Spin-spin Relaxation Rate Research Articles

Scalar Relaxation of the Second Kind. A Potential Source of Information on the Dynamics of Molecular Movements. 3. A 13C Nuclear Spin Relaxation Study of CBrX3 (X = Cl, CH3, Br) Molecules

Continuing studies based on measurements of the nuclear spin relaxation rates running via the SC2 mechanism (scalar relaxation of the second kind), we present in this work the results obtained for three bromo compounds: CBrCl3, (CH3)3CBr, and CBr4. A careful separation of saturation-recovery curves, measured for signals of (13)C nuclei at 7.05 and 11.7 T on two components, has provided the longitudinal SC2 relaxation rates of carbon signals in (79)Br and (81)Br containing isotopomers of the investigated compounds. These data have enabled experimental determination of spin-spin coupling constants and relaxation rates of quadrupole bromine nuclei, both types of parameters being hardly accessible by direct measurements. Investigation of the relaxation behavior of these molecules, being of similar size and shape, has provided quite different practical and interpretational problems which are likely to be encountered in relaxation studies of many other carbon-bromine systems. In order to evaluate the quality of the obtained experimental results, advanced theoretical calculations of the indirect (1)J((13)C,(79)Br) coupling constants, magnetic shielding of carbon nuclei, and quadrupole coupling constants of bromines in the investigated compounds have been performed and compared with the experimental values. Relatively small divergences between experiment and theory have been found. The contributions of the relativistic effects to the values of the discussed parameters have been tentatively estimated.

Scalar Relaxation of the Second Kind — A Potential Source of Information on the Dynamics of Molecular Movements. 2. Magnetic Dipole Moments and Magnetic Shielding of Bromine Nuclei

In this paper, we continue the exploration of possibilities, limitations, and methodological problems of the studies based on measurements of the nuclear spin relaxation rates running via the scalar relaxation of the second kind (SC2) mechanism. The attention has been focused on the (13)C-(79)Br and (13)C-(81)Br systems in organic bromo compounds, which are characterized by exceptionally small differences of Larmor frequencies, ΔωCBr, of the coupled nuclei. This unique property enables experimental observation of longitudinal SC2 relaxation of (13)C nuclei, which makes investigation of the SC2 relaxation rates an attractive experimental method of determination of spin-spin coupling constants and relaxation rates of quadrupole bromine nuclei, both types of parameters being hardly accessible by direct measurements. A careful examination of the methodology used in SC2 relaxation studies of carbon-bromine systems reveals, however, some disturbing facts that could burden the results with systematic inaccuracies. Namely, the way of calculating the Larmor frequency differences between (13)C and bromine isotopes, ΔωCBr, may cause some reservations. In this work, the values of (79)Br and (81)Br magnetogyric ratios have been rechecked using bromine NMR data for the KBr·Kryptofix 222 complex in acetonitrile solution and the results of the advanced calculations of the magnetic shielding of the bromine nucleus in the Br(-) anion. Moreover, it has been pointed out that in the case of (13)C-(79)Br, the magnetic shielding of the bromine nucleus in the investigated molecule must not be neglected during the calculation of the ΔωCBr parameter. Some recommendations concerning the exploitation of available theoretical methods to calculate bromine shielding constants for bromo compounds have also been formulated, keeping in mind relativistic effects.

Evidence of a rattling transition in the caged compounds LaRu2Zn20 and LaIr2Zn20: 139La NMR studies

We report a study of 139La(I=7/2) nuclear magnetic resonance (NMR) to investigate the structural phase transition in the two caged compounds LaIr2Zn20 and LaRu2Zn20 from microscopic viewpoints. The former compound shows a second-order structural phase transition around Ts = 200 K whereas the latter one shows a first-order structural phase transition at Ts = 150 K. For both compounds, quite narrow La-NMR lines of less that 10 kHz without any electric field gradient (EFG) at the La site were observed at temperatures above Ts, indicating that the local symmetry at the La site holds a cubic symmetry. On the other hand, an EFG at La site appears at temperatures below Ts, evidencing symmetry lowering occurs at the La site at temperatures below Ts. At temperatures around Ts, both the nuclear spin-lattice relaxation rate (1/T1) and the nuclear spin-spin relaxation rate (1/T2) show unusual enhancements associated with the slowing down of the EFG fluctuations. However, the temperature dependences of 1/T1T and 1/T2 are different from the typical slowingdown phenomena of the EFG fluctuations due to the classical motional narrowing. The lowering of the local symmetry at the La site is ascribed to a freezing of the rattling motion.

BaV3O8: A possible Majumdar-Ghosh system withS=12

BaV${}_{\text{3}}$O${}_{\text{8}}$ contains magnetic V${}^{\text{4+}}$($S=1/2$) ions and also nonmagnetic V${}^{\text{5+}}$($S=0$) ions. The V${}^{4+}$ ions are arranged in a coupled Majumdar-Ghosh chainlike network. A Curie-Weiss fit of our magnetic susceptibility $\ensuremath{\chi}(T)$ data in the temperature region of $80--300$ K yields a Curie constant $C=0.39$ cm${}^{\text{3}}$K/mole V${}^{\text{4+}}$ and an antiferromagnetic Weiss temperature $\ensuremath{\theta}=\ensuremath{-}26\phantom{\rule{0.28em}{0ex}}\mathrm{K}$. The $\ensuremath{\chi}$(T) curve shows a broad maximum at $T\ensuremath{\simeq}25$ K indicative of short-range order (SRO) and an anomaly corresponding to long-range order (LRO) at ${T}_{\mathrm{N}}$$\phantom{\rule{0.16em}{0ex}}\ensuremath{\sim}6$ K. The value of the ``frustration parameter'' ($f=|\ensuremath{\theta}/{T}_{\text{N}}|\ensuremath{\sim}5$) suggests that the system is moderately frustrated. Above the LRO temperature, the experimental magnetic susceptibility data match well with the coupled Majumdar-Ghosh (or ${J}_{\mathrm{nn}}\ensuremath{-}{J}_{\mathrm{nnn}}$ Heisenberg) chain model with the ratio of the nnn (next-nearest neighbor) to nn (nearest neighbor) magnetic coupling $\ensuremath{\alpha}=2$ and ${J}_{\mathrm{nnn}}/{k}_{B}=40$ K. In a mean-field approach when considering the interchain interactions, we obtain the total interchain coupling to be about 16 K. The LRO anomaly at ${T}_{\mathrm{N}}$ is also observed in the specific heat ${C}_{\mathrm{P}}(T)$ data and is not sensitive to an applied magnetic field up to 90 kOe. A ${}^{\text{51}}$V NMR signal corresponding to the nonmagnetic vanadium was observed. Anomalies at 6 K were observed in the variation with temperature of the ${}^{51}$V NMR linewidth and the spin-lattice relaxation rate $1/{T}_{1}$ indicating that they are sensitive to the LRO onset and fluctuations at the magnetic V sites. The existence of two components (one short and another long) is observed in the spin-spin relaxation rate $1/{T}_{2}$ data in the vicinity of ${T}_{\mathrm{N}}$. The shorter component seems to be intimately connected with the magnetically ordered state. We suggest that both magnetically ordered and nonlong-range-ordered (non-LRO) regions coexist in this compound below the long-range-ordering temperature.

Application of a PAGAT/MgCl2 gel for dose measurements in a 150 MeV proton beam

The purpose of this study is to evaluate the dose response of polyacrylamide-based gel (PAGAT) when irradiated with clinical proton beams. Recently inorganic salt additive in gel has been reported to improve dose sensitivity substantially. We attempted to add MgCl2 (0.5M) to regular PAGAT gel in order to compensate its lower radiation sensitivity. The spin-spin relaxation rates (R2) as dose readout was calculated from MR imaging after irradiation with 150MeV proton beam. The dose sensitivity was discussed from the slope at dose-R2 response curve. As the result, the sensitivity of the gel with MgCl2 is approximately 3 times higher than that of regular PAGAT gel without spoiling dose response stability under the various irradiation conditions such as dose rate and dose integration.

Indigenously developed multipurpose acrylic head phantom for verification of IMRT using film and gel dosimetry

The purpose of this study was to validate the newly designed acrylic phantom for routine dosimetric purpose in radiotherapy. The phantom can be used to evaluate and compare the calculated dose and measured dose using film and gel dosimetric methods. In this study, a doughnut‐shaped planning target volume (8.54 cm3) and inner organ at risk (0.353 cm3) were delineated for an IMRT test plan using the X‐ray CT image of the phantom. The phantom consists of acrylic slabs which are integrated to form a human head with a hole in the middle where several dosimetric inserts can be positioned for measurement. An inverse planning with nine coplanar intensity‐modulated fields was created using Pinnacle TPS. For the film analysis, EBT2 film, flatbed scanner, in‐house developed MATLAB codes and ImageJ software were used. The 3D dose distribution recorded in the MAGAT gel dosimeter was read using a 1.5 T MRI scanner. Scanning parameters were CPMG pulse sequence with 8 equidistant echoes, TR=5600, echo step=22 ms, pixel size=0.5 times 0.5, slice thickness=2 mm. Using a calibration relationship between absorbed dose and spin‐spin relaxation rate (R2), R2 images were converted to dose images. The dose comparison was accomplished using in‐house MATLAB‐based graphical user interface named “IMRT3DCMP”. For gel measurement dose grid from the TPS was extracted and compared with the measured dose grid of the gel. Gamma index analysis of film measurement for the tolerance criteria of 2%/2 mm, 1%/1 mm showed more than 90% voxels pass rate. Gamma index analysis of 3D gel measurement data showed more than 90% voxels pass rate for different tolerance criteria of 2%/2 mm and 1%/1 mm. Overall both 2D and 3D measurement were in close agreement with the Pinnacle TPS calculated dose. The phantom designed is cost‐effective and the results are promising, but further investigation is required to validate the phantom with other 3D conformal techniques for dosimetric purpose.PACS numbers: 87.53.Kn, 87.55.km, 87.56.N‐

Relaxation of biofunctionalized magnetic nanoparticles in ultra-low magnetic fields

In this work, the spin-spin relaxation rate, 1/T2, and spin-lattice relaxation rate, 1/T1, of protons’ spins induced by biofunctionalized magnetic nanoparticles and ferrofluids are investigated using a high-Tc superconducting quantum interference device-detected magnetometer in ultra-low fields. The biofunctionalized magnetic nanoparticles are the anti-human C-reactive protein (antiCRP) coated onto dextran-coated superparamagnetic iron oxides Fe3O4, which is labeled as Fe3O4-antiCRP. The ferrofluids are dextran-coated iron oxides. It was found that both 1/T2 and 1/T1 of protons in Fe3O4-antiCRP are enhanced by the presence of magnetic nanoparticles. Additionally, both the 1/T1 and 1/T2 of Fe3O4-antiCRP are close to that of ferrofluids, which are dextran-coated Fe3O4 dispersed in phosphate buffer saline. Characterizing the relaxation of Fe3O4-antiCRP can be useful for biomedical applications.

Influence of water-insoluble nonionic copolymer E6P39E6 on the microstructure and self-aggregation dynamics of aqueous SDS solution—NMR and SANS investigations

The influence of water-insoluble nonionic triblock copolymer PEO-PPO-PEO [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] i.e., E6P39E6 with molecular weight 2800, on the microstructure and self-aggregation dynamics of anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution (D2O) were investigated using high resolution nuclear magnetic resonance (NMR) and small-angle neutron scattering (SANS) measurements. Variable concentration and temperature proton ((1)H), carbon ((13)C) NMR chemical shifts, (1)H self-diffusion coefficients, (1)H spin-lattice and spin-spin relaxation rates data indicate that the higher hydrophobic nature of copolymer significantly influenced aggregation characteristics of SDS. The salient features of the NMR investigations include (i) the onset of mixed micelles at lower SDS concentrations (<3 mM) relative to the copolymer-free case and their evolution into SDS free micelles at higher SDS concentrations (~30 mM), (ii) disintegration of copolymer-SDS mixed aggregate at moderate SDS concentrations (~10 mM) and still binding of a copolymer with SDS and (iii) preferential localization of the copolymer occurred at the SDS micelle surface. SANS investigations indicate prolate ellipsoidal shaped mixed aggregates with an increase in SDS aggregation number, while a contrasting behavior in the copolymer aggregation is observed. The aggregation features of SDS and the copolymer, the sizes of mixed aggregates and the degree of counterion dissociation (α) extracted from SANS data analysis corroborate reasonably well with those of (1)H NMR self-diffusion and sodium ((23)Na) spin-lattice relaxation data.

NMR Study of HD Adsorbed in a Z-type Metal-Organic Framework

We report the results of measurements of the nuclear spin-lattice and spin-spin relaxation rates of hydrogen deuteride trapped in the mesoporous cages of a metal organic framework (MOF) for temperatures 2.2 < T < 50 K There is considerable interest in the use of this class of materials for hydrogen storage because of the high density of adsorption. NMR studies can provide important information about the molecular interactions and dynamics inside the cages of the MOF structure. Samples were studied with filling factors of 0.1 and 1.0 molecules per cage as determined by the adsorption isotherm at 77 K The results show strong peaks in the relaxation times at several well defined temperatures that are very different from the adsorption energy levels. The origin of these peaks is discussed in terms of the quantization of the translational degrees of freedom of the molecules inside the cages and the associated discrete energy levels. Measurements of the nuclear spin-spin relaxation times also provide an important measure of the diffusivity of hydrogen through the MOF structure which is a critical parameter for the use of MOFs for storage and transport.

Co-NQR Study on Successive Magnetic Phase under Pressure in Non-centrosymmetric CeCoGe3

We have performed Co-NQR study to clarify the complex magnetic phases in approaching to the quantum critical point (QCP). The successive transitions at TN2=12 K and TN3=8 K after the ferrimagnetic-like order at TN1=21 K in ambient pressure are confirmed by the spectral changes of Co-NQR However no critical slowing down of the nuclear spin-lattice relaxation rate 1/T1 or the nuclear spin-spin relaxation rate 1/T2 at TN2 and TN3 was observed, suggesting 1st order transitions. In applying pressure, a large spectral change of Co-NQR occurs in relatively low pressure of 0.3 Gpa. The Co-NQR spectrum becomes simple above about 0.7 GPa, consisting of the two Co sites with spectral weight ratio of 2. No successive transitions were observed in 1.5 GPa, indicating that the successive transitions are confined to relatively low pressure region. The extremely slower decrease of the sublattice magnetization than that expected in the mean field approximation is seen in 1.5 GPa.

Spin-spin relaxation of protons in ferrofluids characterized with a high-Tc superconducting quantum interference device-detected magnetometer in microtesla fields

In this work, the spin-spin relaxation of protons in ferrofluids is characterized using a high-Tc SQUID-based detector in microtesla fields. We found that spin-spin relaxation rate is enhanced in the presence of superparamagnetic nanoparticles. The enhanced relaxation rates are attributed to the microscopic field gradients from magnetic nanoparticles that dephase protons’ spins nearby. The relaxation rates decrease when temperatures increase. Additionally, the alternating current magnetic susceptibility was inversely proportional to temperature. Those characteristics explained the enhanced Brownian motion of nanoparticles at high temperatures. Characterizing the relaxation will be helpful for assaying bio-molecules and magnetic resonance imaging in microtesla fields.

The serial effect of iodinated contrast media on renal hemodynamics and oxygenation as evaluated by ASL and BOLD MRI

Contrast-induced nephropathy is a prevalent cause of renal failure, and the mechanisms underlying this injury are not fully understood. We utilized noninvasive functional MRI in order to determine the serial effect of a single administration of iodinated contrast media (CM) on renal hemodynamics and oxygenation. Fifteen rabbits were randomized to receive an intravenous injection of CM (i.e. iopamidol-370; 6 ml kg(-1) body weight) or an equivalent amount of 0.9% saline. Both arterial spin-labeling and blood oxygen level-dependent imaging sequences were performed at 24 h before and at intervals of 1, 24, 48 and 72 h after injection to obtain serial renal blood flow (RBF) and relative spin-spin relaxation rate (R(2)*). Results showed that, in the iopamidol group, the mean cortical RBF decreased at 1 h (p = 0.04 vs baseline), reached its minimum at 24 h (p = 0.01) and gradually returned to baseline by 48 h (p = nonsignificant, NS). The outer medullary RBF decreased to its minimum by 24 h (p = 0.00) and remained less than baseline until 72 h. R(2)* in inner stripes was dramatically increased at 1 h (p = 0.00), remained elevated at 24 h (p = 0.05), but returned to baseline by 48 h (p = NS). R(2)* values within the cortex and outer stripes and inner medulla were slightly increased, but the changes did not reach a statistical significance (p = NS). Saline did not produce positive change in either RBF or R(2)* within different compartments of the kidney. We conclude that iopamidol is associated with a relatively longer-term hypoperfusion in whole kidney and decreased oxygen level in the inner stripes of the outer medulla.

INTERACTION BETWEEN DRUGS AND BIOMEDICAL MATERIALS I: BINDING POSITION OF BEZAFIBRATE TO HUMAN SERUM ALUBMIN

The interaction between bezafibrate (BZF) and human serum albumin (HSA) was investigated by equilibrium dialysis. Since the binding constant of BZF to HSA was independent of ionic strength and decreased with the addition of fatty acid, the interaction between BZF and HSA was considered to be due to hydrophobic mechanism. Chemical shifts in 1H-NMR spectra of BZF were independent of the concentration of BZF and addition of HSA. Spin-lattice relaxation time (T1) and spin-spin relaxation time (T2) of respective protons of BZF were independent of the concentration, but depended on the concentration of HSA added. The binding position of BZF to HSA was considered to involve the hydrophobic aromatic moiety of BZF from the ratio of spin-spin relaxation rates (1/T2) of BZF bound to HSA and free BZF.

Characterizing longitudinal and transverse relaxation rates of ferrofluids in microtesla magnetic fields

Shortening spin-lattice relaxation rates (1/T1) or spin-spin relaxation rates (1/T2) is the purpose of magnetic resonance imaging contrast agents. In this work, an ultralow field nuclear magnetic resonance spectrometer and imager are set up to characterize the spin relaxation rates of Fe3O4 superparamagnetic iron oxide (SPIO) for image contrast. It was found that both 1/T1 and 1/T2 increase linearly when the magnetic susceptibility χ of SPIO increases by increasing the concentration of SPIO dispersed in water. In an applied field, magnetic moments of SPIO generate microscopic field gradients that weaken the field homogeneity, in turn de-phasing the proton’s nuclear spin and enhancing the relaxation rates. A T1-contrast image is demonstrated, using SPIO as the contrast agent and high-Tc superconducting quantum interference devices as the detector. T1-contrast imaging in microtesla fields might provide a potential modality for discriminating cancer.

Development of BANG-3?? Polymer Gel Dosimetry System in Small Radiosurgical Fields

In this study we focused on relative output factor, radiation field profile and three-dimensional dose distribution measurements of small radiosurgical fields using BANG-3r polymer gel. Polymer gel phantom was irradiated by 5 and 30 mm radiosugical beam size with 6 MV radiosurgery beam. MR scan was performed under the condition of same slice thickness and different resolutions. Output factor measurements with the PinPoint ion chamber, diode and EBT are compared with BANG-3r polymer gel. We used a spherical phantom filled with BANG-3r polymer gel to measure 3D dose distributions. The irradiated phantom was scanned with an MRI scanner. Relative otput factor and dose distribution were obtained by calibrating the polymer gel and the spin-spin relaxation rate of the magnetic resistance signal. Results showed that polymer gel output factor agreeds with diode as a reference 30 mm beam size. The gel dosimetry was useful tool available for overcome tissue-equivalence, beam perturbation implications, volume averaging and positioning uncertainties in small radiosurgical dosimetry. In three-dimensional dose distribution, the MRI artifacts cause a geometrical distortion of less than 2 mm and less than 10% change in the distribution. The gel dosimetry has the potential to qualitatively characterize the relative output factor, beam profile and the dose distributions.

Lysine Nζ-Decarboxylation Switch and Activation of the β-Lactam Sensor Domain of BlaR1 Protein of Methicillin-resistant Staphylococcus aureus

The integral membrane protein BlaR1 of methicillin-resistant Staphylococcus aureus senses the presence of β-lactam antibiotics in the milieu and transduces the information to the cytoplasm, where the biochemical events that unleash induction of antibiotic resistance mechanisms take place. We report herein by two-dimensional and three-dimensional NMR experiments of the sensor domain of BlaR1 in solution and by determination of an x-ray structure for the apo protein that Lys-392 of the antibiotic-binding site is posttranslationally modified by N(ζ)-carboxylation. Additional crystallographic and NMR data reveal that on acylation of Ser-389 by antibiotics, Lys-392 experiences N(ζ)-decarboxylation. This unique process, termed the lysine N(ζ)-decarboxylation switch, arrests the sensor domain in the activated ("on") state, necessary for signal transduction and all the subsequent biochemical processes. We present structural information on how this receptor activation process takes place, imparting longevity to the antibiotic-receptor complex that is needed for the induction of the antibiotic-resistant phenotype in methicillin-resistant S. aureus.

Pulse electron spin resonance investigation of bismuth-doped silicon: Relaxation and electron spin echo envelope modulation

Donors in silicon represent good candidates for the realization of several innovative devices exploiting classical as well as quantum information processing functionalities. Although most of the current work in the field is focused on the technological donors (P, As), the more exotic Bi offers interesting properties due to its nuclear spin and electronic structure. We present a detailed pulsed electron paramagnetic resonance study of the spin-spin and spin-lattice relaxation rates along with a full angular analysis of electron spin echo envelope modulation (ESEEM) spectra in bismuth-doped silicon samples having two different donor concentrations. The measurements were performed up to $40$ K. ESEEM spectra provide information on the donor wave function via the leading superhyperfine interactions between donor nuclei and nearby $^{29}\mathrm{Si}$ coordination shells. The assignment of the most intense contributions was made on the basis of the angular variation of ESEEM resonances and elementary considerations on the deep donor states.

An MRI digital brain phantom for validation of segmentation methods

Knowledge of the exact spatial distribution of brain tissues in images acquired by magnetic resonance imaging (MRI) is necessary to measure and compare the performance of segmentation algorithms. Currently available physical phantoms do not satisfy this requirement. State-of-the-art digital brain phantoms also fall short because they do not handle separately anatomical structures (e.g. basal ganglia) and provide relatively rough simulations of tissue fine structure and inhomogeneity. We present a software procedure for the construction of a realistic MRI digital brain phantom. The phantom consists of hydrogen nuclear magnetic resonance spin-lattice relaxation rate (R1), spin-spin relaxation rate (R2), and proton density (PD) values for a 24 × 19 × 15.5 cm volume of a "normal" head. The phantom includes 17 normal tissues, each characterized by both mean value and variations in R1, R2, and PD. In addition, an optional tissue class for multiple sclerosis (MS) lesions is simulated. The phantom was used to create realistic magnetic resonance (MR) images of the brain using simulated conventional spin-echo (CSE) and fast field-echo (FFE) sequences. Results of mono-parametric segmentation of simulations of sequences with different noise and slice thickness are presented as an example of possible applications of the phantom. The phantom data and simulated images are available online at http://lab.ibb.cnr.it/.

A variable echo‐number method for estimating in MRI‐based polymer gel dosimetry

Spin-spin relaxation rate R2 is commonly used to quantify absorbed dose for magnetic resonance imaging (MRI)-based polymer gel dosimetry. R2 is estimated by applying a parameter fitting algorithm to a train of spin-echo signals. However, a careless application of a large number of echoes can result in anomalous R2 values because the echo signal intensity decreases to the background signal offset level for a long echo time. In this article, the authors proposed and evaluated a variable echo-number (VAREC) method to remedy the problem. The VAREC algorithm uses only echo signals, whose intensities are greater than a preset threshold. Here, the threshold is defined as the standard deviation of Gaussian noise times a multiplier alpha. The authors implemented three R2 estimation methods in an in-house program: The nonlinear least-squares algorithm (NLLS), the VAREC method, and the maximum likelihood estimator with the Rician signal intensity distribution (MLE_R). Those methods were used to estimate the R2 values of test phantoms with known R2 values and BANG3-type polymer gels, which were irradiated to 12 different doses ranging from 0 to 50 Gy. The R2 values were measured by using a 32-echo CPMG pulse sequence on 3 T MRI scanners. The R2 values of the VAREC method were compared with those of NLLS and MLE_R. The R2 values of the NLLS method incorrectly decreased to the zero-dose level for doses greater than 10 Gy. The R2 values of the VAREC method with alpha=2 agreed with those of MLE_R within the measurement uncertainty. The uncertainties of the R2 values were the smallest for alpha=2 or 3 among various alpha values. The VAREC algorithm is simple, fast, and robust for the R2 estimation. The authors recommend this method with alpha=2 or 3 for R2 estimation using multispin echo MRI protocols.

Ionic mobility in Nasicon-type LiMIV2(PO4)3 materials followed by 7Li NMR spectroscopy.

AbstractLithium mobility in LiM2(PO4)3 compounds, with M= Ge, Ti, Sn, Zr and Hf, has been investigated by 7Li Nuclear Magnetic Resonance (NMR) spectroscopy in the temperature range 100-500 K. From the analysis of 7Li NMR quadrupole interactions (CQ and η parameters), Li sites occupancy and exchange processes between structural sites have been studied. Below 250K, Li ions are preferentially located at M1 sites in rhombohedral phases, but occupy M12 sites in triclinic ones. At increasing temperatures, Li mobility has been deduced from spin-spin () and spin-lattice relaxation () rates. In this analysis, the presence of two relaxation mechanisms in plots has been associated with departures of conductivity from the Arrhenius behavior. At high temperatures, residence times at M12−T11−T11−T1 and M12 sites become similar and conductivity significantly increase. This superionic state can be achieved by enlarged order-disorder transformations in rhombohedral phases, or by sharp first order transitions in triclinic ones. Results described in the LiTi2(PO4)3 sample have been compared with those obtained in rhombohedral Li1+xTi2-xAlx(PO4)3 and LiTi2-xZrx(PO4)3 series showing respectively higher and lower conductivities. In the case of Li1.2Ti1.8Al0.2(PO4)3, displaying the highest reported conductivity, NMR results are discussed in relation with those obtained by Neutron Diffraction (ND) and Impedance Spectroscopy (IS). Diffusion coefficients determined by NMR Pulse Field Gradient (PFG) technique are similar to those deduced from Impedance Spectroscopy and NMR relaxation data.