A molecular–mechanical link in shear-induced self-assembly of a functionalized biopolymeric fluid

23Na multiple quantum filtered (MQF) rheo-NMR methods were applied to probe the molecular foundation for flow induced self-assembly in 0.5% κ-carrageenan fluid. This method is sensitive enough to utilize an endogenous sodium ion concentration of approximately 0.02%. Rheo-NMR experiments were conducted at different temperatures and shear rates to explore varying molecular dynamics of the biopolymer in the fluid under shear. The temperature in the rheo-NMR experiments was changes from 288 K to 313 K to capture transition of κ-carrageenan molecules from helices to coils. At each temperature, the fluid was also tested for flow and oscillatory shear behaviour using bulk rheometry methods. It was found that the 23Na MQF signals were observed for the 0.5% κ-carrageenan solution only under shear and when the fluid demonstrated yielding and/or shear-thinning behaviour. At temperatures of 303 K and above, no 23Na MQF signals were observed independent of the presence or absence of shear as the molecular phase transition to random coils occurs and the fluid becomes Newtonian

Fluid flow in a porous medium with transverse permeability discontinuity

Magnetic Resonance Imaging (MRI) velocimetry methods were used to study fully developed axially symmetric fluid flow in a model porous medium of cylindrical symmetry with a transverse permeability discontinuity. Spatial mapping of fluid ow resulted in radial velocity profiles. High spatial resolution of these profiles allowed the estimating of the slip in velocities at the boundary with a permeability discontinuity zone in a sample. The profiles were compared to theoretical velocity fields for a fully developed axially symmetric flow in a cylinder derived from the Joseph and Beavers and the Brinkman models. Velocity fields were also computed using pore-scale lattice Boltzmann Modelling (LBM) where the assumption about the boundary could be omitted. Both approaches gave a good agreement between theory and experiment though LBM velocity fields followed experiment more closely. This work shows great promise for MRI velocimetry methods in addressing the boundary behavior of fluids in opaque heterogeneous porous media

NMR Imaging of low pressure, gas-phase transport in packed beds using hyperpolarized xenon-129

Gas-phase magnetic resonance imaging (MRI) has been used to investigate heterogeneity in mass transport in a packed bed of commercial, alumina, catalyst supports. Hyperpolarized 129Xe MRI enables study of transient diffusion for micro- scopic porous systems using xenon chemical shift to selectively image gas within the pores, and, thence, permits study of low-density, gas-phase mass-transport, such that diffusion can be studied in the Knudsen regime, and not just the molecular regime, which is the limitation with other current techniques. Knudsen-regime diffusion is common in many industrial, catalytic processes. Significantly, larger spatial variability in mass transport rates across the packed bed was found compared to techniques using only molecular diffusion. It has thus been found that that these heterogeneities arise over length-scales much larger tha

Pathway to cryogen free production of hyperpolarized krypton-83 and xenon-129

yperpolarized (hp) 129Xe and hp 83Kr for magnetic resonance imaging (MRI) are typically obtained through spin-exchange optical pumping (SEOP) in gas mixtures with dilute concentrations of the respective noble gas. The usage of dilute noble gases mixtures requires cryogenic gas separation after SEOP, a step that makes clinical and preclinical applications of hp 129Xe MRI cumbersome. For hp 83Kr MRI, cryogenic concentration is not practical due to depolarization that is caused by quadrupolar relaxation in the condensed phase. In this work, the concept of stopped flow SEOP with concentrated noble gas mixtures at low pressures was explored using a laser with 23.3 W of output power and 0.25 nm linewidth. For 129Xe SEOP without cryogenic separation, the highest obtained MR signal intensity from the hp xenon-nitrogen gas mixture was equivalent to that arising from 15.561.9% spin polarized 129Xe in pure xenon gas. The production rate of the hp gas mixture, measured at 298 K, was 1.8 cm3/min. For hp 83Kr, the equivalent of 4.460.5% spin polarization in pure krypton at a production rate of 2 cm3/min was produced. The general dependency of spin polarization upon gas pressure obtained in stopped flow SEOP is reported for various noble gas concentrations. Aspects of SEOP specific to the two noble gas isotopes are discussed and compared with current theoretical opinions. A non-linear pressure broadening of the Rb D1 transition was observed and taken into account for the qualitative description of the SEOP process

Molecular sensing with hyperpolarized 129Xe using switchable chemical exchange relaxation transfer

A new approach for hyperpolarized 129Xe molecular sensors is explored using paramagnetic relaxation agents that can be deactivated upon chemical or enzymatic reaction with an analyte. Cryptophane encapsulated 129Xe within the vicinity of the paramagnetic center experiences fast relaxation that, through chemical exchange of xenon atoms between cage and solvent pool, causes accelerated hyperpolarized 129Xe signal decay in the dissolved phase. In this work, the relaxivity of GadoliniumIII-DOTA on 129Xe in the solvent was increased eightfold through tethering of the paramagnetic molecule to a cryptophane cage. This potent relaxation agent can be ‘turned off’ specifically for 129Xe through chemical reactions that spatially separate the GdIII centre from the attached cryptophane cage. Unlike 129Xe chemical shift based sensors, the new concept does not require high spectral resolution and may lead to a new generation of responsive contrast agents for molecular MRI

Structural and chemical heterogeneity in ancient glass probed using gas overcondensation, X-ray tomography, and solid-state NMR

Rare ancient glasses have complex, multi-scale structures requiring more sophisticated and non-destructive pore characterisation techniques than usual. Homotattic patch models for nitrogen adsorption gave better fits to the isotherm data, more accurate void space descriptors, and also greater understanding of the underlying physical factors affecting adsorption, than standard BET. These homotattic patch models revealed the critical role of iron impurities in determining adsorption behaviour. Non-destructive sodium-23 NMR relaxometry validated the homotattic patch model for some natron glasses, and, in turn, was validated using multiple quantum magic-angle spinning (MQMAS) 23Na NMR. X-ray tomography images of the glasses showed the presence of large macroporous bubbles, while FEG-SEM revealed nanopores within the glass matrix. A newly-developed, gas overcondensation technique, suitable for small amounts of low porosity material, assessed the inter-relationship between the disparate levels in this hierarchical porosity. This technique demonstrated that the nanoporosity did not form a ‘corona’ around the bubbles, due to leaching from the glass, as initially supposed from tomography data, but was completely disconnected, and, thus, is probably associated with glass alkalinity. Gas overcondensation is demonstrated as a non-destructive alternative to mercury porosimetry for probing multi-scale porosity in rare artefacts

Imaging Sodium Dendrite Growth in All‐Solid‐State Sodium Batteries using 23Na T2‐weighted MRI

Two‐dimensional, Knight‐shifted, T2‐contrasted 23Na magnetic resonance imaging of an all‐solid‐state cell with Na electrode and a ceramic electrolyte is employed to directly observe Na microstructural growth. A spalling dendritic morphology is observed and confirmed by more conventional post‐mortem analysis; X‐ray tomography and scanning electron microscopy. A significantly greater 23Na T2 for the dendritic growth, compared with the bulk metal electrode, is attributed to increased sodium ion mobility in the dendrite. 23Na T2‐contrast MRI of metallic sodium offers a clear, routine method for observing and isolating microstructural growths and can supplement the current suite of techniques utilised to analyse dendritic growth in all‐solid‐state cells

Operando visualisation of battery chemistry in a sodium-ion battery by 23Na magnetic resonance imaging

© 2020, The Author(s). Sodium-ion batteries are a promising battery technology for their cost and sustainability. This has led to increasing interest in the development of new sodium-ion batteries and new analytical methods to non-invasively, directly visualise battery chemistry. Here we report operando 1H and 23Na nuclear magnetic resonance spectroscopy and imaging experiments to observe the speciation and distribution of sodium in the electrode and electrolyte during sodiation and desodiation of hard carbon in a sodium metal cell and a sodium-ion full-cell configuration. The evolution of the hard carbon sodiation and subsequent formation and evolution of sodium dendrites, upon over-sodiation of the hard carbon, are observed and mapped by 23Na nuclear magnetic resonance spectroscopy and imaging, and their three-dimensional microstructure visualised by 1H magnetic resonance imaging. We also observe, for the first time, the formation of metallic sodium species on hard carbon upon first charge (formation) in a full-cell configuration

Molecular hydrogen and catalytic combustion in the production of hyperpolarized 83Kr and 129Xe MRI contrast agents

Hyperpolarized (hp) 83Kr is a promising MRI contrast agent for the diagnosis of pulmonary diseases affecting the surface of the respiratory zone. However, the distinct physical properties of 83Kr that enable unique MRI contrast also complicate the production of hp 83Kr. This work presents a radically new approach in the generation of hp 83Kr that can likewise be utilized for the production of hp 129Xe. Molecular nitrogen, typically used as buffer gas in spin exchange optical pumping (SEOP), was replaced by molecular hydrogen without penalty for the achievable hyperpolarization. In this particular study, the highest obtained nuclear spin polarizations were P = 29 % for 83Kr and P = 63 % for 129Xe. The results were reproduced over many SEOP cycles despite the laser induced on-resonance formation of rubidium hydride (RbH). Following SEOP, the H2 was reactively removed via catalytic combustion without measurable losses in hyperpolarized spin state of either 83Kr or 129Xe. Highly spin polarized 83Kr can now be purified for the first time to provide high signal intensity for the advancement of in vivo hp 83Kr MRI. More generally, a chemical reaction appears as a viable alternative to the cryogenic separation process, the primary purification method of hp 129Xe for the past 2 . decades. The inherent simplicity of the combustion process will facilitate hp 129Xe production and should allow for on-demand continuous flow of purified and highly spin polarized 129Xe

Pulmonary MRI contrast using Surface Quadrupolar Relaxation (SQUARE) of hyperpolarized 83Kr

Hyperpolarized 83Kr has previously been demonstrated to enable MRI contrast that is sensitive to the chemical composition of the surface in a porous model system. Methodological advances have lead to a substantial increase in the 83Kr hyperpolarization and the resulting signal intensity. Using the improved methodology for spin exchange optical pumping of isotopically enriched 83Kr, internal anatomical details of ex vivo rodent lung were resolved with hyperpolarized 83Kr MRI after krypton inhalation. Different 83Kr relaxation times were found between the main bronchi and the parenchymal regions in ex vivo rat lungs. The T1 weighted hyperpolarized 83Kr MRI provided a first demonstration of surface quadrupolar relaxation (SQUARE) pulmonary MRI contrast