A new view of the spin echo diffusive diffraction on porous structures

Analysis with the characteristic functional of stochastic motion is used for the gradient spin echo measurement of restricted motion to clarify details of the diffraction-like effect in a porous structure. It gives the diffusive diffraction as an interference of spin phase shifts due to the back-flow of spins bouncing at the boundaries, when mean displacement of scattered spins is equal to the spin phase grating prepared by applied magnetic field gradients. The diffraction patterns convey information about morphology of the surrounding media at times long enough that opposite boundaries are restricting displacements. The method explains the dependence of diffraction on the time and width of gradient pulses, as observed at the experiments and the simulations. It also enlightens the analysis of transport properties by the spin echo, particularly in systems, where the motion is restricted by structure or configuration

Flavonoid glycosides from Persea caerulea. Unraveling their interactions with SDS-micelles through matrix-assisted DOSY, PGSE, mass spectrometry, and NOESY

Two flavonoid glycosides derived from rhamnopyranoside (1) and arabinofuranoside (2) have been isolated from leaves of Persea caerulea for the first time. The structures of 1 and 2 have been established by 1H NMR, 13C NMR, and IR spectroscopy, together with LC–ESI–TOF and LC–ESI–IT MS spectrometry. From the MS and MS/MS data, the molecular weights of the intact molecules as well as those of quercetin and kaempferol together with their sugar moieties were deduced. The NMR data provided information on the identity of the compounds, as well as the α and β configurations and the position of the glycosides on quercetin and kaempferol. We have also explored the application of sodium dodecyl sulfate (SDS) normal micelles in binary aqueous solution, at a range of concentrations, to the diffusion resolution of these two glycosides, by the application of matrix‐assisted diffusion ordered spectroscopy (DOSY) and pulse field gradient spin echo (PGSE) methodologies, showing that SDS micelles offer a significant resolution which can, in part, be rationalized in terms of differing degrees of hydrophobicity, amphiphilicity, and steric effects. In addition, intra‐residue and inter‐residue proton–proton distances using nuclear Overhauser effect build‐up curves were used to elucidate the conformational preferences of these two flavonoid glycosides when interacting with the micelles. By the combination of both diffusion and nuclear Overhauser spectroscopy techniques, the average location site of kaempferol and quercetin glycosides has been postulated, with the former exhibiting a clear insertion into the interior of the SDS‐micelle, whereas the latter is placed closer to the surface.Junta de Andalucía P12-FQM-266

Spatial correlations in chaotic nanoscale systems with spin-orbit coupling

We investigate the statistical properties of wave functions in chaotic nanostructures with spin-orbit coupling (SOC), focussing in particular on spatial correlations of eigenfunctions. Numerical results from a microscopic model are compared with results from random matrix theory in the crossover from the gaussian orthogonal to the gaussian symplectic ensembles (with increasing SOC); one- and two-point distribution functions were computed to understand the properties of eigenfunctions in this crossover. It is found that correlations of wave function amplitudes are suppressed with SOC; nevertheless, eigenfunction correlations play a more important role in the two-point distribution function(s), compared to the case with vanishing SOC. Experimental consequences of our results are discussed.Comment: Submitted to PR

Molecular diffusion between walls with adsorption and desorption

The time dependency of the diffusion coefficient of particles in porous media is an efficient probe of their geometry. The analysis of this quantity, measured e.g. by nuclear magnetic resonance (PGSE-NMR), can provide rich information pertaining to porosity, pore size distribution, permeability and surface-to-volume ratio of porous materials. Nevertheless, in numerous if not all practical situations, transport is confined by walls where adsorption and desorption processes may occur. In this article, we derive explicitly the expression of the time-dependent diffusion coefficient between two confining walls in the presence of adsorption and desorption. We show that they strongly modify the time-dependency of the diffusion coefficient, even in this simple geometry. We finally propose several applications, from sorption rates measurements to the use as a reference for numerical implementations for more complex geometries.Comment: 4 pages, 2 figures, 1 supplementary material of 3 page