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.     

Spiraling spin structure in an exchange-coupled antiferromagnetic layer

Using trilayers of permalloy/FeMn/Co with various thicknesses t(AF) of the antiferromagnetic FeMn, we have observed evidence of a spiraling spin structure within FeMn. For t(AF)<90 A, the turn angle straight theta of the spiral varies as straight theta = (1.76 degrees /A)t(AF).     

Tortuosity measurement and the effects of finite pulse widths on xenon gas diffusion NMR studies of porous media.

We have extended the utility of NMR as a technique to probe porous media structure over length scales of approximately 100-2000 microm by using the spin 1/2 noble gas 129Xe imbibed into the system's pore space. Such length scales are much greater than can be probed with NMR diffusion studies of water-saturated porous media. We utilized Pulsed Gradient Spin Echo NMR measurements of the time-dependent diffusion coefficient, D(t), of the xenon gas filling the pore space to study further the measurements of both the pore surface-area-to-volume ratio, S/V(p), and the tortuosity (pore connectivity) of the medium. In uniform-size glass bead packs, we observed D(t) decreasing with increasing t, reaching an observed asymptote of approximately 0.62-0.65D(0), that could be measured over diffusion distances extending over multiple bead diameters. Measurements of D(t)/D(0) at differing gas pressures showed this tortuosity limit was not affected by changing the characteristic diffusion length of the spins during the diffusion encoding gradient pulse. This was not the case at the short time limit, where D(t)/D(0) was noticeably affected by the gas pressure in the sample. Increasing the gas pressure, and hence reducing D(0) and the diffusion during the gradient pulse served to reduce the previously observed deviation of D(t)/D(0) from the S/V(p) relation. The Pade approximation is used to interpolate between the long and short time limits in D(t). While the short time D(t) points lay above the interpolation line in the case of small beads, due to diffusion during the gradient pulse on the order of the pore size, it was also noted that the experimental D(t) data fell below the Pade line in the case of large beads, most likely due to finite size effects.     

Sensitivity enhanced recoupling experiments in solid-state NMR by gamma preparation

In this paper, we introduce a class of dipolar recoupling experiments under magic angle spinning (MAS), which use gamma dependent antiphase polarization during the t1 evolution period. We show that this helps us to design dipolar recoupling experiments that transfer both components of the transverse magnetization of spin S to a coupled spin I in the mixing step of a 2D NMR experiment. We show that it is possible to design such transfer schemes and make them insensitive to the orientation dependency of the couplings in powders. This helps us to develop sensitivity enhanced 2D NMR experiments of powder samples under MAS.     

Measurement of the local 1H spin-diffusion coefficient in polymers

Proton spin diffusion is widely used to determine domain sizes in heterogeneous organic solids. For an accurate analysis, spin diffusion coefficients are required. However, in most cases they are not directly measured, but instead derived from model systems. The effects of magic-angle spinning (MAS), mobility, or spin-lock fields on spin-diffusion coefficients have also been difficult to quantify. In this work, direct measurement of local (1)H spin-diffusion coefficients in any rigid polymer is achieved in experiments with heteronuclear dephasing of the (1)H magnetization, a mixing time for (1)H spin diffusion, and (13)C detection after cross-polarization. In the presence of (1)H homonuclear decoupling and (13)C 180 degrees-pulse recoupling, each (13)C spin dephases a significant number (3-20) of protons, depending on the dephasing time. For (13)C and other sufficiently dilute heteronuclei, the dephasing of the protons is described by simple spin-pair REDOR curves. As a result, every (13)C nucleus will "burn" a spherical hole of known diameter and profile into the proton magnetization distribution. (1)H spin diffusion into the hole during the mixing time can be monitored and simulated accurately for every resolved (13)C site, with the spin-diffusion coefficient as the only significant unknown parameter. By varying the dephasing time, holes with diameters of 0.4-0.8 nm can be burned into the proton magnetization profile and thus the dependence of the local spin-diffusion coefficients on the proton density or partial mobility can be explored. The effects of transverse or magic-angle spin-lock fields on spin diffusion can be quantified conveniently by this method. Analytical and numerical fits yield short-range spin-diffusion coefficients of 0.2-0.5 nm(2)/ms on the 0.5-nm scale, which is smaller than the value of 0.8 nm(2)/ms for organic solids previously measured on the 10-nm scale.     

Interaction-driven spin precession in quantum-dot spin valves

We analyze spin-dependent transport through spin valves composed of an interacting quantum dot coupled to two ferromagnetic leads. The spin on the quantum dot and the linear conductance as a function of the relative angle theta of the leads' magnetization directions is derived to lowest order in the dot-lead coupling strength. Because of the applied bias voltage spin accumulates on the quantum dot, which for finite charging energy experiences a torque, resulting in spin precession. The latter leads to a nontrivial, interaction-dependent, theta dependence of the conductance. In particular, we find that the spin-valve effect is reduced for all theta not equal pi.     

Dynamics of paramagnetic agents by off-resonance rotating frame technique

Off-resonance rotating frame technique offers a novel tool to explore the dynamics of paramagnetic agents at high magnetic fields (B0 > 3T). Based on the effect of paramagnetic relaxation enhancement in the off-resonance rotating frame, a new method is described here for determining the dynamics of paramagnetic ion chelates from the residual z-magnetizations of water protons. In this method, the dynamics of the chelates are identified by the difference magnetization profiles, which are the subtraction of the residual z-magnetization as a function of frequency offset obtained at two sets of RF amplitude omega(1) and pulse duration tau. The choices of omega(1) and tau are guided by a 2-D magnetization map that is created numerically by plotting the residual z-magnetization as a function of effective field angle theta and off-resonance pulse duration tau. From the region of magnetization map that is the most sensitive to the alteration of the paramagnetic relaxation enhancement efficiency R(1rho)/R1, the ratio of the off-resonance rotating frame relaxation rate constant R(1rho) verse the laboratory frame relaxation rate constant R(1), three types of difference magnetization profiles can be generated. The magnetization map and the difference magnetization profiles are correlated with the rotational correlation time tauR of Gd-DTPA through numerical simulations, and further validated by the experimental data for a series of macromolecule conjugated Gd-DTPA in aqueous solutions. Effects of hydration water number q, diffusion coefficient D, magnetic field strength B0 and multiple rotational correlation times are explored with the simulations of the magnetization map. This method not only provides a simple and reliable approach to determine the dynamics of paramagnetic labeling of molecular/cellular events at high magnetic fields, but also a new strategy for spectral editing in NMR/MRI based on the dynamics of paramagnetic labeling in vivo.     

Solid-state NMR spectroscopy using the lost I spin magnetization in polarization transfer experiments

A variation of the cross polarization (CP) experiment is discussed. The method requires two scans where the difference signal is equivalent to the I spin magnetization that is transferred to the S spins. The acquired signal is equivalent to F1 sum projection of a two-dimensional (2D) heteronuclear correlation experiment and is obtained by just two scans without the need to increment the indirect time domain t(1). Any polarization transfer method and any kind of spin manipulations during the t(1) incrementation period of a 2D NMR experiment can be applied. The method allows fast measurements of the CP transfer, particularly if various S spins signal overlap and is good for spectral editing of I spin signals with contact to S spins. Various examples for biomaterials are presented. Most importantly, this novel approach is ideal for detailed investigations of organic-mineral interfaces in bone, here demonstrated for O-phospho-l-serine as simple model compound.     

2D CP/MASC Isotropic Chemical Shift Correlation Established byH Spin Diffusion

A new 2D solid-state CP/MAS¹³C NMR exchange experiment for through-space isotropic chemical shift correlation is proposed and demonstrated. Through-space correlation is established via a second cross polarization from¹³C to¹H and subsequent¹H spin diffusion. A third cross polarization results in the final¹³C–¹³C isotropic chemical shift correlation. The¹H spin diffusion time is a variable parameter allowing different mean square magnetization displacements to be probed. Experimental results on mixtures of differently¹³C-labeled alanine and polyethylene indicate that this site-selective 2D technique can be used to characterize domain sizes and proximities over a wide range of length scales (1–200 nm) in solids such as polymers or biological materials.     

Conformally invariant fractals and potential theory

The multifractal (MF) distribution of the electrostatic potential near any conformally invariant fractal boundary, like a critical O(N) loop or a Q-state Potts cluster, is solved in two dimensions. The dimension &fcirc;(straight theta) of the boundary set with local wedge angle straight theta is &fcirc;(straight theta) = pi / straight theta-25-c / 12 (pi-straight theta)(2) / straight theta(2pi-straight theta), with c the central charge of the model. As a corollary, the dimensions D(EP) of the external perimeter and D(H) of the hull of a Potts cluster obey the duality equation (D(EP)-1) (D(H)-1) = 1 / 4. A related covariant MF spectrum is obtained for self-avoiding walks anchored at cluster boundaries.     

Homo- and heteronuclear 2D NMR approaches to analyse a mixture of deuterated unlike/like stereoisomers using weakly ordering chiral liquid crystals

We describe several homo- and heteronuclear 2D NMR strategies dedicated to the analysis of anisotropic (2)H spectra of a mixture of dideuterated unlike/like stereoisomers with two remote stereogenic centers, using weakly orienting chiral liquid crystals. To this end, we propose various 2D correlation experiments, denoted "D(H)(n)D" or "D(H)(n)C" (with n=1, 2), that involve two heteronuclear polarization transfers of INEPT-type with one or two proton relays. The analytical expressions of correlation signals for four pulse sequences reported here were calculated using the product-operators formalism for spin I=1 and S=1/2. The features and advantages of each scheme are presented and discussed. The efficiency of these 2D sequences is illustrated using various deuterated model molecules, dissolved in organic solutions of polypeptides made of poly-gamma-benzyl-L-glutamate (PBLG) or poly-epsilon-carbobenzyloxy-L-lysine (PCBLL) and NMR numerical simulations.     

Measurement of thermal diffusivity by magnetic resonance imaging

Nuclear magnetic resonance (NMR) may be used for monitoring temperature changes within samples based on measurements of relaxation times, the diffusion coefficient of liquids, proton resonance frequency or phase shifts. Such methods may be extended to the explicit measurement of the thermal diffusivity of materials by NMR imaging. A method based on measuring nuclear spin phase shifts or changes in the equilibrium nuclear magnetization has been developed for measuring transient thermal diffusion effects and thermal diffusivity with potential applications in NMR thermotherapy and materials science. In this method, a thermal pulse is applied to a medium, and the resultant temporal variations of the nuclear spin phase or of the magnitude of the nuclear magnetization produced by the thermal pulse are monitored at a spatial distance. The results obtained on common fluids agree well with the data from other methods.     

3He spin diffusion measurements in 3He- 4He mixture films

3He spin diffusion measurements for 3He-4He mixture films on Nuclepore are reported as a function of 3He coverage for 0. 030相似文献   

On the role of experimental imperfections in constructing 1H spin diffusion NMR plots for domain size measurements

We discuss the precision of 1D chemical-shift-based ¹H spin diffusion NMR experiments as well as straightforward experimental protocols for reducing errors. The ¹H spin diffusion NMR experiments described herein are useful for samples that contain components with significant spectral overlap in the ¹H NMR spectrum and also for samples of small mass (<1 mg). We show that even in samples that display little spectral contrast, domain sizes can be determined to a relatively high degree of certainty if common experimental variability is accounted for and known. In particular, one should (1) measure flip angles to high precision (≈±1° flip angle), (2) establish a metric for phase transients to ensure their repeatability, (3) establish a reliable spectral deconvolution procedure to ascertain the deconvolved spectra of the neat components in the composite or blend spin diffusion spectrum, and (4) when possible, perform 1D chemical-shift-based ¹H spin diffusion experiments with zero total integral to partially correct for errors and uncertainties if these requirements cannot fully be implemented. We show that minimizing the degree of phase transients is not a requirement for reliable domain size measurement, but their repeatability is essential, as is knowing their contribution to the spectral offset (i.e. the J₁ coefficient). When performing experiments with zero total integral in the spin diffusion NMR spectrum with carefully measured flip angles and known phase transient effects, the largest contribution to error arises from an uncertainty in the component lineshapes which can be as high as 7%. This uncertainty can be reduced considerably if the component lineshapes deconvolved from the composite or blend spin diffusion spectra adequately match previously acquired pure component spectra.     

NMR evidence for the persistence of a spin superlattice beyond the 1/8 magnetization plateau in SrCu2(BO3)_{2}

We present 11B NMR studies of the 2D frustrated dimer spin system SrCu2(BO3)_{2} in the field range 27-31 T covering the upper phase boundary of the 1/8 magnetization plateau, identified at 28.4 T. Our data provide a clear evidence that above 28.4 T the spin superlattice of the 1/8 plateau is modified but does not melt even though the magnetization increases. Although this is precisely what is expected for a supersolid phase, the microscopic nature of this new phase is much more complex. We discuss the field-temperature phase diagram on the basis of our NMR data.     

Spin-state-selective excitation in selective 1D inverse NMR experiments

A general and very simple strategy for achieving clean spin-state-selective excitation with full sensitivity in carbon-selective gradient-enhanced 1D HMQC and HSQC pulse schemes is presented. The incorporation of an additional hard 90 degrees (13)C pulse applied along a specific orthogonal axis just prior to acquisition into the conventional sequences allows us to select a simultaneous coherence transfer pathway which usually is not detected. The superimposition of this resulting antiphase magnetization to the conventional in-phase magnetization gives the exclusive excitation of the directly attached proton showing only the alpha or beta spin state of the passive (13)C nucleus. The propagation of this particular spin state to other protons can be accomplished by adding any homonuclear mixing process just after this supplementary pulse. Such an approach affords a suite of powerful selective 1D (13)C-edited NMR experiments which are helpful for resonance assignment purposes in overcrowded proton spin systems and also for the accurate determination of the magnitude and sign of long-range proton-carbon coupling constants in CH spin sytems for samples at natural abundance. Such measurements are performed by measuring the relative displacement of relayed signals in the corresponding alpha and beta 1D subspectra.     

Spin-diffusion NMR at low field for the study of multiphase solids

The use of spin-diffusion NMR for the measurement of domain sizes in multiphase materials is becoming increasingly popular, in particular for the study of heterogeneous polymers. Under conditions where T(1) relaxation can be neglected, which is mostly the case at high field, analytical and approximate solutions to the evolution of spin diffusion are available. In order to extend the technique to more general conditions, we performed a comprehensive study of the diffusion of magnetization in a model copolymer at low field, where T(1) tends to be of the same order of magnitude as the typical spin-diffusion time. In order to study the effects of T(1) and to delineate the optimal T(1) values for back correction prior to applying the initial-rate approximation, we developed a numerical simulation based on the diffusion equation and including longitudinal relaxation. We present and discuss the limits of simple correction strategies for initial-slope analysis based on apparent relaxation times from saturation-recovery experiments or the spin-diffusion experiments themselves. Our best strategy faithfully reproduces domain sizes obtained by both TEM investigations and full simultaneous fitting of spin-diffusion and saturation-recovery curves. Full fitting of such independent data sets not only yields correct domain sizes, but also the true longitudinal relaxation times, as well as spin-diffusion coefficients. Effects of interphases with distinct mobility on spin-diffusion curves, as well as practical hints concerning the reliable component decomposition of the detected low-resolution FID signal by help of different magnetization filters are also discussed in detail.     

Correction of spin diffusion during iterative automated NOE assignment

Indirect magnetization transfer increases the observed nuclear Overhauser enhancement (NOE) between two protons in many cases, leading to an underestimation of target distances. Wider distance bounds are necessary to account for this error. However, this leads to a loss of information and may reduce the quality of the structures generated from the inter-proton distances. Although several methods for spin diffusion correction have been published, they are often not employed to derive distance restraints. This prompted us to write a user-friendly and CPU-efficient method to correct for spin diffusion that is fully integrated in our program ambiguous restraints for iterative assignment (ARIA). ARIA thus allows automated iterative NOE assignment and structure calculation with spin diffusion corrected distances. The method relies on numerical integration of the coupled differential equations which govern relaxation by matrix squaring and sparse matrix techniques. We derive a correction factor for the distance restraints from calculated NOE volumes and inter-proton distances. To evaluate the impact of our spin diffusion correction, we tested the new calibration process extensively with data from the Pleckstrin homology (PH) domain of Mus musculus beta-spectrin. By comparing structures refined with and without spin diffusion correction, we show that spin diffusion corrected distance restraints give rise to structures of higher quality (notably fewer NOE violations and a more regular Ramachandran map). Furthermore, spin diffusion correction permits the use of tighter error bounds which improves the distinction between signal and noise in an automated NOE assignment scheme.     

Spatial persistence of fluctuating interfaces

We show that the probability, P0(l), that the height of a fluctuating (d+1)-dimensional interface in its steady state stays above its initial value up to a distance l, along any linear cut in the d-dimensional space, decays as P0(l) approximately l(theta). Here straight theta is a "spatial" persistence exponent, and takes different values, straight theta(s) or straight theta(0), depending on how the point from which l is measured is specified. These exponents are shown to map onto corresponding temporal persistence exponents for a generalized d = 1 random-walk equation. The exponent straight theta(0) is nontrivial even for Gaussian interfaces.     

Fractional magnetization plateaus and magnetic order in the Shastry-Sutherland magnet TmB4

We investigate the phase diagram of TmB4, an Ising magnet on a frustrated Shastry-Sutherland lattice, by neutron diffraction and magnetization experiments. At low temperature we find Néel order at low field, ferrimagnetic order at high field, and an intermediate phase with magnetization plateaus at fractional values M/M_(sat)=1/7,1/8,1/9,... and spatial stripe structures. Using an effective S=1/2 model and its equivalent two-dimensional fermion gas we suggest that the magnetic properties of TmB4 are related to the fractional quantum Hall effect of a 2D electron gas.