at its critical point does not change sign up to time t. For d'>0 we find three distinct late-time decay forms for P(t): exponential, stretched exponential, and power law, depending on a single parameter zeta=(D-2+eta)/z, where D=d-d' and eta,z are standard critical exponents. In particular, we predict that for a line magnetization in the critical d=2 Ising model, P(t) decays as a power law while, for d=3, P(t) decays as a power of t for a plane magnetization but as a stretched exponential for a line magnetization. Numerical results are consistent with these predictions.     

Diffusion and relaxation effects in general stray field NMR experiments

We analyze the evolution of magnetization following any series of radiofrequency pulses in strongly inhomogeneous fields, with particular attention to diffusion and relaxation effects. When the inhomogeneity of the static magnetic field approaches or exceeds the strength of the RF field, the magnetization has contributions from different coherence pathways. The diffusion or relaxation induced decay of the signal amplitude is in general nonexponential, even if the sample has single relaxation times T(1), T(2) and a single diffusion coefficient D. In addition, the shape of the echo depends on diffusion and relaxation. It is possible to separate contributions from different coherence pathways by phase cycling of the RF pulses. The general analysis is tested on stray field measurements using two different pulse sequences. We find excellent agreement between measurements and calculations. The inversion recovery sequence is used to study the relaxation effects. We demonstrate two different approaches of data analysis to extract the relaxation time T(1). Finite pulse width effects on the timing of the echo formation are also studied. Diffusion effects are analyzed using the Carr--Purcell--Meiboom--Gill sequence. In a stray field of a constant gradient g, we find that unrestricted diffusion leads to nonexponential signal decay versus echo number N, but within experimental error the diffusion attenuation is still only a function of g(2)Dt(3)(E)N, where t(E) is the echo spacing.     

An MRI perfusion model incorporating nonequilibrium exchange between vascular and extravascular compartments

A model of MRI signal intensity which is a function of perfusion is developed based upon the assumption that biological tissue can be represented by a blood and tissue compartment. The longitudinal magnetization is derived from the Bloch equations which are modified to model the magnetization in both the blood and tissue as a function of the following physiological parameters: blood flow velocity; perfusion fraction, which in the model is parameterized in terms of the ratio of the cross-sectional areas of the tissue and blood compartments; diffusion; rate of exchange between the blood and extravascular tissue compartments. Simulations of slice profiles excited by a repetitive sequence of 90 degrees slice-selective pulses show that the signal intensity in the blood and tissue compartments are modulated by the physiological parameters. A key factor in the modulation of the MRI signal is a time-of-flight effect whereby unexcited spins perfuse the excited region and exchange with blood and tissue compartments, thus immediately increasing the slice signal intensity but also delaying the spin exits from the slice, thereby decreasing their contribution to slice signal intensity in future repetitive pulse measurements.     

Random-walk technique for simulating NMR measurements and 2D NMR maps of porous media with relaxing and permeable boundaries

We revisit random-walk methods to simulate the NMR response of fluids in porous media. Simulations reproduce the effects of diffusion within external inhomogeneous background magnetic fields, imperfect and finite-duration B(1) pulses, T(1)/T(2) contrasts, and relaxing or permeable boundaries. The simulation approach consolidates existing NMR numerical methods used in biology and engineering into a single formulation that expands on the magnetic-dipole equivalent of spin packets. When fluids exhibit low T(1)/T(2) contrasts and when CPMG pulse sequences are used to acquire NMR measurements, we verify that classical NMR numerical models that neglect T(1) effects accurately reproduce surface magnetization decays of saturated granular porous media regardless of the diffusion/relaxation regime. Currently, analytical expressions exist only for the case of arbitrary pore shapes within the fast-diffusion limit. However, when fluids include several components or when magnetic fields are strongly inhomogeneous, we show that simulations results obtained using the complete set of Bloch's equations differ substantially from those of classical NMR models. In addition, our random-walk formulation accurately reproduces magnetization echoes stemming from coherent-pathway calculations. We show that the random-walk approach is especially suited to generate parametric multi-dimensional T(1)/T(2)/D NMR maps to improve the characterization of pore structures and saturating fluids.     

Quantum phase diffusions of a spinor condensate

We discuss the quantum phases and their diffusion in a spinor-1 atomic Bose-Einstein condensate. For ferromagnetic interactions, we obtain the exact ground state distribution of the phase fluctuations corresponding to the total atom number (N), the magnetization (M), and the alignment (or hypercharge) (Y) of the system. The mean-field ground state is shown to be stable against these fluctuations, which dynamically recover the two continuous symmetries associated with the conservation of N and M as in current experiments.     

Measurement of the relaxation rate of the magnetization in Mn12O12-acetate using proton NMR echo

We present a novel method to measure the relaxation rate W of the magnetization of Mn 12O (12)-acetate (Mn12) magnetic molecular cluster in its S = 10 ground state at low T. It is based on the observation of an exponential growth in time of the proton NMR signal during the thermal equilibration of the magnetization of the molecules. We can explain the novel effect with a simple model which relates the intensity of the proton echo signal to the microscopic reversal of the magnetization of each individual Mn12 molecule during the equilibration process. The method should find wide application in the study of magnetic molecular clusters in off-equilibrium conditions.