Bulk Magnetic Susceptibility Effects Research Articles

NMR Spectroscopic Investigations of the Performance Limiting Mechanisms of Lithium-Sulfur Batteries

During the past decades, the development of alternative energy sources has become increasingly important as the growing consumption of non-regenerative fossil energy poses a threat to the environment. Hence, developing of next-generation batteries featuring high capacity, reduced costs and improved safety, such as in lithium-sulfur batteries, is of utmost importance. The benefits of lithium-sulfur batteries have led to widespread efforts to understand the fundamentals of the sulfur redox chemistry that drives their operation, as capacity fade has been observed in almost all Li-S batteries.[1] Therefore, the involved local structural changes that correlate with the (electro)chemical processes need to be unveiled during the operation of Li-S batteries, suitably by in situ and in operando methods. This presentation will demonstrate the development and application of one such (operando) technique: nuclear magnetic resonance (NMR) spectroscopy. NMR spectroscopic measurements allow the probing of the structural changes in a battery during electrochemical cycling. In particular, the application of a non-invasive experimental set-up, which can follow the reaction inside the battery in operando is highly desirable as it provides real-time structural information compared to ex situ analysis.[2] Lithium-sulfur batteries contain various NMR-active nuclear isotopes, like 7Li, 6Li and 33S, which allow the following of the chemical reactions during the charge-discharge process. This includes the transition between elemental sulfur and polysulfides on the cathode side, the formation of the solid-electrolyte interface (SEI) and the metal plating and stripping on the anode side. Herein, we use for the first time a combination of lithium and sulfur in operando NMR spectroscopy to reveal a fundamental understanding of the reaction pathway of lithium-sulfur batteries during the cycling process.Lithium NMR spectroscopy is a powerful technique to apply to batteries, as demonstrated by many previous investigations on different lithium battery systems, since it enables the detection of the chemical environments of lithium species during electrochemical cycling and parasitic reactions in the cell.[3] The great advantage of in operando 7Li NMR spectroscopy is that the 7Li signals of the lithium anode and the deposited metal differ due to the bulk magnetic susceptibility effects and the surface area, bringing the skin depth effect into play. Thus, this method enables a time-resolved and quantitative evaluation of the electrochemical metal deposition during electrochemical cycling. Therefore, it is possible to investigate a critical problem that reduces the cell performance – the formation of lithium dendrites. This lithium deposition is particularly problematic if it occurs uncontrolled and inhomogeneous and the exact mechanism of nucleation and propagation of dendrites is not yet fully understood.[4] The developed technique helps to understand this deposition to improve the safety during cycling. The interpretation of the electrolyte signal in the in operando 7Li spectra is much more difficult because of the overlapping signals. Therefore, in situ 33S and 6Li NMR spectroscopy supports the identification and quantification of (poly-)sulfides during the charge-discharge-process. 33S NMR experiments are rarely reported since 33S is a quadrupolar nucleus characterized by a low natural abundance and magnetogyric ratio, resulting in a very low receptivity. Nevertheless, the developed 33S NMR technique allows the detection of the formation Li2S under in operando conditions.[5] Additional in operando 6Li NMR experiments allow to follow the (poly-)sulfide formation as the spectra yield much sharper lines in asymmetric lithium environments in comparison to 7Li NMR experiments.[6] Thus, these techniques provide complementary results to the 7Li NMR spectroscopic studies and help to elucidate the sulfur redox mechanism in lithium-sulfur batteries.Our developed in situ NMR spectroscopic set-up is a powerful analytical method since real-time qualitative and quantitative detection of different sulfur and lithium species is crucial for understanding the electrochemical process in sulfur batteries. The first time, a combination of in operando lithium and sulfur NMR spectroscopy is presented, providing new insights at the molecular level that are essential for accelerating the development of lithium-sulfur battery technologies.[1] H. Wang, N. Sa, et al., The Journal of Physical Chemistry C 2017, 121, 6011–6017.[2] J. B. Richter, et al., Chemical Communications 2019, 55, 6042–6045.[3] R. Bhattacharyya, et al., Nat Mater 2010, 9, 504–510.[4] A. B. Gunnarsdóttir, et al., J Mater Chem A Mater 2020, 8, 14975–14992.[5] R. Musio, in Annu Rep NMR Spectrosc, 2006, pp. 1–88.[6] L. A. Huff, et al., Surf Sci 2015, 631, 295–300.

Operando benchtop NMR reveals reaction intermediates and crossover in redox flow batteries

Redox flow batteries (RFBs) provide a promising battery technology for grid-scale energy storage. High-field operando NMR analyses of RFBs have yielded useful insight into their working mechanisms and helped improve battery performance. Nevertheless, the high cost and large footprint of a high-field NMR system limit its implementation by a wider electrochemistry community. Here, we demonstrate an operando NMR study of an anthraquinone/ferrocyanide-based RFB on a low-cost and compact 43 MHz benchtop system. The chemical shifts induced by bulk magnetic susceptibility effects differ remarkably from those obtained in high-field NMR experiments, due to the different orientations of the sample relative to the external magnetic field. We apply Evans method to estimate the concentrations of paramagnetic anthraquinone radical and ferricyanide anions. The degradation of 2,6-dihydroxy-anthraquinone (DHAQ) to 2,6-dihydroxy-anthrone and 2,6-dihydroxy-anthranol has been quantified. We further identified the impurities commonly present in the DHAQ solution to be acetone, methanol and formamide. The crossover of DHAQ and impurity molecules through the sseparation Nafion® membrane was captured and quantified, and a negative correlation between the molecular size and crossover rate was established. We show that a benchtop NMR system has sufficient spectral and temporal resolution and sensitivity for the operando study of RFBs, and anticipate a broad application of operando benchtop NMR methods for studying flow electrochemistry targeted for different applications.

Comparison of Lanthanide Macrocyclic Complexes as 23Na NMR Sensors.

Nuclear magnetic resonance (NMR) agents, composed of paramagnetic lanthanide ions (Ln3+) complexed with negatively charged cyclic chelating agents (Che(n+3)-) forming polyanionic lanthanide complexes (LnChen-), perturb sodium-23 (23Na) signals, a phenomenon which depends sodium ions (Na+) exchanging with LnChen-. We analyzed 23Na shiftability and broadening due to hyperfine and bulk magnetic susceptibility (BMS) effects that arise from LnChen- designs using selective Ln3+ ions (i.e., thulium, Tm3+; gadolinium, Gd3+; and europium, Eu3+) and macrocyclics derived from 1,4,7,10-tetraazacyclododecane (cyclen) [i.e., with phosphonate (DOTP8-) and carboxylate (DOTMA4-) arms] and 1,4,7-triazacyclononane (TACN) [i.e., with phosphonate (NOTP6-) arms]. All LnChen- complexes showed downfield shifts, but Gd3+ and Tm3+ agents, respectively, were dominated by BMS and hyperfine effects, in good agreement with theory. While 23Na shiftability and broadening were minimally affected by pH and competing cations (K+, Ca2+, and Mg2+) within physiological ranges, the 23Na shiftability and broadening were most sensitive to LnChen- concentration in relation to the interstitial Na+ level in vivo. Greatest 23Na shiftability and broadening were obtained with Tm3+ and Gd3+ agents, respectively. While BMS contribution to shiftability was most impacted by the number of unpaired electrons on Ln3+, negative charge on LnChen- regulated Na+ exchange for line broadening. In brain tumor models, TmDOTP5- with 23Na-NMR has been used previously to separate Na+ in intracellular, blood, and interstitial pools, while evidence here shows that GdDOTP5- can distinguish Na+ within intracellular and extracellular (i.e., blood and interstitial) pools. Given the biological importance of Na+ in vivo, future macrocyclic designs of LnChen- should be sought for 23Na-NMR biomedical applications.

Noninvasive In Situ NMR Study of "Dead Lithium" Formation and Lithium Corrosion in Full-Cell Lithium Metal Batteries.

Capacity retention in lithium metal batteries needs to be improved if they are to be commercially viable, the low cycling stability and Li corrosion during storage of lithium metal batteries being even more problematic when there is no excess lithium in the cell. Herein, we develop in situ NMR metrology to study “anode-free” lithium metal batteries where lithium is plated directly onto a bare copper current collector from a LiFePO4 cathode. The methodology allows inactive or “dead lithium” formation during plating and stripping of lithium in a full-cell lithium metal battery to be tracked: dead lithium and SEI formation can be quantified by NMR and their relative rates of formation are here compared in carbonate and ether-electrolytes. Little-to-no dead Li was observed when FEC is used as an additive. The bulk magnetic susceptibility effects arising from the paramagnetic lithium metal were used to distinguish between different surface coverages of lithium deposits. The amount of lithium metal was monitored during rest periods, and lithium metal dissolution (corrosion) was observed in all electrolytes, even during the periods when the battery is not in use, i.e., when no current is flowing, demonstrating that dissolution of lithium remains a critical issue for lithium metal batteries. The high rate of corrosion is attributed to SEI formation on both lithium metal and copper (and Cu+, Cu2+ reduction). Strategies to mitigate the corrosion are explored, the work demonstrating that both polymer coatings and the modification of the copper surface chemistry help to stabilize the lithium metal surface.

Measurement and correction of the bulk magnetic susceptibility effects of fat: application in venous oxygen saturation imaging.

To develop a correction method for the effects of the magnetic susceptibility of fat (χFat ) on the calculation of venous oxygen saturation (SvO2 ). The magnetic field shifts associated with the magnetic susceptibility of deoxyhemoglobin can be used to estimate SvO2 , a measure of oxygen extraction and metabolism. However, the distinct magnetic susceptibility of fat surrounding targeted veins will give rise to magnetic field perturbations that will extend into the vein and surrounding tissues, potentially confounding the calculation of SvO2 . Multi-echo modified Dixon fat-water separated imaging was used to quantify fat-water distributions around the superficial femoral vein (venous return from the lower leg). Fat fraction images were used to generate χFat images, to calculate and remove the associated fat-susceptibility-induced magnetic field shifts before the estimation of SvO2 . This approach was evaluated at rest and with plantar flexion exercise to evaluate calf muscle oxygen extraction in 10 healthy subjects. The presence of fat around the vein resulted in complex magnetic field shifts and errors in estimated SvO2 . Corrected resting SvO2 values were significantly larger than those measured with conventional methods, at rest (72.6 ± 11.0% vs. 65.2 ± 12.2%, P < 0.05) and post-exercise (37.4 ± 12.3% vs. 31.7 ± 12.7%, P < 0.05), with larger errors in individuals and/or regions with increased fat volumes. Estimation and removal of the field-effects from χFat enabled the use of fat tissues for the measurement and removal of the background magnetic field. The magnetic susceptibility effects of fat can confound SvO2 estimation, but the susceptibility field effects can estimated and removed with the use of modified Dixon fat-water separated imaging.

In Situ Solid-State NMR Spectroscopy of Electrochemical Cells: Batteries, Supercapacitors, and Fuel Cells

Electrochemical cells, in the form of batteries (or supercapacitors) and fuel cells, are efficient devices for energy storage and conversion. These devices show considerable promise for use in portable and static devices to power electronics and various modes of transport and to produce and store electricity both locally and on the grid. For example, high power and energy density lithium-ion batteries are being developed for use in hybrid electric vehicles where they improve the efficiency of fuel use and help to reduce greenhouse gas emissions. To gain insight into the chemical reactions involving the multiple components (electrodes, electrolytes, interfaces) in the electrochemical cells and to determine how cells operate and how they fail, researchers ideally should employ techniques that allow real-time characterization of the behavior of the cells under operating conditions. This Account reviews the recent use of in situ solid-state NMR spectroscopy, a technique that probes local structure and dynamics, to study these devices. In situ NMR studies of lithium-ion batteries are performed on the entire battery, by using a coin cell design, a flat sealed plastic bag, or a cylindrical cell. The battery is placed inside the NMR coil, leads are connected to a potentiostat, and the NMR spectra are recorded as a function of state of charge. (7)Li is used for many of these experiments because of its high sensitivity, straightforward spectral interpretation, and relevance to these devices. For example, (7)Li spectroscopy was used to detect intermediates formed during electrochemical cycling such as LixC and LiySiz species in batteries with carbon and silicon anodes, respectively. It was also used to observe and quantify the formation and growth of metallic lithium microstructures, which can cause short circuits and battery failure. This approach can be utilized to identify conditions that promote dendrite formation and whether different electrolytes and additives can help prevent dendrite formation. The in situ method was also applied to monitor (by (11)B NMR) electrochemical double-layer formation in supercapacitors in real time. Though this method is useful, it comes with challenges. The separation of the contributions from the different cell components in the NMR spectra is not trivial because of overlapping resonances. In addition, orientation-dependent NMR interactions, including the spatial- and orientation-dependent bulk magnetic susceptibility (BMS) effects, can lead to resonance broadening. Efforts to understand and mitigate these BMS effects are discussed in this Account. The in situ NMR investigation of fuel cells initially focused on the surface electrochemistry at the electrodes and the electrochemical oxidation of methanol and CO to CO2 on the Pt cathode. On the basis of the (13)C and (195)Pt NMR spectra of the adsorbates and electrodes, CO adsorbed on Pt and other reaction intermediates and complete oxidation products were detected and their mode of binding to the electrodes investigated. Appropriate design and engineering of the NMR hardware has allowed researchers to integrate intact direct methanol fuel cells into NMR probes. Chemical transformations of the circulating methanol could be followed and reaction intermediates could be detected in real time by either (2)H or (13)C NMR spectroscopy. By use of the in situ NMR approach, factors that control fuel cell performance, such as methanol cross over and catalyst performance, were identified.

Paramagnetic electrodes and bulk magnetic susceptibility effects in the in situ NMR studies of batteries: Application to Li1.08Mn1.92O4 spinels

To date, in situ nuclear magnetic resonance (NMR) studies of working batteries have been performed in static mode, i.e., in the absence of magic angle spinning (MAS). Thus, it is extremely challenging to apply the method to paramagnetic systems such as the cathodes spinels Li1+xMn2−xO4 primarily due to three factors: (1) the resonance lines are broadened severely; (2) spectral analysis is made more complicated by bulk magnetic susceptibility (BMS) effects, which depend on the orientation and shape of the object under investigation; (3) the difficulty in untangling the BMS effects induced by the paramagnetic and metallic components on other (often diamagnetic) components in the system, which result in additional shifts and line broadening. Here we evaluate the orientation-dependence of the BMS effect of Li1.08Mn1.92O4, analyzing the experimental results by using a simple long-distance Li-electron dipolar coupling model. In addition, we discuss the shape and packing density dependence of the BMS effect and its influence on the observed frequencies of other components, such as the Li metal and the electrolyte in the battery. Finally, we show that by taking these effects into account we are able to minimize the BMS induced shift by orienting the cell at a rotation angle, αi=54.7° which facilitates the interpretation of the in situ NMR spectra of a working battery with the paramagnetic Li1.08Mn1.92O4 cathode.

In situ NMR of lithium ion batteries: Bulk susceptibility effects and practical considerations

The application of in situ nuclear magnetic resonance (NMR) to investigate batteries in real time (i.e., as they are cycling) provides fruitful insight into the electrochemical structural changes that occur in the battery. A major challenge for in situ static NMR spectroscopy of a battery is, however, to separate the resonances from the different components. Many resonances overlap and are broadened since spectra are acquired, to date, in static mode. Spectral analysis is also complicated by bulk magnetic susceptibility (BMS) effects. Here we describe some of the BMS effects that arise in lithium ion battery (LIB) materials and provide an outline of some of the practical considerations associated with the application of in situ NMR spectroscopy to study structural changes in energy materials.

X-ray Diffraction and NMR Studies of Na3−nLinAlH6 (n = 0, 1, 2) Alanates Synthesized by High-Pressure Reactive Ball Milling

The present work combines X-ray diffraction (XRD) analysis and NMR study of Na3−nLinAlH6 (n = 0, 1, 2) alanates synthesized by high-pressure reactive ball milling. Reactive ball-milling of alkali hydrides and Al under a hydrogen pressure of 10 MPa allows for the synthesis of Na3AlH6 and Na2LiAlH6 with a yield higher than 90 wt % when using 2 mol % of TiCl3 as a dopant. The synthesis of NaLi2AlH6 compound by reactive ball milling was not successful. The crystal structure of both Na3AlH6 and Na2LiAlH6 phases are in agreement with previous publications. The phase compositions of the synthesized samples obtained from XRD analysis are in good agreement with the results determined from NMR refinements. Without the addition of TiCl3, Na3AlH6 compound could also be formed, although the reaction was not complete due to slow kinetics. For the magic angle spinning NMR 27Al, 23Na, 6Li, and 1H spectra, strong bulk magnetic susceptibility (BMS) effects have been observed to affect to the same extent all detected lines and thus indicates that paramagnetic species (Ti3+ or Ti0 bearing phase) are present and well dispersed in the samples. 23Na and 27Al NMR spectra can be refined with very similar NMR parameters for both doped and nondoped samples, suggesting that Ti does not incorporate the crystal structure of these materials. Accurate values of 23Na and 27Al NMR parameters and quantification of the studied phases have been obtained thanks to a new treatment allowing for taking into account the BMS effects. Finally, a good agreement of experimental 23Na and 27Al quadrupolar parameters with density functional theory using the gauge-including projector augmented wave (DFT-GIPAW) predicted values is obtained. This work validates the use of DFT-GIPAW calculations for future NMR studies.

On 29Si NMR relaxation as a structural criterion for studying paramagnetic supermicroporous silica-based materials: Silica-based materials incorporating Mn 2+ ions into the silica matrix of SiO 2–Al 2O 3–MnO

Supermicroporous paramagnetic materials SiO 2–Al 2O 3–MnO and SiO 2–MnO with different manganese concentrations have been probed by solid-state 29Si NMR and magnetic susceptibility measurements. The 29Si T 1 and T 2 experiments, performed in static and spinning samples, have resulted in determination of electron relaxation times, providing, in turn, quantitative interpretations of 29Si T 1 times in terms of distances Mn–Si. The NMR relaxation data have revealed 29Si T 1 time distributions, which are close to Gaussian and observed as different T 1 values obtained in MAS NMR experiments for isotropic 29Si resonances and their sidebands. Such 29Si T 1 distributions, being a common phenomenon in paramagnetic silica-based materials, can be however masked by the bulk magnetic susceptibility (BMS) effects increasing with concentrations of paramagnetic centers. The presence of T 1 distributions, in itself, is not a criterion for incorporation of paramagnetic ions into the silica matrix or its surface. However, a quantitative analysis of the experimentally-observed short 29Si T 1 components, based on the well-determined electron relaxation times, can provide such a criterion.

The 29Si T1 and T2 NMR relaxation in porous paramagnetic material SiO 2–MnO–Al 2O 3

The 29Si spin–lattice relaxation in porous silica-based material 1, doped by ions Mn 2+ at a Si/Mn ratio of 3.5, is non-exponential, independent of magic-angle spinning (MAS) rates and governed by direct dipolar coupling between electron and nucleus where an electron relaxation time is estimated to be about 10 −8 s. In the absence of mutual energy-conserving spin flips (spin diffusion) in 1, the 29Si T 2 time increases linearly with spinning rates. None was observed in diamagnetic porous system 2. The unexpected 29Si T 2 dependence has been interpreted in terms of the large bulk magnetic susceptibility (BMS) effects. It has been shown that editing the 29Si Hahn-echo MAS NMR spectra eliminates wide lines, belonging to 29Si nuclei in the proximity of paramagnetic centers, and reduces the BMS broadenings in sideband patterns for nuclei remote from these centers.

PH and Cell Volume Effects on H 2O and Phosphoryl Resonance Splitting in Rapid-Spinning NMR of Red Cells

Two resonances are seen in the 1H-NMR spectrum of water in erythrocyte suspensions spun at the magic angle, a broad signal from water inside the cells and a sharp signal from extracellular water. The splitting is a result of a true chemical shift difference between the two populations, as bulk magnetic susceptibility effects are negated at the magic angle. The pH dependence of this chemical shift difference in erythrocyte suspensions was investigated. Splittings of 16.7 ± 0.1, 18.9 ± 0.9, and 21.0 ± 0.2 Hz were observed at pH 6.0, 7.0, and 8.5, respectively; however, this was accompanied by a change in the mean cell volume. To account for any contribution from the volume change, the osmolality of the pH 6.0 and 8.5 suspensions was adjusted to equalize the cell volume between samples at the three pHs. Under these conditions, the splitting was 18.3 ± 0.1 and 18.6 ± 0.1 Hz at pH 6.0 and 8.5, respectively. Thus the observed chemical shift difference between the two water resonances was independent of pH. Therefore the splitting of the water resonance was concluded to be directly proportional to the protein concentration within the cell. Measurements of the magnetic susceptibility difference between the two compartments were also carried out, yielding a value of 2.0 ± 0.2 × 10 −7 (SI units) for erythrocytes in isotonic saline at pH 7.0.

Gadolinium‐enhanced off‐resonance contrast angiography

We describe a novel physical basis and methodology for gadolinium (Gd)-enhanced MRA, which we call "off-resonance contrast angiography" (ORCA). Unlike standard contrast-enhanced (CE) MR angiography (MRA), ORCA contrast depends not on T(1) but on Gd-induced shifts in intravascular resonance frequency due to the bulk magnetic susceptibility (BMS) effects of Gd. The method was tested at 3 Tesla in phantoms with a range of dilutions of Gd-DTPA and ultrasmall iron oxide contrast agent (CA). With the use of ORCA, complete background suppression was obtained without image subtraction. As a result, catheters filled with various Gd dilutions proved to be highly conspicuous in ORCA projection images. This feature may make ORCA particularly attractive for passive catheter tracking during MR-guided endovascular procedures. Gd-induced intravascular frequency shifts were measured in human subjects and found to be in the expected range. ORCA was used to create angiograms of forearm veins that were comparable in quality to standard CE-MRA. In addition, ORCA images of the extracranial carotid bifurcation were successfully acquired during intravenous contrast administration. However, significant technical restrictions also exist, including a dependence on vessel orientation with respect to B(0), and sensitivity to static field inhomogeneities. Further study is needed to determine the practicality and potential clinical utility of this method.

Role of proton MR for the study of muscle lipid metabolism

1H-MR spectroscopy (MRS) of intramyocellular lipids (IMCL) became particularly important when it was recognized that IMCL levels are related to insulin sensitivity. While this relation is rather complex and depends on the training status of the subjects, various other influences such as exercise and diet also influence IMCL concentrations. This may open insight into many metabolic interactions; however, it also requires careful planning of studies in order to control all these confounding influences. This review summarizes various historical, methodological, and practical aspects of 1H-MR spectroscopy (MRS) of muscular lipids. That includes a differentiation of bulk magnetic susceptibility effects and residual dipolar coupling that can both be observed in MRS of skeletal muscle, yet affecting different metabolites in a specific way. Fitting of the intra- (IMCL) and extramyocellular (EMCL) signals with complex line shapes and the transformation into absolute concentrations is discussed. Since the determination of IMCL in muscle groups with oblique fiber orientation or in obese subjects is still difficult, potential improvement with high-resolution spectroscopic imaging or at higher field strength is considered. Fat selective imaging is presented as a possible alternative to MRS and the potential of multinuclear MRS is discussed. 1H-MRS of muscle lipids allows non-invasive and repeated studies of muscle metabolism that lead to highly relevant findings in clinics and patho-physiology.

Susceptibility corrections in solid-state NMR experiments with oriented membrane samples. Part I: applications

Chemical shift referencing of solid-state NMR experiments on oriented membranes has to compensate for bulk magnetic susceptibility effects that are associated with the non-spherical sample shape, as described in the accompanying paper [J. Magn. Reson. 164 (2003) 115–127]. The resulting frequency deviations can be on the order of 10 ppm, which is serious for nuclei with a narrow chemical shift anisotropy such as 1H or 13C, and in some cases even 19F. Two referencing schemes are proposed here to compensate for these effects: A flat (0.4 mm) glass container with an isotropic reference molecule dissolved in a thin film of liquid is stacked on top of the oriented membrane sample. Alternatively, the intrinsic proton signal of the hydrated lipid can be used for chemical shift referencing. Further aspects related to magnetic susceptibility are discussed, such as air gaps in susceptibility-matched probeheads, the benefits of shimming, and limitations in the accuracy of orientational constraints. A biological application is illustrated by a series of experiments on the antimicrobial peptide PGLa, aimed at understanding its concentration-dependent membranolytic effect. To address a wide range of molar peptide/lipid ratios between 1:3000 and 1:8, multilayers of hydrated DMPC containing a 19F-labeled peptide were oriented between stacked glass plates. Maintaining an approximately constant amount of peptide gives rise to thick samples (18 plates) at low, and thin samples (3 plates) at high peptide/lipid ratio. Accurate referencing was critical to reveal a small but significant change over 5 ppm in the anisotropic chemical shift of the 19F label on the peptide, indicative of a change in the orientation and/or dynamics of PGLa in the membrane.

High-resolution BOLD venographic imaging: a window into brain function.

This paper reviews the recent development of a new high-resolution magnetic resonance imaging approach to visualizing small veins in the human brain with diameters in the sub-millimeter range, which is smaller than a voxel. It briefly introduces the physical background of the underlying bulk magnetic susceptibility effects, on which this approach is based, and it demonstrates the successful application of the method for imaging different intracranial lesions, like venous anomalies, arteriovenous malformations and brain tumors. The susceptibility difference between venous blood and the surrounding tissue is used to generate contrast. Using this method it is possible to visualize draining veins in lesions better than conventional magnetic resonance imaging methods, which often require application of a contrast medium or even conventional catheter angiography. Limitations of the method are discussed. The ability to highlight deoxygenated blood with high spatial resolution yields important vascular parameters which may be helpful for improved modeling of MR signal changes during functional brain activation, it may lead to a better understanding of brain function in diseased states, or it may even offer the possibility of differentiating benign from malignant tumors non-invasively.

Toroid Cavity Detectors for High-Resolution NMR Spectroscopy and Rotating Frame Imaging: Capabilities and Limitations

The capabilities of toroid cavity detectors for simultaneous rotating frame imaging and NMR spectroscopy have been investigated by means of experiments and computer simulations. The following problems are described: (a) magnetic field inhomogeneity and subsequent loss of chemical shift resolution resulting from bulk magnetic susceptibility effects, (b) image distortions resulting from off-resonance excitation and saturation effects, and (c) distortion of lineshapes and images resulting from radiation damping. Also, special features of signal analysis including truncation effects and the propagation of noise are discussed. B0 inhomogeneity resulting from susceptibility mismatch is a serious problem for applications requiring high spectral resolution. Image distortions resulting from off-resonance excitation are not serious within the rather narrow spectral range permitted by the RF pulse lengths required to read out the image. Incomplete relaxation effects are easily recognized and can be avoided. Also, radiation damping produces unexpectedly small effects because of self-cancellation of magnetization and short free induction decay times. The results are encouraging, but with present designs only modest spectral resolution can be achieved.

Magnetic susceptibility shift selected imaging (MESSI) and localized (1)H(2)O spectroscopy in living plant tissues.

Maize root segments permeated with aqueous solutions of the paramagnetic agents GdDTPA(2-) or DyDTPA-BMA display two well-resolved NMR peaks corresponding to the signals from intracellular and extracellular (1)H(2)O, which arise from well-understood bulk magnetic susceptibility effects. This allows each component to be studied separately. Images obtained at each frequency with MESSI editing, and single- and multiple-voxel ('spectroscopic imaging') localized spectra, clearly indicate that the agents permeate into the interstitial spaces, and into the longitudinal (xylem/phloem) channels in the stele (core) of the root, confirming earlier assessments. We believe these are the first images of a multicellular tissue acquired in vivo exclusively from the intracellular water proton resonance. This method can be further exploited to study water transport in similar systems.

NMR spectroscopy and MRI investigation of a potential bioartificial liver.

NMR feasibility was established for a coaxial hydrophobic-membrane bioreactor containing isolated rat hepatocytes with features designed to mimic the human liver. A novel triple-tuned NMR probe and a perfusion system controlling temperature, gas concentrations, flow-rate, and pH were used. We determined the optimum coaxial interfiber distance (i.e. diffusion distance) for maintaining hepatocyte viability in two bioreactor prototypes. Prototype no. 1 and no. 2 had diffusion distances of 500 microns and 200 microns, respectively. Cell viability was established by 31P NMR and trypan blue exclusion. Only prototype no. 2 maintained cell viability for more than 6 h, indicating the importance of diffusion distance. 31P spectra obtained over this 6 h time period were similar to in vivo spectra of rat liver. The 31P spectra were found to be more sensitive to subacute cell viability than trypan blue exclusion. In the 1H and 31P spectra, 1H2O and inorganic phosphate signals were split in two at all flow-rates, probably due to bulk magnetic susceptibility effects originating from the three bioreactor compartments. MRI was useful for quality control and determining flow dynamics, fiber integrity, and cell inoculate distribution. MRI revealed that the inner fibers were not centered in either prototype. Although an increased flow-rate did not influence spectral resolution or chemical shifts, significant degradation of MRI quality occurred above 50 mL/min. NMR spectroscopy and imaging provide valuable, real-time information on cell biochemistry and flow dynamics which can be used in development and monitoring of bioreactors designed as artificial livers.

In vivo sodium chemical shift imaging

The shift reagents thulium(III) 1,4,7,10-tetraazacyclododecane N,N',N",N"'tetramethylenephosphonate (TmDOTP5-), and dysprosium(III)triethylenetetramine-hexaacetate (DyTTHA3-) are compared in this work for their uses in sodium chemical shift imaging (NaCSI). In a series of experiments using phantoms we evaluated the relative contributions of bulk magnetic susceptibility (BMS) effects and hyperfine shifts to the induced 23Na chemical shift for these two shift reagents. The ratios of BMS effects to hyperfine shifts suggest that TmDOTP5- should be a more effective shift reagent than DyTTHA3- for 23Na NMR spectroscopy as well as NaCSI. The dependence on pH and free Ca2+ concentration of the 23Na NMR frequency shift induced by TmDOTP5- was evaluated. It was found that TmDOTP5- produces good spectral resolution under physiologic conditions. Examples presented from in vivo NaCSI experiments using TmDOTP5- to study diffusion in the posterior chamber of the rabbit eye and to monitor the rate of clearance of aqueous fluid from the anterior chamber demonstrate the effectiveness of this new shift reagent and of the NaCSI technique for in vivo studies.