Magnetic-field-induced enhancements of nuclear spin-lattice relaxation rates in the heavy-fermion superconductor CeCoIn5 using 59Co nuclear magnetic resonance

(59)Co nuclear spin-lattice relaxation has been measured for the heavy-fermion superconductor CeCoIn(5) in a range of applied fields directed parallel to the c axis. An enhanced normal-state relaxation rate, observed at low temperatures and fields just above H(c2)(0), is taken as a direct measure of the dynamical susceptibility and provides microscopic evidence for an antiferromagnetic instability. The results are well described using the self-consistent renormalized theory for two-dimensional antiferromagnetic spin fluctuations, and parameters obtained in the analysis are applied to previously reported specific heat and thermal expansion data with good agreement.     

Measurement of spin-lattice relaxation times in EPR with enhanced orientation selectivity

Two schemes for the measurement of orientation-dependent spin-lattice relaxation times are introduced, which combine the inversion-recovery experiment with electron-Zeeman-resolved or right-angle wiggling EPR. The principles of the experiments are outlined and their performance is illustrated by examples of application. With the electron Zeeman-resolved approach the relaxation times of two metal complexes with different g values are unraveled, whereas with right-angle wiggling the orientation-dependent relaxation behavior of a metal complex with large hyperfine anisotropy is analyzed.     

Measurement of proton spin-lattice relaxation rates of model phantoms in chemical imaging

A conventional, high-resolution NMR spectrometer has been adapted for measurement of the two-dimensional spatial distribution of spin-lattice relaxation rates using the inversion-recovery pulse sequence incorporated into the two-dimensional “spin-warp” imaging method. The approach is illustrated using a phantom made of capillary tubes containing aqueous manganese ethylenediaminetetracetic acid.     

New aspects of critical sound attenuation in magnetic systems with spin-lattice relaxation

A general theory of critical sound propagation, including phonon-spin-energy coupling, is studied in anisotropic magnets above their transition temperature. The Kawasaki weak singularity in the ultrasonic attenuation is found as a nonasymptotic effect. A new nonasymptotic regime similar to the one in the binary mixture is also determined. The role of coupling constants and the bare relaxation times in establishing the dominance region of particular terms, is discussed. Received: 9 December 1997 / Accepted: 24 February 1998     

On neglecting chemical exchange when correcting in vivo (31)P MRS data for partial saturation: commentary on: "Pitfalls in the measurement of metabolite concentrations using the one-pulse experiment in in Vivo NMR"

This article replies to Spencer et al. (J. Magn. Reson. 149, 251--257, 2001) concerning the degree to which chemical exchange affects partial saturation corrections using saturation factors. Considering the important case of in vivo (31)P NMR, we employ differential analysis to demonstrate a broad range of experimental conditions over which chemical exchange minimally affects saturation factors, and near-optimum signal-to-noise ratio is preserved. The analysis contradicts Spencer et al.'s broad claim that chemical exchange results in a strong dependence of saturation factors upon M(0)'s and T(1) and exchange parameters. For Spencer et al.'s example of a dynamic (31)P NMR experiment in which phosphocreatine varies 20-fold, we show that our strategy of measuring saturation factors at the start and end of the study reduces errors in saturation corrections to 2% for the high-energy phosphates.     

Pitfalls in the measurement of metabolite concentrations using the one-pulse experiment in in Vivo NMR: commentary on "On neglecting chemical exchange effects when correcting in vivo (31)P MRS data for partial saturation"

In an article in a previous issue of the Journal of Magnetic Resonance, Ouwerkerk and Bottomley (J. Magn. Reson. 148, pp. 425--435, 2001) show that even in the presence of chemical exchange, the dependence of saturation factors on repetition time in the one-pulse experiment is approximately monoexponential. They conclude from this fact that the effect of chemical exchange on the use of saturation factors when correcting for partial saturation is negligible. We take issue with this conclusion and demonstrate that because saturation factors in the presence of chemical exchange are strongly dependent upon all of the chemical parameters of the system, that is, upon all T(1)'s and M(0)'s of resonances in the exchange network and upon the reaction rates themselves, it is problematic to apply saturation factor corrections in situations in which any of these parameters may change. The error criterion we establish reflects actual errors in quantitation, rather than departures from monoexponentiality.     

Investigation of the mobility of paraffin molecules in channel urea clathrates by nuclear magnetic resonance relaxation spectroscopy

The temperature dependence of the proton spin-lattice relaxation time (T ₁) is investigated for channel urea clathrates with paraffin molecules. The results obtained are interpreted within the reorientational model of paraffin molecules and their fragments in clathrate channels. The specific features of the dynamics of normal paraffins in urea clathrates are associated with incommensurate regions in the structure of these compounds.     

Analysis of the magnetic field dependence of the nuclear magnetic relaxation times in solid He

We have analyzed the field dependence of the magnetic relaxation time T₁ in solid He³ and find that the experimental data are in good agreement with the theory of Blume and Hubbard for the time dependence of the spin correlation function.     

Proton nuclear magnetic resonance spectroscopy of normal and edematous brain tissue in vitro: Changes in relaxation during tissue storage

Proton nuclear magnetic resonance relaxation times, T₁ and T₂, of water in unfixed gray and white matter from normal and edematous rabbit brain tissues were measured in vitro at 23°C and 100 MHz to evaluate the effects of the temperature (?25°C to 37°C) and duration (0 to 96 h) of tissue storage on relaxation times. T₁ and T₂ tended to decrease during storage, probably from slow dehydration of the tissue. This effect was greatest in tissues stored at 37°C and least in those stored at 4 and ?25°C; decreases in T₁ and T₂ were greater in white matter than in gray matter. Freezing brain tissue to ?25°C caused a sudden decrease in the T₂ of normal white matter. Relaxation times were constant for 5 h in tissues stored at 23°C and for 40 h at 4°C. These results correlated well with corresponding tissue water loss.     

Average Liouvillian theory revisited: cross-correlated relaxation between chemical shift anisotropy and dipolar couplings in the rotating frame in nuclear magnetic resonance

A review is given of the mathematical foundations of average Liouvillian theory and examples are provided of average Liouvillian expressions derived for sequences in nuclear magnetic resonance which possess temporal symmetry or antisymmetry. The utility of this approach is demonstrated in the design of pulse sequences to measure the effect of cross-correlation between chemical shift anisotropy and dipolar couplings on relaxation rates in biomolecules. Experimental verification of the theory is carried out on a ¹⁵N labelled sample of ubiquitin.     

Separation of the impurity and lattice components of the spin-lattice relaxation of Al27 nuclei in corundum crystals under magnetic saturation conditions

The impurity and lattice contributions to the spin-lattice relaxation of Al²⁷ nuclei in nominally pure and lightly chromium-doped corundum (Al₂O₃) crystals are separated experimentally under the conditions of additional stationary resonance magnetic saturation of a pulsed NMR signal. The relaxation time T _i ^lat due to the lattice mechanism of the spin-phonon interaction is determined. Fiz. Tverd. Tela (St. Petersburg) 39, 1041–1043 (June 1997)     

Long repetition time experiments for measurement of concentrations in systems with chemical exchange and undergoing temporal variation-comparison of methods with and without correction for saturation

The purpose of this paper is to compare two methods for quantifying metabolite concentrations using the one-pulse experiment for a sample undergoing chemical exchange and subject to an intervention or other temporal variation. The methods, LATR-C (Long Acquisition TR (interpulse delay); Corrected for partial saturation) and LATR-NC (Long Acquisition TR; Not Corrected), are compared in terms of signal-to-noise ratio, SNR, per unit time and quantitation errors. Parameters relevant to the isolated perfused rat heart are used as a specific application, although the results are general. We assume throughout that spin-lattice relaxation times, T(1), do not change. For a given flip angle, theta, TR's are calculated which result in maximal SNR per unit time under 10%, 5%, and 1% constraints on quantitation errors. Additional simulations were performed to demonstrate explicitly the dependence of the quantitation errors on TR for a fixed theta. We find (i) if the allowed error is large, and when both metabolite concentrations and rate constants vary, LATR-C permits use of shorter TR, and hence yields greater SNR per unit time, than LATR-NC; (ii) for small allowed error, the two methods give similar TR's and SNR per unit time, so that the simpler LATR-NC experiment may be preferred; (iii) large values of theta result in similar constrained TR's and hence SNR per unit time for the two methods; (iv) the ratio of concentrations of metabolites with similar T(1) exhibit similar errors for the two methods.     

Assessment of the patellofemoral cartilage: Correlation of knee pain score with magnetic resonance cartilage grading and magnetization transfer ratio asymmetry of glycosaminoglycan chemical exchange saturation transfer

PurposeBiochemical imaging of glycosaminoglycan chemical exchange saturation transfer (gagCEST) could predict the depletion of glycosaminoglycans (GAG) in early osteoarthritis. The purpose of this study was to evaluate the relationship between the magnetization transfer ratio asymmetry (MTR_asym) of gagCEST images and visual analog scale (VAS) pain scores in the knee joint.Materials and methodsThis retrospective study was approved by the institutional review board. A phantom study was performed using hyaluronic acid to validate the MTR_asym values of gagCEST images. Knee magnetic resonance (MR) images of 22 patients (male, 9; female, 13; mean age, 50.3 years; age range; 25–79 years) with knee pain were included in this study. The MR imaging (MRI) protocol involved standard knee MRI as well as gagCEST imaging, which allowed region-of-interest analyses of the patellar facet and femoral trochlea. The MTR_asym at 1.0 ppm was calculated at each region. The cartilages of the patellar facets and femoral trochlea were graded according to the Outerbridge classification system. Data regarding the VAS scores of knee pain were collected from the electronic medical records of the patients. Statistical analysis was performed using Spearman's correlation.ResultsThe results of the phantom study revealed excellent correlation between the MTR_asym values and the concentration of GAGs (r = 0.961; p = 0.003). The cartilage grades on the MR images showed significant negative correlation with the MTR_asym values in the patellar facet and femoral trochlea (r = −0.460; p = 0.031 and r = −0.543; p = 0.009, respectively). The VAS pain scores showed significant negative correlation with the MTR_asym values in the patellar facet and femoral trochlea (r = −0.435; p = 0.043 and r = −0.671; p = 0.001, respectively).ConclusionThe pain scores were associated with the morphological and biochemical changes in articular cartilages visualized on knee MR images. The biochemical changes, visualized in terms of the MTR_asym values of the gagCEST images, exhibited greater correlation with the pain scores than the morphological changes visualized on conventional MR images; these results provide evidence supporting the theory regarding the association of patellofemoral osteoarthritis with knee pain scores.     

Spin-lattice relaxation times and nuclear overhauser enhancement effect for P metabolites in model solutions at two frequencies: Implications for in vivo spectroscopy

The relaxation time T₁ values and nuclear Overhauser enhancement factor for ³¹P signal were determined in model solutions of metabolites ATP, PCr and Pi, and AMP at two frequencies and in H₂O and ²H₂O solutions. The data were analyzed to resolve the contribution of different relaxation mechanisms. A knowledge of NOE is important in the light of recent applications of double resonance methods to enhance the sensitivity of in vivo ³¹P spectroscopy. The results show that chemical shift anisotropy is the dominant mechanism for ³¹P in ATP at the high field, whereas the dipolar interaction mechanism is the main feature for the ³¹P relaxation of PCr and Pi. The dipolar mechanism responsible for NOE originates from interactions of solvent water with ³¹P moiety. Implications for in vivo spectroscopy are indicated.     

Measurement of sample temperatures under magic-angle spinning from the chemical shift and spin-lattice relaxation rate of 79Br in KBr powder

Accurate determination of sample temperatures in solid state nuclear magnetic resonance (NMR) with magic-angle spinning (MAS) can be problematic, particularly because frictional heating and heating by radio-frequency irradiation can make the internal sample temperature significantly different from the temperature outside the MAS rotor. This paper demonstrates the use of (79)Br chemical shifts and spin-lattice relaxation rates in KBr powder as temperature-dependent parameters for the determination of internal sample temperatures. Advantages of this method include high signal-to-noise, proximity of the (79)Br NMR frequency to that of (13)C, applicability from 20 K to 320 K or higher, and simultaneity with adjustment of the MAS axis direction. We show that spin-lattice relaxation in KBr is driven by a quadrupolar mechanism. We demonstrate a simple approach to including KBr powder in hydrated samples, such as biological membrane samples, hydrated amyloid fibrils, and hydrated microcrystalline proteins, that allows direct assessment of the effects of frictional and radio-frequency heating under experimentally relevant conditions.     

Proton spectroscopy of human stroke: Assessment of transverse relaxation times and partial volume effects in single volume STEAM MRS

Proton T₂ relaxation times were measured in 13 stroke patients and 13 aged-matched normal subjects at 2.1 T. Spectra were acquired from an 8-cc volume using the STEAM sequence with echo times (TE) of 30.4 ms and 270.0 ms and repetition time of 2.8 s. Transverse relaxation times were estimated using two-point calculations. Percentage volume of infarct in the STEAM voxel was measured on spin-echo MRI encompassing the infarct and correlated with the peak amplitude of N-acetylated compounds (NA). T₂ values of NA, creatine, and choline resonances showed no significant difference between patients and controls. T₂ for lactate in patients was 780 ± 257 ms, respectively (mean ± SE, n = 7). In stroke patients, high inverse correlation was found between the absolute NA signal and partial volume of normal brain contributing to each spectrum (p < .001, r = 0.97). Together with unchanged T₂, this suggests that NAA largely disappears from infarcted tissue within 24 hr postinfarct.