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

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

Hyperpolarized 83Kr magnetic resonance imaging of alveolar degradation in a rat model of emphysema

Hyperpolarized 83Kr surface quadrupolar relaxation (SQUARE) generates MRI contrast that was previously shown to correlate to surface to volume ratios in porous model surface systems. The underlying physics of SQUARE contrast is conceptually different from any other current MRI methodology as the method utilizes the nuclear electric properties of the spin I = 9/2 isotope 83Kr. To explore the usage of this non-radioactive isotope for pulmonary pathophysiology, MRI SQUARE contrast was acquired in excised rat lungs obtained from an elastase induced model of emphysema. A significant 83Kr T1 relaxation time increase in the SQUARE contrast was found in the elastase treated lungs compared to the baseline data from control lungs. The SQUARE contrast suggests a reduction in pulmonary surface to volume ratio in the emphysema model that was validated by histology. The finding supports usage of 83Kr SQUARE as new biomarker for surface to volume ratio changes in emphysema

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

Sodium in the dermis colocates to glycosaminoglycan scaffold, with diminishment in type 2 diabetes mellitus

BACKGROUND. Dietary sodium intake mismatches urinary sodium excretion over prolonged periods. Our aims were to localize and quantify electrostatically bound sodium within human skin using triple-quantum–filtered (TQF) protocols for MRI and magnetic resonance spectroscopy (MRS) and to explore dermal sodium in type 2 diabetes mellitus (T2D). METHODS. We recruited adult participants with T2D (n = 9) and euglycemic participants with no history of diabetes mellitus (n = 8). All had undergone lower limb amputations or abdominal skin reduction surgery for clinical purposes. We used 20 μm in-plane resolution 1H MRI to visualize anatomical skin regions ex vivo from skin biopsies taken intraoperatively, 23Na TQF MRI/MRS to explore distribution and quantification of freely dissolved and bound sodium, and inductively coupled plasma mass spectrometry to quantify sodium in selected skin samples. RESULTS. Human dermis has a preponderance (>90%) of bound sodium that colocalizes with the glycosaminoglycan (GAG) scaffold. Bound and free sodium have similar anatomical locations. T2D associates with a severely reduced dermal bound sodium capacity. CONCLUSION. We provide the first evidence to our knowledge for high levels of bound sodium within human dermis, colocating to the GAG scaffold, consistent with a dermal “third space repository” for sodium. T2D associates with diminished dermal electrostatic binding capacity for sodium