Saturation Recovery Experiments Research Articles

Biexponential I = 3/2 Spin-Lattice Relaxation in the Solid State: Multiple-Quantum 7Li NMR as a Probe of Fast Ion Dynamics.

Spin-lattice relaxation measurements are used in 7Li NMR studies of materials of potential use in solid-state Li-ion batteries as a probe of ion mobility on a fast (nanosecond to picosecond) time scale. The relaxation behavior is often analyzed by assuming exponential behavior or, equivalently, a single T1 time constant. However, the spin-lattice relaxation of spin I = 3/2 nuclei, such as 7Li, is in general biexponential; this is a fundamental property of I = 3/2 nuclei and unrelated to any compartmentalization within the solid. Although the possibility of biexponential 7Li (and other I = 3/2 nuclei) spin-lattice relaxation in the solid state has been noted by a number of authors, it can be difficult to observe unambiguously using conventional experimental NMR techniques, such as inversion or saturation recovery. In this work, we show that triple-quantum-filtered NMR experiments, as previously exploited in I = 3/2 NMR of liquids, can be used in favorable circumstances to observe and readily quantify biexponential 7Li spin-lattice relaxation in solids with high ion mobility. We demonstrate a triple-quantum-filtered inversion-recovery experiment on the candidate solid electrolyte material Li2OHCl at 325 K, which has previously been shown to exhibit fast ion mobility, and we also introduce a novel triple-quantum-filtered saturation-recovery experiment. The results of these solid-state NMR experiments are less straightforward than those in liquids as a consequence of the unwanted direct excitation of triple-quantum coherences by the weak (compared with the unaveraged 7Li quadrupolar interaction) pulses used, but we show that this unwanted excitation can be accounted for and, in the example shown here, does not impede the extraction of the two 7Li spin-lattice relaxation times.

Molecular-Engineered Biradicals Based on the YIII-Phthalocyanine Platform

A mixed-ligand phthalocyanine/porphyrin yttrium(III) radical double-decker complex (DD) was synthesized using the custom-made 5,10,15-tris(4-methoxyphenyl)-20-(4-((trimethylsilyl)ethynyl)phenyl)porphyrin. The trimethylsilyl functionality was then used to couple two such complexes into biradicals through rigid tethers. Glaser coupling was used to synthesize a short-tethered biradical (C1) and Sonogashira coupling to synthesize longer-tethered ones (C2 and C3). Field-swept echo-detected (FSED), saturation recovery, and spin nutation-pulsed electron paramagnetic resonance experiments revealed marked similarities of the magnetic properties of DD with those of the parent [Y(pc)2]• complex, both in the solid state and in CD2Cl2/CDCl3 4:1 frozen glasses. FSED experiments on the biradicals C2 and C3 revealed a spectral broadening with respect to the spectra of DD and [Y(pc)2]• assigned to the effect of dipolar interactions in solution. Apart from the main resonance, satellite features were also observed, which were simulated with dipole-dipole pairs of shortest distances, suggesting spin delocalization on the organic tether. FSED experiments on C1 yielded spectral line shapes that could not be simulated as the integration of the off-resonance echoes was complicated by field-dependent modulations. While, for all dimers, the on-resonance spin nutation experiments yielded Rabi oscillations of the same frequencies, off-resonance nutations on C1 yielded Rabi oscillations that could be assigned to a MS = -1 to MS = 0 transition within a S = 1 multiplet. The DFT calculations showed that the trans conformation of the complexes was significantly more stable than the cis one and that it induced a marked spin delocalization over the rigid organic tether. This "spin leakage" was most pronounced for the shortest biradical C1.

A focus on detection of polymorphs by dynamic nuclear polarization solid-state nuclear magnetic resonance spectroscopy.

Solid-state nuclear magnetic resonance (ssNMR) spectroscopy has found increasing application as a method for quantification and structure determination of solid forms (polymorphs) of organic solids and active pharmaceutical ingredients (APIs). However, ssNMR spectroscopy suffers from low sensitivity and resolution, making it challenging to detect dilute solid forms that may be present after recrystallization or reaction with co-formers. Cousin et al. (S. F. Cousin et al., Chem. Sci., 2023, https://doi.org/10.1039/D3SC02063K) have demonstrated that dynamic nuclear polarization (DNP) enhanced 13C cross-polarization (CP) saturation recovery experiments can be used to detect dilute polymorphic forms that are present within a mixture of solid forms. Enhancement of the NMR signal by DNP and differences in signal build-up rates for different polymorphs provide the sensitivity and contrast needed to resolve NMR signals from minor polymorphic forms. This method demonstrated by Cousin et al. should aid the discovery of solid drug forms.

Investigating bone resorption in Atlantic herring fish intermuscular bones with solid-state NMR.

Bones are connective tissues mainly made of collagen proteins with calcium phosphate deposits. They undergo constant remodeling, including destroying existing bones tissues (known as bone resorption) and rebuilding new ones. Bone remodeling has been well-described in mammals, but it is not the case in fish. Here, we focused on the mobile phase of the bone vascular system by carefully preserving moisture in adult Atlantic herring intermuscular bones. We detected pore water with high ionic strength and soluble degraded peptides whose 1H-transverse relaxation times, T2s, exceed 15 milliseconds. With favorable T2s, we incorporated a solution state spinlock scheme into the INEPT techniques to unequivocally demonstrate collagen degradation. In addition, we detected a substantial amount of inorganic phosphate in solution with 31P-NMR in the considerable background of solid hydroxyapatite calcium phosphate by saturation recovery experiment. It is consistent with the idea that bone resorption degrades bone collagen and releases calcium ions and phosphate ions in the pore water with increased ionic strength. Our report is the first to probe the resorption process in the heterogenous bone microstructure with a rigorous characterization of 1H and 13C relaxation behavior and direct assignments. In addition, we contribute to the fish bones literature by investigating fish bone remodeling using NMR for the first time.

Magic angle spinning NMR below 6 K with a computational fluid dynamics analysis of fluid flow and temperature gradients

We report magic angle spinning (MAS) up to 8.5 kHz with a sample temperature below 6 K using liquid helium as a variable temperature fluid. Cross polarization 13C NMR spectra exhibit exquisite sensitivity with a single transient. Remarkably, 1H saturation recovery experiments show a 1H T1 of 21 s with MAS below 6 K in the presence of trityl radicals in a glassy matrix. Leveraging the thermal spin polarization available at 4.2 K versus 298 K should result in 71 times higher signal intensity. Taking the 1H longitudinal relaxation into account, signal averaging times are therefore predicted to be expedited by a factor of >500. Computer assisted design (CAD) and finite element analysis were employed in both the design and diagnostic stages of this cryogenic MAS technology development. Computational fluid dynamics (CFD) models describing temperature gradients and fluid flow are presented. The CFD models bearing and drive gas maintained at 100 K, while a colder helium variable temperature fluid stream cools the center of a zirconia rotor. Results from the CFD were used to optimize the helium exhaust path and determine the sample temperature. This novel cryogenic experimental platform will be integrated with pulsed dynamic nuclear polarization and electron decoupling to interrogate biomolecular structure within intact human cells.

Improved post-processing strategy for MOLLI based tissue characterization allows application in patients with dyspnoe and impaired left ventricular function

Contrast and non-contrast MRI based characterization of myocardium by T1-mapping will be of paramount importance to obtain biomarkers, e.g. fibrosis, which determines the risk of heart failure patients.T1-mapping by the standard post-processing of the modified look-locker inversion recovery (MOLLI) lacks of accuracy when trying to reduce its duration, which on the other hand, is highly desirable in patients with heart failure. The recently suggested inversion group fitting (IGF) technique, which considers more parameters for fitting, has a superior accuracy for long T1 times despite a shorter duration. However, for short T1 values, the standard method has a superior precision. A conditional fitting routine is proposed which ideally takes advantage of both algorithms. Materials and methodsAll measurements were performed on a 1.5T clinical scanner (ACHIEVA, Philips Healthcare, The Netherlands) using a MOLLI 5(n)3(n)3 prototype with n(heart beats) being a variable waiting time between inversion experiments. Phantom experiments covered a broad range of T1 times, waiting times and heart rates. A saturation recovery experiment served as a gold standard for T1 measurement. All data were analyzed with the standard MOLLI, the IGF fit and the conditional fitting routine and the obtained T1 values were compared with the gold standard. In vivo measurements were performed in a healthy volunteer and a total of 34 patients with normal findings, dilative cardiomyopathy and amyloidosis. ResultsTheoretical analysis and phantom experiments provided a threshold value for an apparent IGF T1* determining processing with IGF post processing for values above, or switching to the standard technique for values below. This was validated in phantoms and patients measurements. A reduction of the waiting time to 1 instead of 3 heart beats between the inversion experiments showed reliable results. The acquisition time was reduced from 17 to 13 heart beats. The in vivo measurements showed ECV values between 25% (18–33%; SD 0.03) in the healthy, 30% (22–40%; SD 0.04) in patients with DCM and 45% (30–60%; SD 0.9) in patients with amyloidosis. ConclusionThe adopted post-processing algorithm determines long T1 values with high accuracy and short T1 values while maintaining a high precision. Based on reduction of waiting time, and independence of heart rate, it shortens breath hold duration and allows fast T1-mapping, which is frequently a prerequisite in patients with cardiac diseases.

In vivo proton T1 relaxation times of mouse myocardial metabolites at 9.4 T.

Proton magnetic resonance spectroscopy ((1) H-MRS) for quantitative in vivo assessment of mouse myocardial metabolism requires accurate acquisition timing to minimize motion artifacts and corrections for T1 -dependent partial saturation effects. In this study, mouse myocardial water and metabolite T1 relaxation time constants were quantified. Cardiac-triggered and respiratory-gated PRESS-localized (1) H-MRS was employed at 9.4 T to acquire signal from a 4-µL voxel in the septum of healthy mice (n = 10) while maintaining a steady state of magnetization using dummy scans during respiratory gates. Signal stability was assessed via standard deviations (SD) of zero-order phases and amplitudes of water spectra. Saturation-recovery experiments were performed to determine T1 values. Phase SD did not vary for different repetition times (TR), and was 13.1° ± 4.5°. Maximal amplitude SD was 14.2% ± 5.1% at TR = 500 ms. Myocardial T1 values (mean ± SD) were quantified for water (1.71 ± 0.25 s), taurine (2.18 ± 0.62 s), trimethylamine from choline-containing compounds and carnitine (1.67 ± 0.25 s), creatine-methyl (1.34 ± 0.19 s), triglyceride-methylene (0.60 ± 0.15 s), and triglyceride-methyl (0.90 ± 0.17 s) protons. This work provides in vivo quantifications of proton T1 values for mouse myocardial water and metabolites at 9.4 T.

Investigation on Relationship Between Energy Storage and Special Performance of L-arginine Phosphate Monohydrate (LAP) Crystal

Phosphate arginine (PA) has been known as the medium carriers for bioenergy storage, while the similar structural substance L-arginine phosphate monohydrate (LAP) crystal is an excellent nonlinear optical crystal with a high laser-induced damage threshold. Energy storage in organism and laser-induced damage in crystals are both correlative to energy. Temperature dependence X-ray diffraction (XRD) and solid state NMR spectroscopy were performed to explore the impact of energy (heat and magnetic) fields on LAP crystal. XRD results reveal that LAP processes a reversible specific phase transition as the temperature changed. Saturation recovery experiments have shown that the crystal has a long proton spin-lattice relaxation time (1H T1) of 184 s with an amazing solid-state stability. The nuclear magnetic resonance (NMR) and fluorescence emission spectra of LAP solution compared with several amino salt solutions have also been investigated. The results show that the emission wavelength of LAP solution is blue-shifted from 415 to 380 nm. When energy (laser, heat, magnetic and etc.) fields are applied on LAP crystal, it processes a various of distinctive properties which make LAP a special material worthy of further detailed investigation.

Multi-nuclear NMR study of polytype and defect distribution in neutron irradiated silicon carbide

Silicon carbide containing 92% β-SiC has been irradiated in a material test reactor at a fast neutron fluence (>0.1MeV) of 3.39×1021ncm−2 at an average temperature of 796°C, and subsequently studied by 29Si and 13C MAS NMR spectroscopy. A small amount of structural alteration was measured with the α-SiC polytypes increasing from around 8–14%. Based on the assumption that the primary dominant defect is the paramagnetic SiV- defect. The defect concentration has been measured in both the irradiated and unirradiated sample using spin lattice relaxation time (T1) data obtained via a saturation-recovery experiment and was found to increase from 4.6×1018cm−3 to 1.5×1020cm−3. A case is presented to show that a small residual internuclear dipolar coupling contribution (at 3.80×10−6% of its total value) towards the T1 in the unirradiated reference sample significantly modifies the relaxation time from a value based solely on the dominant nuclear defect coupling mechanism.

Measuring Cu2+-Nitroxide Distances Using Double Electron–Electron Resonance and Saturation Recovery

Distance measurements were obtained between a bound Cu2+ and a spin label on two polypeptides of differing length using the double electron–electron resonance (DEER) and saturation recovery experiments. Distance distributions obtained from the DEER results resolved differences between the average distance and distribution of distances for each peptide. An average distance was also obtained for each peptide using the relaxation-based saturation recovery experiment. Predicted average distances for the relaxation-based method, , were calculated using the distance distributions from the DEER experiment. The predicted values were similar to those measured by saturation recovery; both were biased to shorter values compared with the DEER results. The breadth of the distance distributions had a significant effect on the average distance measured by saturation recovery. This work highlights the advantage of using DEER to measure metal-nitroxide distances in that the average distances measured are less biased than in relaxation-based techniques.

Practical considerations in T1 mapping of prostate for dynamic contrast enhancement pharmacokinetic analyses

There are many challenges in developing robust imaging biomarkers that can be reliably applied in a clinical trial setting. In the case of dynamic contrast-enhanced (DCE) MRI, one such challenge is to obtain accurate precontrast T1 maps for subsequent use in two-compartment pharmacokinetic models commonly used to fit the MR enhancement time courses. In the prostate, a convenient and common approach for this task has been to use the same 3D spoiled gradient-echo sequence used to collect the DCE data, but with variable flip angles (VFAs) to collect data suitable for T1 mapping prior to contrast injection. However, inhomogeneous radiofrequency conditions within the prostate have been found to adversely affect the accuracy of this technique. Herein we demonstrate the sensitivity of DCE pharmacokinetic parameters to precontrast T1 values and examine methods to improve the accuracy of T1 mapping with flip angle-corrected VFA SPGR methods, comparing T1 maps from such methods with “gold standard” reference T1 maps generated with saturation recovery experiments performed with fast spin-echo (FSE) sequences.

Radiofrequency pulse sequences which compensate their own imperfections

Radiofrequency pulse sequences are described which have the same overall effect as a single 90° or 180° pulse but which compensate the undesirable effects of resonance offset and spatial inhomogeneity of the radiofrequency field H 1. These “composite” pulses are built up from a small number of conventional pulses which rotate the nuclear magnetization vectors about different axes in the rotating frame, while in the intervals between pulses a limited amount of free precession may be allowed to occur. Insight into the way in which pulse imperfections are compensated is obtained by computer simulation of trajectories of families of nuclear spin “isochromats” representing a distribution of H 1 intensity or resonance offset. Composite 90° pulses are suggested as a method of reducing systematic errors in spin-lattice relaxation times derived from progressive saturation or saturation-recovery experiments, and as the preparation pulse of a spin-locking experiment. A test of the effectiveness of the composite 180° pulse sequence has been made by using it for population inversion in a spin-lattice relaxation measurement, where T 1 is derived from the null point in the recovery curve, a technique known to be very sensitive to pulse imperfections.

A Fluorinated Dendrimer-Based Nanotechnology Platform

We aimed to develop a directly detected magnetic resonance imaging (MRI) contrast agent for use with high fields based on a nanoscale fluorinated dendrimer-based platform for F MRI and overcome some of the problems with F MRI. The dendrimers were prepared in a convergent manner by making the appropriate dendron, followed by coupling to a central core. The dendrons were prepared by attaching 3 equivalents of the fluorinated amino acid to the 3 carboxylic acids of the repeat branch unit followed by deprotection of the amine branch point, and either coupling to another repeat branch unit (increasing the generation G) or used directly allowing the precise growth of the dendrimer. The size of the dendrimers was determined by diffusion nuclear magnetic resonance (NMR) spectroscopy. The toxicity of the dendrimers was measured using the MTT assay. Fluorine longitudinal relaxation time measurements were performed on a Bruker ACP-500 NMR using a saturation recovery experiment at 470.59 MHz frequency. Healthy 150 g Sprague-Dawley female rats were imaged using a dendrimer solution. The size of the dendrimers is generally less than 3 nm, 2 orders of magnitude smaller than the size of the perfluorocarbon nanoparticles (about 200 nm). The longitudinal relaxation time, T1, decreases with increasing dendrimer generation. A significant improvement in relaxation rate and signal-to-noise ratio can be achieved by either the chemical modification of the dendrimer with a gadolinium-chelate or by the physical addition of exogenous contrast agent. Although the dendrimers with fluorine in the surface layer are toxic, this toxicity is easily reduced by burying the fluorine further into the dendrimer interior. (19)F MR images of the rat using the dendrimer solution were rapidly obtained at 7 Tesla, the strong contrast in the heart generated by the dendrimer can be seen. A novel fluorinated dendrimer-based nanotechnology platform in (19)F MRI and a new bifunctional DOTA chelate were prepared and characterized. We introduce 2 methods for reducing the (19)F longitudinal relaxation time: (a) Increasing the generation; (b) covalent and noncovalent introduction of Gd(III)-chelates. A new bifunctional Gd(III)-chelate is presented. The investigations of imaging on rats suggest potential importance of the dendrimers in (19)F MRI application.

Solid-State Carbon NMR Characterization and Investigation of Intrinsic Dissolution Behavior of Fluconazole Polymorphs, Anhydrate Forms I and II

Solid-state (13)C nuclear magnetic resonance ((13)C-SSNMR) revealed significant differences in the chemical shift of specific carbon atoms between two fluconazole polymorphs, reflecting a change in molecular conformation. A single resonance signal without splitting was observed in the spectrum of anhydrate form II, while the spectrum of anhydrate form I showed signals with splitting, indicating the presence of two dissimilar molecular conformations in the unit cell of anhydrate form I. The Fourier transform infrared (FT-IR) and Raman spectra associated with the triazole group, the 2,4-difluorobenzyl group, and the propane backbone provided also evidence of structural differences between forms I and II accompanying with (13)C-SSNMR. (1)H T(1) relaxation times, measured using saturation recovery experiments, showed that the metastable anhydrate form II was more mobile than the stable form I. The solubility and intrinsic dissolution tests showed that the anhydrate form II was more soluble and dissolved faster than the anhydrate form I.

Spin-diffusion NMR at low field for the study of multiphase solids

The use of spin-diffusion NMR for the measurement of domain sizes in multiphase materials is becoming increasingly popular, in particular for the study of heterogeneous polymers. Under conditions where T 1 relaxation can be neglected, which is mostly the case at high field, analytical and approximate solutions to the evolution of spin diffusion are available. In order to extend the technique to more general conditions, we performed a comprehensive study of the diffusion of magnetization in a model copolymer at low field, where T 1 tends to be of the same order of magnitude as the typical spin-diffusion time. In order to study the effects of T 1 and to delineate the optimal T 1 values for back correction prior to applying the initial-rate approximation, we developed a numerical simulation based on the diffusion equation and including longitudinal relaxation. We present and discuss the limits of simple correction strategies for initial-slope analysis based on apparent relaxation times from saturation-recovery experiments or the spin-diffusion experiments themselves. Our best strategy faithfully reproduces domain sizes obtained by both TEM investigations and full simultaneous fitting of spin-diffusion and saturation-recovery curves. Full fitting of such independent data sets not only yields correct domain sizes, but also the true longitudinal relaxation times, as well as spin-diffusion coefficients. Effects of interphases with distinct mobility on spin-diffusion curves, as well as practical hints concerning the reliable component decomposition of the detected low-resolution FID signal by help of different magnetization filters are also discussed in detail.

EPR Free Induction Decay Coherence Observed after a Single Pulse in Saturation Recovery Experiments for Samples with Resolved Multiline CW Spectra

An electron paramagnetic resonance (EPR) spin-coherence signal has been observed following a single pulse for rapidly tumbling radicals with well-resolved nuclear hyperfine splitting in fluid solution when B1 is large enough to excite multiple hyperfine lines. This signal, which has the shape of a spin echo, arises from constructive interference of overlapping free induction decays (FIDs) from the hyperfine lines. It has been observed for 2,6-di-t-butyl-1,4-benzosemiquinone, 2,5-di-t-butyl-1,4-benzosemiquinone, 2,3,5,6-tetramethoxy-1,4-benzosemiquinone, 2,4,6-tri-t-butylphenoxyl radical, and 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy. It occurs at a time after the pulse that is equal to the inverse of the nuclear hyperfine splitting, independent of EPR resonance frequency from 250 MHz to 9.1 GHz. As the length of the pulse is increased, separate coherence signals can be observed that correspond to the beginning and end of the pulse. This coherence is distinct from the "single-pulse echo" signals discussed in the literature. For 2,6-di-t-butyl-1,4-benzosemiquinone, which has two resolved couplings (1.24 and 0.052 G), FID oscillations with a period that corresponds to the larger hyperfine coupling are observed on the coherence signal that arises from the smaller hyperfine coupling. If phase cycling is not perfect, the coherence signal can interfere with measurements of T1 by saturation recovery.

Investigation of the Effects of Pharmaceutical Processing Upon Solid-State NMR Relaxation Times and Implications to Solid-State Formulation Stability

Crystalline lactose was subjected to various forms of pharmaceutical processing including compaction, lyophilization, spray drying, and cryogrinding. 13C cross polarization and magic-angle spinning (CPMAS) NMR spectra were acquired for bulk crystalline lactose as well as the processed samples. Saturation recovery experiments to determine proton spin-lattice relaxation times (1H T1) showed that the α-monohydrate form had a 1H T1 of 243 s, while compaction resulted in a threefold reduction in T1 (79 s), with little change in the spectrum. Lyophilization and spray drying both produced amorphous lactose, with relaxation times around 4s. Cryogrinding for various times produced mixtures of crystalline and amorphous material, with the amount of amorphous material increasing with grinding time. Sixty minutes of grinding time produced mostly amorphous material, with some crystalline material remaining. The 1H T1 of this sample was 2.0s. Reducing particle size, introducing crystal defect sites, and producing amorphous material all serve to reduce the T1 by creating sites of high mobility. Spin diffusion to the high-energy sites creates a uniform 1H T1 across the sample. The result is shorter relaxation times for the high-energy mixtures. Relaxation measurements performed on dosage forms could potentially be used to predict stability of pharmaceutical formulations.

Magnetization-recovery experiments for static and MAS-NMR of I = 3/2 nuclei

Multifrequency pulsed NMR experiments on quadrupole-perturbed I = 3/2 spins in single crystals are shown to be useful for measuring spin–lattice relaxation parameters even for a mixture of quadrupolar plus magnetic relaxation mechanisms. Such measurements can then be related to other MAS-NMR experiments on powders. This strategy is demonstrated by studies of 71Ga and 69Ga (both I = 3/2) spin–lattice relaxation behavior in a single-crystal (film) sample of gallium nitride, GaN, at various orientations of the axially symmetric nuclear quadrupole coupling tensor. Observation of apparent single-exponential relaxation behavior in I = 3/2 saturation-recovery experiments can be misleading when individual contributing rate processes are neglected in the interpretation. The quadrupolar mechanism (dominant in this study) has both a single-quantum process ( T 1Q1) and a double-quantum process ( T 1Q2), whose time constants are not necessarily equal. Magnetic relaxation (in this study most likely arising from hyperfine couplings to unpaired delocalized electron spins in the conduction band) also contributes to a single-quantum process ( T 1M). A strategy of multifrequency irradiation with observation of satellite and/or central transitions, incorporating different initial conditions for the level populations, provides a means of obtaining these three relaxation time constants from single-crystal 71Ga data alone. The 69Ga results provide a further check of internal consistency, since magnetic and quadrupolar contributions to its relaxation scale in opposite directions compared to 71Ga. For both perpendicular and parallel quadrupole coupling tensor symmetry axis orientations small but significant differences between T 1Q1 and T 1Q2 were measured, whereas for a tensor symmetry axis oriented at the magic-angle (54.74°) the values were essentially equal. Magic-angle spinning introduces a number of complications into the measurement and interpretation of the spin–lattice relaxation. Comparison of 71Ga and 69Ga MAS-NMR saturation-recovery curves with both central and satellite transitions completely saturated by a train of 90° pulses incommensurate with the rotor period provides the simplest means of assessing the contribution from magnetic relaxation, and yields results for the quadrupolar mechanism contribution that are consistent with those obtained from the film sample.

Spin-Label EPR T1 Values Using Saturation Recovery from 2 to 35 GHz

EPR saturation-recovery (SR) measurements of the electron spin-lattice relaxation time, T1, of nitroxide-radical spin probes have been made from 2 to 35 GHz. T1 values of small water-soluble spin probes increase linearly with microwave frequency throughout the full range of available frequencies. T1 values of four commonly used hydrophobic probes in lipid bilayers also increase with frequency, but the dependence is weaker and complex. Contributions of dissolved molecular oxygen to relaxation rates were independent of microwave frequency. T1 values of 15N-containing labels are always somewhat longer than for 14N labels. Details of the Q-band SR spectrometer, which is based on frequency translation technology, are provided. A new way to suppress free induction decay signals in SR experiments has been found: pump and observing frequencies time-locked and separated by about 1 kHz in frequency. A novel three-loop−two-gap resonator with a sample volume of 30 nl was used for the Q-band measurements. It is concluded that Q-band is a favorable frequency for SR spin-label oximetry studies.

Fast chemical-shiftT 1 imaging in toroid cavities for the structural analysis of gels and emulsions

Fast chemical-shiftT1 imaging in toroid cavity cells (TCCs) is introduced and applications to diagnostic ultrasound gel and skin-care ointment are presented. TCCs are an advancement over previously used toroid cavity detectors because they combine resonator and sample container into one part. Additionally, they are removable from the top of the probe and facilitate convenient probe and sample handling. Radially resolvedT1 relaxation times in TCCs are obtained through combination of SR (saturation recovery) experiments with the RIPT (rapid imaging with a pulse train) technique. Because of the strong radialB1 gradient in TCCs, only pulse-burst saturation was found satisfactory to generate the most even starting condition for SR experiments. Because RIPT does not resolve chemical-shift information, magnetization andT1 profiles of individual components in mixed samples are monitored by double-transient experiments with selective on-resonance saturation, which is achieved by converging trains of sinc pulses. The new techniques were applied to cellulose hydrogel and oil-in-water emulsion both exposed to significant shear stress deformation during the charging of the TCC. In both cases,T1 profiles as a function of time reveal structural recovery (thixotropy) that slowly progresses from one or more sample interfaces into the bulk.