Sorbate Transport in Carbon Molecular Sieve Membranes and FAU/EMT Intergrowth by Diffusion NMR.

In this paper we present and discuss selected results of our recent studies of sorbate self-diffusion in microporous materials. The main focus is given to transport properties of carbon molecular sieve (CMS) membranes as well as of the intergrowth of FAU-type and EMT-type zeolites. CMS membranes show promise for applications in separations of mixtures of small gas molecules, while FAU/EMT intergrowth can be used as an active and selective cracking catalyst. For both types of applications diffusion of guest molecules in the micropore networks of these materials is expected to play an important role. Diffusion studies were performed by a pulsed field gradient (PFG) NMR technique that combines advantages of high field (17.6 T) NMR and high magnetic field gradients (up to 30 T/m). This technique has been recently introduced at the University of Florida in collaboration with the National Magnet Lab. In addition to a more conventional proton PFG NMR, also carbon-13 PFG NMR was used.

Pulsed field gradient nuclear magnetic resonance study of time-dependent diffusion behavior and exchange of lipids in planar-supported lipid bilayers.

This work reports the direct experimental observation of lipid exchange between liquid-ordered domains and their liquid-disordered surroundings in 3-component planar-supported multibilayers (1,2-dioleoyl-sn-glycerol-3-phosphocholine/1,2-dipalmitoyl-sn-glycero-3-phosphocholine/cholesterol). The measurements of lipid lateral diffusion and exchange were carried out using proton pulsed field gradient (PFG) NMR spectroscopy with high field strength (17.6 T) and high gradient amplitudes (up to 30 T/m). Application of large gradients affords the use of sufficiently small diffusion times under the condition that the width of the gradient pulses is much smaller than the diffusion time. As a result, PFG NMR studies of time-dependent diffusion behavior in lipid bilayers become possible over submicrometer length scales of displacements, which are comparable with the domain size. Comparison of the PFG NMR diffusion data and the corresponding results of dynamic Monte Carlo simulations allowed for the estimation of domain boundary permeability and domain size at temperatures near the transition temperature for the studied bilayers.

Influence of water on diffusion in imidazolium-based ionic liquids: a pulsed field gradient NMR study.

In this work, we applied a novel pulsed field gradient (PFG) NMR option, which combines advantages of high-field (17.6 T) NMR and high magnetic field gradients (up to 30 T/m), to study diffusion of anions, cations and water in two 1-ethyl-3-methylimidazolium-based ionic liquids. Application of high field allows for an easy recording of an NMR signal from small amounts of water added to the ionic liquids. Using high gradients is advantageous because under conditions of such gradients any susceptibility-induced inhomogeneities in the local magnetic field are expected to be negligibly small in comparison with the applied gradients. PFG NMR studies have been performed in a broad range of temperatures and for different diffusion times. The effect of water addition on the diffusion behavior of the anions and cations is discussed in the context of the presence of polar and nonpolar domains in the ionic liquids. A partial screening of the electrostatic interaction between the cations and anions in the polar domains by water is believed to be responsible for the following changes in the diffusion behavior, which were observed experimentally: (i) increase in the ion diffusivities with increasing water concentration, and (ii) decrease in the difference between the diffusion coefficient of the cation and that of the anion as water concentration increases.

Heterogeneity of polyelectrolyte diffusion in polyelectrolyte-protein coacervates: a 1H pulsed field gradient NMR study.

Proton pulsed field gradient (PFG) NMR was used to study the diffusion of poly(diallyldimethylammonium chloride) (PDADMAC) in coacervates formed from this polycation and the protein bovine serum albumin (BSA). Application of high (up to 30 T/m) magnetic field gradients in PFG NMR measurements allowed probing the diffusion of PDADMAC on a length scale of displacements as small as 100 nm in coacervates formed at different pH's and ionic strengths, i.e., conditions of varying protein-polycation interaction energy. Studies were carried out for a broad range of diffusion times and corresponding values of the mean square displacements. Several ensembles of PDADMAC polycations with different diffusivities were observed in the measured range of diffusion times. The existence of these ensembles and the pattern of their changes with increasing diffusion time support the hypothesis about the microscopic heterogeneity of PDADMAC-BSA coacervates and also provide evidence for the dynamic disintegration and reformation of dense domains.