23Na Relaxation Research Articles

Sodium MRI of the Lumbar Intervertebral Discs of the Human Spine: An Ex Vivo Study.

Lower back pain affects 75%-85% of people at some point in their lives. The detection of biochemical changes with sodium (23Na) MRI has potential to enable an earlier and more accurate diagnosis. To measure 23Na relaxation times and apparent tissue sodium concentration (aTSC) in ex-vivo intervertebral discs (IVDs), and to investigate the relationship between aTSC and histological Thompson grade. Ex-vivo. Thirty IVDs from the lumbar spines of 11 human body donors (4 female, 7 male, mean age 86 ± 8 years). 3 T; density-adapted 3D radial sequence (DA-3D-RAD). IVD 23Na longitudinal (T1), short and long transverse (T2s* and T2l*) relaxation times and the proportion of the short transverse relaxation (ps) were calculated for one IVD per spine sample (11 IVDs). Furthermore, aTSCs were calculated for all IVDs. The degradation of the IVDs was assessed via histological Thompson grading. A Kendall Tau correlation (τ) test was performed between the aTSCs and the Thompson grades. The significance level was set to P < 0.05. Mean 23Na relaxation parameters of a subset of 11 IVDs were T1 = 9.8 ± 1.3 msec, T2s* = 0.7 ± 0.1 msec, T2l* = 7.3 ± 1.1 msec, and ps = 32.7 ± 4.0%. A total of 30 IVDs were examined, of which 3 had Thompson grade 1, 4 had grade 2, 5 had grade 3, 5 had grade 4, and 13 had grade 5. The aTSC decreased with increasing degradation, being 274.6 ± 18.9 mM for Thompson grade 1 and 190.5 ± 29.5 mM for Thompson grade 5. The correlation between whole IVD aTSC and Thompson grade was significant and strongly negative (τ = -0.56). This study showed a significant correlation between aTSC and degenerative IVD changes. Consequently, aTSC has potential to be useful as an indicator of degenerative spinal changes. 2 TECHNICAL EFFICACY: Stage 1.

Reduction of the Spin–Phonon Coupling of Quadrupole Nuclei in NaF Crystals under Magnetic Saturation

The rate of nuclear spin-lattice relaxation is determined by the efficiency of interaction between thermal phonons and nuclear spins. The results on reducing the efficiency of spin–phonon coupling by suppressing the contribution from paramagnetic centers to quadrupole nucleus relaxation are presented. The suppression has been performed by stationary magnetic effect at the Larmor frequency. It is shown that, as in the presence of an acoustic field, the rate of spin-lattice relaxation of 23Na nuclei in a sodium fluoride crystal at magnetic saturation of the NMR signal does not change in the region of a negative average spin temperature.In the region of positive spin temperature, the rate of relaxation of 23Na spins significantly decreases and nuclear magnetization recovery with time is described by the sum of two exponentials. The contribution from nuclear spins with a lower efficiency of spin–phonon coupling, corresponding to the exponential with a long relaxation time, increases with increasing saturating field intensity. It is demonstrated that the efficiency of spin–phonon coupling for 19F nuclei without quadrupole moment does not change under the saturation conditions.The results obtained can be used for analyzing the structure of real crystals.

PH Effects on the Conformations of Galacturonan in Solution: Conformational Transition and Loosening, Extension and Stiffness

Calorimetric (from both isothermal micro-calorimetry and DSC), chiro-optical, viscometric and rheological data on aqueous solutions of pectic acid and low-methoxyl pectin (LMP), published over decades from different laboratories, have been comparatively revisited. The aim was to arrive at a consistent and detailed description of the behavior of galacturonan as a function of pH, i.e., of the degree of charging (as degree of dissociation, α) of the polyanion. The previously hypothesized pH-induced transition from a 31 to a 21 helix was definitely confirmed, but it has been shown, for the first time, that the transition is always coupled with loosening/tightening effects brought about by an increase in charge. The latter property has a twofold effect: the former effect is a purely physical one (polyelectrolytic), which is always a loosening one. However, in the very low range of pH and before the beginning of the transition, an increase in charge tightens the 31 helix by strengthening an intramolecular—but inter-residue—hydrogen bond. The value of the enthalpy change of 31 → 21 transition—+0.59 kcal·mol−1—is bracketed by those provided by theoretical modeling, namely +0.3 and +0.8 kcal·mol−1; the corresponding entropy value is also positive: +1.84 cal·mole r.u.−1·K−1. The enthalpic and the entropic changes in chain loosening amount only to about 23% of the corresponding 31 → 21 changes, respectively. Much like poly(galacturonic acid), the 31 conformation of LMP also stiffens on passing from pH = 2.5 to 3.0, to then start loosening and transforming into the 21 one on passing to pH = 4.0. Lowering the pH of a salt-free aqueous solution of LMP down to 1.6 brings about a substantial chain–chain association, which is at the root of the interchain junctions stabilizing the acid pH gels, in full agreement with the rheological results. A comparison of the enthalpic data reveals that, at 85 °C, LMP in acidic pH conditions has lost its initial order by about 2.3 times more than pectic acid brought from low charging to full neutralization (at α = 1.0) at 25 °C. A proper combination of experiments (enthalpic measurements) and theory (counterion condensation polyelectrolyte theory) succeeded in demonstrating, for the first time ever, a lyotropic/Hofmeister effect of the anion perchlorate in stabilizing the more disordered form of the 21 helix of galacturonan. The viscometric results in water showed that the 31 helix is capable of forming longer rheologically cooperative units compared with the 21 helix. Extrapolation to infinite ionic strength confirmed that, once all electrostatic interactions are cancelled, the elongation of the two helical forms is practically the same. At the same time, however, they indicated that the flexibility of the two-fold helix is more than fifteen times larger than that of the three-fold one. The result is nicely corroborated by a critical revisiting of 23Na relaxation experiments.

Hydration and Mobility of Alkaline Metal Cations in Sulfonic Cation Exchange Membranes.

The interconnection of ionogenic channel structure, cation hydration, water and ionic translational mobility was revealed in Nafion and MSC membranes based on polyethylene and grafted sulfonated polystyrene. A local mobility of Li+, Na+ and Cs+ cations and water molecules was estimated via the 1H, 7Li, 23Na and 133Cs spin relaxation technique. The calculated cation and water molecule self-diffusion coefficients were compared with experimental values measured using pulsed field gradient NMR. It was shown that macroscopic mass transfer is controlled by molecule and ion motion near sulfonate groups. Lithium and sodium cations whose hydrated energy is higher than water hydrogen bond energy move together with water molecules. Cesium cations in possession of low hydrated energy are directly jumping between neighboring sulfonate groups. Cation Li+, Na+ and Cs+ hydration numbers (h) in membranes were calculated from 1H chemical shift water molecule temperature dependences. The values calculated from the Nernst-Einstein equation and the experimental conductivity values were close to each other in Nafion membranes. In MSC membranes, calculated conductivities were one order of magnitude more compared to the experimental ones, which is explained by the heterogeneity of the membrane pore and channel system.

Sodium Dynamics in the Cellular Environment.

Sodium ions are essential for the functions of biological cells, and they are maintained at the balance between intra- and extracellular environments. The quantitative assessment of intra- and extracellular sodium as well as its dynamics can provide crucial physiological information on a living system. 23Na nuclear magnetic resonance (NMR) is a powerful and noninvasive technique to probe the local environment and dynamics of sodium ions. However, due to the complex relaxation behavior of the quadrupolar nucleus in the intermediate-motion regime and because of the heterogeneous compartments and diverse molecular interactions in the cellular environment, the understanding of the 23Na NMR signal in biological systems is still at the early stage. In this work, we characterize the relaxation and diffusion of sodium ions in the solutions of proteins and polysaccharides, as well as in the in vitro samples of living cells. The multi-exponential behavior of 23Na transverse relaxation has been analyzed according to the relaxation theory to derive the crucial information related to the ionic dynamics and molecular binding in the solutions. The bi-compartment model of transverse relaxation and diffusion measurements can corroborate each other to quantify the fractions of intra- and extracellular sodium. We show that 23Na relaxation and diffusion can be used to monitor the viability of human cells, which offers versatile NMR metrics for in vivo studies.

Mobility of Li+, Na+, and Cs+ cations in Nafion membrane, as studied by NMR techniques

The local mobility and diffusion of Li+, Na+, and Cs+ cations in Nafion 117 membrane were explored by 7Li, 23Na, and 133Cs spin relaxation and pulsed field gradient NMR techniques. It was shown that the macroscopic mass transfer of cations is controlled by ion motion near sulfonate groups. Lithium and sodium cations, whose hydrated energy is higher than the water hydrogen bond energy, are moving together with water molecules, but cesium cations possessing a low hydrated energy are jumping directly between the neighboring sulfonate groups.

Evaluation of Sodium Relaxation Times and Concentrations in the Achilles Tendon Using MRI.

Sodium magnetic resonance imaging (MRI) can be used to evaluate the change in the proteoglycan content in Achilles tendons (ATs) of patients with different AT pathologies by measuring the 23Na signal-to-noise ratio (SNR). As 23Na SNR alone is difficult to compare between different studies, because of the high influence of hardware configurations and sequence settings on the SNR, we further set out to measure the apparent tissue sodium content (aTSC) in the AT as a better comparable parameter. Ten healthy controls and one patient with tendinopathy in the AT were examined using a clinical 3 Tesla (T) MRI scanner in conjunction with a dual tuned 1H/23Na surface coil to measure 23Na SNR and aTSC in their ATs. 23Na T1 and T2* of the AT were also measured for three controls to correct for different relaxation behavior. The results were as follows: 23Na SNR = 11.7 ± 2.2, aTSC = 82.2 ± 13.9 mM, 23Na T1 = 20.4 ± 2.4 ms, 23Na T2s* = 1.4 ± 0.4 ms, and 23Na T2l* = 13.9 ± 0.8 ms for the whole AT of healthy controls with significant regional differences. These are the first reported aTSCs and 23Na relaxation times for the AT using sodium MRI and may serve for future comparability in different studies regarding examinations of diseased ATs with sodium MRI.

Cl- and Na+ ions binding in slag and fly ash cement paste during early hydration as studied by 1H, 35Cl and 23Na NMR

Lacking effective and in particular direct methods, the study on Cl- and Na+ ion binding during hydration has rarely been reported. In this study, a specially developed Nuclear Magnetic Resonance setup was employed to study the Cl- and Na+ ion binding of cement pastes during hydration. Influence factors, such as slag and fly ash replacement, on the 1H, 35Cl and 23Na relaxation of the cement paste made with 1 mol/L NaCl solutions were investigated. It was found that the increase of slag in the cement gives rise to bigger pores during hydration, and the fly ash resulted in less water being consumed. The Cl- signals would first be stable then gradually decrease as a function of time. The slag in cement has minor impacts on the Cl- ions binding, and the fly ash replacement in the cement would result in less Cl- ions binding during the hydration. Results also suggest that the slag could result in later Na+ binding, and the fly ash in the cement will significantly reduce the Na+ binding. Besides, the Cl- ions will bind earlier compared to the Na+ ions, which is probably related to the characteristics of the hydrates. The normalized 35Cl and 23Na signal intensity, in general, decrease with water consumption reflecting the hydration. Furthermore, the early formed hydrates would consume relatively less water but bind more Cl- and Na- ions.

Microstructural correlates of 23Na relaxation in human brain at 7 Tesla

23Na provides the second strongest MR-observable signal in biological tissue and exhibits bi-exponential T2∗ relaxation in micro-environments such as the brain. There is significant interest in developing 23Na biomarkers for neurological diseases that are associated with sodium channel dysfunction such as multiple sclerosis and epilepsy. We have previously reported methods for acquisition of multi-echo sodium MRI and continuous distribution modelling of sodium relaxation properties as surrogate markers of brain microstructure. This study aimed to compare 23Na T2∗ relaxation times to more established measures of tissue microstructure derived from advanced diffusion MRI at 7 ​T. Six healthy volunteers were scanned using a 3D multi-echo radial ultra-short TE sequence using a dual-tuned 1H/23Na birdcage coil, and a high-resolution multi-shell, high angular resolution diffusion imaging sequence using a 32-channel 1H receive coil. 23Na T2∗ relaxation parameters [mean T2∗ (T2∗mean) and fast relaxation fraction (T2∗ff)] were calculated from a voxel-wise continuous gamma distribution signal model. White matter (restricted anisotropic diffusion) and grey matter (restricted isotropic diffusion) density were calculated from multi-shell multi-tissue constrained spherical deconvolution. Sodium parameters were compared with white and grey matter diffusion properties. Sodium T2∗mean and T2∗ff showed little variation across a range of white matter axonal fibre and grey matter densities. We conclude that sodium T2∗ relaxation parameters are not greatly influenced by relative differences in intra- and extracellular partial volumes. We suggest that care be taken when interpreting sodium relaxation changes in terms of tissue microstructure in healthy tissue.

Automated classification of food products using 2D low-field NMR

In this work, low-field proton (1H) and sodium (23Na) relaxation and diffusion measurements are used to detect and classify different types of food products. A compact and low-cost system based on a small 0.5 T permanent magnet has been developed to autonomously authenticate such products. The system uses a simple but efficient double-tuned matching network suitable for 1H/23Na NMR. Various machine learning algorithms are used to classify food samples based on T1-T2 and D-T2 data generated by the system, and the accuracy and prediction speed of these algorithms are studied in detail. The influence of temperature drift upon prediction accuracy is also studied. Experimental results demonstrate reliable classification of cooking oils, milk, and soy sauces.

Structure and Sodium Ion Dynamics in Sodium Strontium Silicate Investigated by Multinuclear Solid-State NMR

The high oxide ion conductivity of the proposed sodium strontium silicate ion conductors Sr0.55Na0.45SiO2.775 (>10–2 S·cm–1 at 525 °C) and its unusual alkali metal substitution strategy have been extensively questioned in the literature. Here, we present a comprehensive understanding of the structure of this material using a combination of XRD and multinuclear 17O, 23Na, and 29Si solid-state NMR spectroscopy data and a detailed investigation of the Na ion dynamics by high temperature 23Na NMR line shape analysis and relaxation rates measurements. Both 23Na and 29Si NMR spectra demonstrate the absence of Na doping in strontium silicate SrSiO3 and the presence of an amorphous phase identified as Na2O·2SiO2 glass as the Na-containing product. Devitrification at 800 °C yields crystallization of the Na2O·2SiO2 glass into the known crystalline α-Na2Si2O5 phase which was positively identified by its XRD pattern and the extensive and clear 17O, 23Na, and 29Si NMR fingerprints. High temperature 23Na NMR reveals that the Na ions are mobile in the Na2O·2SiO2 amorphous component below its glass transition temperature (∼450 °C). In contrast, 23Na NMR data obtained on the crystalline α-Na2Si2O5 shows limited Na dynamics below ∼650 °C, and this result explains the large discrepancy in the conductivity observed in the literature which strongly depends on the thermal history of the Sr0.55Na0.45SiO2.775 material. These insights demonstrate that the high conductivity observed in Sr0.55Na0.45SiO2.775 is due to Na conduction in the Na2O·2SiO2 glass, and this motivates the quest for the discovery of low temperature fast ion conductors in noncrystalline solids.

Exploring the Role of Phosphate Structural Distortions on the Sodium Jump Dynamics in NASICON Phases

ABSTRACTHigh temperature solid state sodium (23Na) magic angle spinning (MAS) NMR spin lattice relaxation times (T1) were evaluated for a series of NASICON (Na3Zr2PSi2O12) materials to directly determine Na jump rates. Simulations of the T1 temperature variations that incorporated distributions in Na jump activation energies, or distribution of jump rates, improved the agreement with experiment. The 23Na NMR T1 relaxation results revealed that distributions in the Na dynamics were present for all of the NASICON materials investigated here. The 23Na relaxation experiments also showed that small differences in material composition and/or changes in the processing conditions impacted the distributions in the Na dynamics. The extent of the distribution was related to the presence of a disordered or glassy phosphate phase present in these different sol-gel processed materials. The 23Na NMR T1 relaxation experiments are a powerful tool to directly probing Na jump dynamics and provide additional molecular level details that could impact transport phenomena.

Intermolecular interactions and 3D structure in cellulose-NaOH-urea aqueous system.

The dissolution of cellulose in NaOH/urea aqueous solution at low temperature is a key finding in cellulose science and technology. In this paper, (15)N and (23)Na NMR experiments were carried out to clarify the intermolecular interactions in cellulose/NaOH/urea aqueous solution. It was found that there are direct interactions between OH(-) anions and amino groups of urea through hydrogen bonds and no direct interaction between urea and cellulose. Moreover, Na(+) ions can interact with both cellulose and urea in an aqueous system. These interactions lead to the formation of cellulose-NaOH-urea-H2O inclusion complexes (ICs). (23)Na relaxation results confirmed that the formation of urea-OH(-) clusters can effectively enhance the stability of Na(+) ions that attracted to cellulose chains. Low temperature can enhance the hydrogen bonding interaction between OH(-) ions and urea and improve the binding ability of the NaOH/urea/H2O clusters that attached to cellulose chains. Cryo-TEM observation confirmed the formation of cellulose-NaOH-urea-H2O ICs, which is in extended conformation with mean diameter of about 3.6 nm and mean length of about 300 nm. Possible 3D structure of the ICs was proposed by the M06-2X/6-31+G(d) theoretical calculation, revealing the O3H···O5 intramolecular hydrogen bonds could remain in the ICs. This work clarified the interactions in cellulose/NaOH/urea aqueous solution and the 3D structure of the cellulose chain in dilute cellulose/NaOH/urea aqueous solution.

Study of the structural phase transitions in Na 3D 0.51H 0.49(SO 4) 2 crystals by 2H and 23Na nuclear magnetic resonance

The mixed Na 3D x H 1− x (SO 4) 2 crystals grown in this study have a deuterium fraction of 51%, and the phase transitions for Na 3D 0.51H 0.49(SO 4) 2 were found to occur at 300 K ( = T C 1 ) and 546 K ( = T C 2 ) . The NMR spectra and the relaxation times of 2H and 23Na in Na 3D 0.51H 0.49(SO 4) 2 crystals were measured as functions of temperature. Although our results for the 2H and 23Na relaxation times provided no evidence of the phase transitions at T C 1 , the 2H and 23Na NMR spectra did change. The phase transitions at 300 K produced changes in the 2H and 23Na NMR spectra that are associated with changes in the atomic positions of the 2H and 23Na ions. The effects of partial deuteration of Na 3H(SO 4) 2 crystals include not only a shift in the phase transition temperature T C but also a change in the local symmetry.

Chemical shift sodium imaging in a mouse model of thromboembolic stroke at 9.4 T

To estimate changes in the (23)Na density and in the (23)Na relaxation time T(2) * in the anatomically small murine brain after stroke. Three-dimensional acquisition weighted chemical shift imaging at a resolution of 0.6 × 0.6 × 1.2 mm(3) was used for sodium imaging and relaxation parameter mapping. In vivo measurements of the mouse brain (n = 4) were performed 24 hours after stroke, induced by microinjection of purified murine thrombin into the right middle cerebral artery. The measurement time was 14 minutes in one mouse and 65 minutes in the other three. An exponential fit estimation of the free induction decay was calculated for each voxel enabling the reconstruction of locally resolved relaxation parameter maps. The infarcted areas showed an increase in sodium density between 160% and 250%, while the T(2) * relaxation time increased by 5%-72% compared to unaffected contralateral brain tissue. (23)Na chemical shift imaging at a resolution of 0.6 × 0.6 × 1.2 mm(3) enabled sodium imaging of the anatomical small mouse brain and the acquired data allowed calculating relaxation parameter maps and hence a more exact evaluation of sodium signal changes after stroke.

NMR Studies of the Hydrogen Storage Compound NaMgH3

Hydrogen and 23Na NMR were performed to 400 °C on NaMgH3 powder produced by reactive ball-milling of NaH and MgH2. The H resonance shows narrowing already at 100 °C as a narrow line superimposed on the broad, rigid-lattice signal. With increasing temperature, the fraction of spins in the narrow component grows smoothly, approaching 100% near 275 °C. This heterogeneous narrowing suggests a wide distribution of H motion rates. After annealing at 400 °C, the narrow component intensity at temperatures below 200 °C was substantially reduced and both H and 23Na relaxation rates 1/T1 were decreased. Thus, it appears that the high rates of H motion, particularly on first heating, are due to regions with poorly organized crystal structure. If this disorder could be maintained, this might be an avenue toward improved reaction kinetics of this or other hydrides. In the annealed sample, the activation energy for H diffusion is approximately 95 kJ/mol.

Melting of the Na Layers in SolidNa0.8CoO2

Data of 23Na NMR spectra and relaxation measurements are interpreted as suggesting that, upon increasing temperature, the Na layers in Na0.8CoO2 adopt a 2D liquid state at T=291 K. The corresponding first order phase transition is preceded by a rapidly increasing mobility and diffusion of Na ions above 200 K. Above 291 K, the 23Na NMR response is similar to that previously observed in superionic conductors with planar Na layers.

Nuclear spin phonon relaxation by Raman process in Na3H(SO4)2 single crystals with the electric–quadrupole-type interaction using 1H and 23Na NMR

Abstract Successive phase transitions in a Na3H(SO4)2 single crystal were found at 296, 513, and 533 K. To investigate the mechanism of the phase transition at 296 K, the 1H and 23Na spin–lattice relaxation time and the spin–spin relaxation time of Na3H(SO4)2 were measured near the phase transition temperature using a FT NMR spectrometer. The spin–lattice relaxation time, T1, for 1H in Na3H(SO4)2 crystals exhibits a minimum below TC1 (=296 K) indicating the presence of distinct molecular motion governed by the Bloembergen–Purcell–Pound (BPP) theory. Although the results for the 1H and 23Na relaxation times provide no evidence of the phase transition at TC1, the separation of the 23Na resonance lines changes abruptly at TC1. The phase transition at 296 K produces a change in the separation of the Na resonance line that is associated with a change in the atomic positions in the vicinity of the Na ions. Also, the nuclear spin–lattice relaxation process in Na3H(SO4)2 crystals with the electric–quadrupole-type interaction proceed via Raman process. These results are compared with those obtained for other M3H(SO4)2 (M=K, Rb, and Cs) crystals, which have similar hydrogen-bonded structures.

NMR and quantum chemistry study of mesoscopic structuring in 3-methylpyridine/water/NaBr mixture in the vicinity of the phase separation boundary

23Na and 81Br NMR spin-lattice relaxation times and signal half widths (Δ1/2) have been measured in 3-methylpyridine (3MP)/H2O/NaBr mixture along T = 294 and 301 K isotherms gradually increasing the mass fractions of salt (X) up to the phase separation boundary. The extreme narrowing condition and thus 1/T 1 = 1/T 2 = πΔ 1/2 was found to be valid in all cases. Discontinuous changes in slope of 1/T 1,2 = f(X) were detected, and then corresponding points on the phase diagram (X, T) were attributed to the borderline between the molecular-ionic solution and the area of enhanced mesoscopic structuring. A very strong relaxation effect was observed for 81Br nuclei reaching relaxation rates of 14,000 s–1. 23Na and 81Br NMR relaxation data together with calculations of quantum chemistry model of electrical field gradient tensor evidence the migration of 3-methylpyridinium at increasing X from the anions hydration shells towards cations. An interchange from migration to steady distribution regimes is observed for anions and vice versa for cations at the borderline of the structured phase.

Dynamical properties of ions confined within dense dispersions of charged anisotropic colloids : A 23Na quadrupolar NMR study

We used 23Na quadrupolar NMR spectroscopy and relaxation measurements to determine the mobility of the sodium counterions confined within dense aqueous dispersions of synthetic Laponite clays as a model of charged anisotropic nano-composite colloids. The lineshape analysis of the 23Na spectra and the measurements of the Hahn echo attenuation are used to determine the critical clay concentration corresponding to the nematic organisation of the dispersion. As validated by numerical simulations of the ion diffusion within partially oriented nematic dispersion of the anisotropic colloids, the angular variation of the apparent relaxation rates is interpreted as an indice of degree of ordering of the dispersion.