Spin-spin Relaxation Rate Research Articles

1H, 31P NMR, Raman and FTIR spectroscopies for investigating phosphoric acid dissociation to understand phosphate ion kinetics in body fluids

The study investigates the formation and transportation of ionic charge carriers in phosphoric acid-water system. This investigation encompasses an analysis of 1H and 31P NMR chemical shifts, self-diffusion coefficients, spin-lattice relaxation rates, spin-spin relaxation rates, activation energies, dissociation constants, electrical conductivity, and Raman shifts, along with FTIR spectra across various water concentrations. Significantly, the maxima observed in these curves at around 0.8 water molar fraction predominantly from the unique molecular arrangement between phosphoric acid and water molecules, influenced by a hydrogen bonding network. These findings yield valuable insights into phosphate ion kinetics within body fluids, covering essential aspects like hydrogen bonding networks, ionization processes, and the energy kinetics of phosphoric dissociation. A customized semiempirical model is applied to calculate dissociated species (water, phosphoric acid, and hydronium ion) at different water contents within a wide range of water mole fraction. Furthermore, this investigation extends to the dissociation of phosphoric acid in DMEM cell culture media, offering a more precise model for phosphate ionic kinetics within body fluids, especially at nominal phosphate concentrations of approximately 1:700μL.

High linear energy transfer (LET) nature of alanine radical yield by soft X-ray irradiations studied by electron spin resonance (ESR) applications

Radicals produced in alanine by irradiation of 2–7 keV X-rays were investigated by ESR applications; i.e., CW-ESR, pulse-ESR and ESR imaging. The relative radical yield decreased with the decreasing photon energy and the increasing dose. The 2D imaging showed that the radical concentration at the surface was extremely low even though the absorption of X-rays exponentially decreased with the penetration depth. The depth of the radical concentration peak was almost the same as the penetration depth for the X-ray irradiation with an energy lower than 5-keV. The product formed by radical recombination was observed by an LC/MS (liquid chromatograph-mass spectrum) analysis. For the soft X-ray irradiation, many radicals will be lost by the efficient radical-radical recombination due to the higher density of the radicals, similar to the high-LET irradiation by heavy ions. The spin-spin relaxation rate (1/T2), which correlates with the radical concentration, increased by the decreasing photon energy. The values of 1/T2 for the soft X-rays were compatible to that for the heavy ions with the high-LET. Based on these observations, it is concluded that the effects of irradiation by soft X-rays are similar to high-LET irradiation.

Hyperoxic BOLD-MRI-Based Characterization of Breast Cancer Molecular Subtypes Is Independent of the Supplied Amount of Oxygen: A Preclinical Study.

Hyperoxic BOLD-MRI targeting tumor hypoxia may provide imaging biomarkers that represent breast cancer molecular subtypes without the use of injected contrast agents. However, the diagnostic performance of hyperoxic BOLD-MRI using different levels of oxygen remains unclear. We hypothesized that molecular subtype characterization with hyperoxic BOLD-MRI is feasible independently of the amount of oxygen. Twenty-three nude mice that were inoculated into the flank with luminal A (n = 9), Her2+ (n = 5), and triple-negative (n = 9) human breast cancer cells were imaged using a 9.4 T Bruker BioSpin system. During BOLD-MRI, anesthesia was supplemented with four different levels of oxygen (normoxic: 21%; hyperoxic: 41%, 71%, 100%). The change in the spin-spin relaxation rate in relation to the normoxic state, ΔR2*, dependent on the amount of erythrocyte-bound oxygen, was calculated using in-house MATLAB code. ΔR2* was significantly different between luminal A and Her2+ as well as between luminal A and triple-negative breast cancer, reflective of the less aggressive luminal A breast cancer's ability to better deliver oxygen-rich hemoglobin to its tissue. Differences in ΔR2* between subtypes were independent of the amount of oxygen, with robust distinction already achieved with 41% oxygen. In conclusion, hyperoxic BOLD-MRI may be used as a biomarker for luminal A breast cancer identification without the use of exogenous contrast agents.

Evaluation of a novel N-(Hydroxymethyl) acrylamide polymer gel dosimeter formulation with organic glucose additive for radiotherapy

In this study, the first evaluation of organic sensitizer material on N-(Hydroxymethyl) acrylamide (NHMA) polymer gel dosimeter was presented. A novel tissue-equivalent polymer gel formula composed of NHMA containing different concentrations of organic glucose additive (GL-NHMA) was developed and evaluated for its potential use to measure 3D dose distributions to compare with treatment planning system. The new polymers of GL-NHMA were irradiated using a linear accelerator (LINAC) with a megavolt X-ray photon beam over a dose range of 2–20 Gy, energies of 6, 10, and 15 MV, and dose rates of 50, 200, and 500 cGy/min. The samples were evaluated using 0.5 T nuclear magnetic resonance (NMR) technique in terms of spin-spin relaxation rate (R2). Comparing with the conventional NHMA composition (i.e., 0 wt% GL concentration), the sensitivity of the GL-NHAM was improved by 53%, 68%, 89%, and 115% with 10, 15, 20, and 25 wt% GL, respectively, with an excellent linear dose response up to 8 Gy. There were no observable effects on the R2 dose response induced by varying the dose rate, photon energy, and irradiation temperature. The polymerization was stable after irradiation for a period of 10 days. Additionally, the R2 values decreased with increasing the scanning temperature. The dosimeter is water equivalent and is energy-independent from 0.1 to 20 MeV when considering the optimum composition. The gel dosimetry accuracy was evaluated in this study by calculating the overall uncertainty and found to be 4.64% (2σ, 95% confidence level). The GL additive acts as an excellent organic sensitizer in the GL-NHMA system, suggesting that this improved polymer formulation may be a useful tool for measuring dose distributions in radiotherapy at clinically relevant dose levels.

Nuclear Magnetic Resonance Studies of Bicontinuous Liquid Crystalline Phases of Cubic Symmetry: Transport Properties from 2H Nuclear Magnetic Resonance Relaxation Rates.

The ternary system didodecyltrimethylammonium bromide, 1-decanol, and water forms an extended reversed continuous phase of cubic symmetry at 25 °C. The cubic phase belongs to the space group Im3m, as shown by small-angle X-ray experiments. We present extensive deuterium NMR relaxation data from this cubic phase for 1-decanol, deuterated at the carbon adjacent to the hydroxyl carbon position. 2H spin-lattice (R1) and spin-spin (R2) relaxation rates were measured over the existence region of the cubic phase, which extends from 0.2 to 0.6 in volume fraction of the dividing bilayer surface of the cubic phase. The data are interpreted with an existing theoretical framework for NMR spin relaxation in bicontinuous cubic phases, which takes its starting point in the description of bicontinuous phases using periodic minimal surfaces. Specifically, we obtain the self-diffusion coefficient over the minimal surface in one unit cell for 1-decanol. We also present pulsed field gradient NMR-derived self-diffusion data for didodecyltrimethylammonium bromide and compare the two sets of data. The diffusion data for both components show a mild, if any, dependence on the volume fraction of the bilayer surface. Furthermore, we present diffusion data for the water component in the cubic phase. Finally, we discuss the influences of the choice of the value of the product of the deuterium quadrupole constant and the order parameter S. Within the framework of the model used to analyze the relaxation data, a value for this parameter is required. As an initial value, we rely on measurements of deuterium quadrupolar splittings from deuterated decanol in an anisotropic phase.

SQUID current sensors with an integrated thermally actuated input current limiter

The development of superconducting quantum interference device (SQUID) current sensors with a thermally actuated input current limiter (TCL) integrated into the input circuit of the sensor is presented. The TCL is based on an unshunted Josephson Junction (JJ) series array, around which meanders a galvanically isolated, but tightly, thermally coupled, resistive heater element. By applying a current to the heater, the JJ critical currents can be reduced or completely suppressed, while the other on-chip SQUID circuit elements remain unaffected. The functional parameters of the TCL are determined by direct transport measurements and by static and dynamic flux coupling tests via the input circuit. In liquid helium, a heater power, which reliably suppresses the critical current of the JJ array to zero, of ∼1.5 mW was needed, with the TCL normal state resistance being at 500 Ω. In this configuration, typical TCL switching times of approximately 20 µs were observed in the direct transport measurements. The TCL can be used to temporarily or even permanently disable malfunctioning channels in multichannel SQUID magnetometer systems, when feedback into their otherwise superconducting input circuits is not possible. In doing so, significant signal distortions in neighbouring channels from screening currents in these input circuits are avoided. Furthermore, by completely suppressing and restoring the TCL critical current, dc offset currents in the superconducting input circuits can be prevented. This is relevant, for instance, in SQUID-based spin precession experiments on hyperpolarized noble gases, in which even dc currents of a few µA in the input circuit can lead to significant magnetic field distortions in the adjacent sample region contributing to the transverse spin-spin relaxation rate .

Quantitative Blood Oxygenation Level Dependent Magnetic Resonance Imaging for Estimating Intra-renal Oxygen Availability Demonstrates Kidneys Are Hypoxemic in Human CKD

Kidney blood oxygenation level dependent (BOLD) magnetic resonance imaging (MRI) has shown great promise in evaluating relative oxygen availability. This method is quite efficacious in evaluating acute responses to physiological and pharmacologic maneuvers. Its outcome parameter, R2∗ is defined as the apparent spin-spin relaxation rate measured in the presence of magnetic susceptibility differences and it is measured using gradient echo MRI. Although associations between R2∗ and renal function decline have been described, it remains uncertain to what extent R2∗ is a true reflection of tissue oxygenation. This is primarily because of not taking into account the confounding factors, especially fractional blood volume (fBV) in tissue. This case-control study included 7 healthy controls and 6 patients with diabetes and chronic kidney disease (CKD). Using data before and after administration of ferumoxytol, a blood pool MRI contrast media, the fBVs in kidney cortex and medulla were measured. This pilot study independently measured fBV in kidney cortex (0.23 ± 0.03 vs. 0.17 ± 0.03) and medulla (0.36 ± 0.08 vs. 0.25 ± 0.03) in a small number of healthy controls (n= 7) versus CKD (n= 6). These were then combined with BOLD MRI measurements to estimate oxygen saturation of hemoglobin (StO2) (0.87 ± 0.03 vs. 0.72 ± 0.10 in cortex; 0.82 ± 0.05 vs. 0.72 ± 0.06 in medulla) and partial pressure of oxygen in blood (bloodPO2) (55.4 ± 6.5 vs. 38.4 ± 7.6 mmHg in cortex; 48.4 ± 6.2 vs. 38.1 ± 4.5 mmHg in medulla) in control versus CKD. The results for the first time demonstrate that cortex is normoxemic in controls and moderately hypoxemic in CKD. In the medulla, it is mildly hypoxemic in controls and moderately hypoxemic in CKD. Whereas fBV, StO2, and bloodPO2 were strongly associated with estimated glomerular filtration rate (eGFR), R2∗ was not. Our results support the feasibility of quantitatively assessing oxygen availability using noninvasive quantitative BOLD MRI that could be translated to the clinic.

Modeling Molecular Interactions with Wetting and Non-Wetting Rock Surfaces by Combining Electron Paramagnetic Resonance and NMR Relaxometry.

Three types of natural rocks─Bentheimer and Berea sandstones, as well as Liège Chalk─have been aged by immersion in a bitumen solution for extended periods of time in two steps, changing the surface conditions from water-wet to oil-wet. NMR relaxation dispersion measurements were carried out on water and oil constituents, with saturated and aromatic molecules considered individually. In order to separate the different relaxation mechanisms discussed in the literature, 1H and 19F relaxation times were compared to 2H for fully deuterated liquids: while 2H relaxes predominantly by quadrupolar coupling, which is an intramolecular process, the remaining nuclei relax by dipolar coupling, which potentially consists of intra- and intermolecular contributions. The wettability change becomes evident in an increase of relaxation rates for oil and a corresponding decrease for water. However, this expected behavior dominates only for the spin-lattice relaxation rate R1 at very low field strengths and for the spin-spin relaxation rate R2, while high-field longitudinal relaxation shows a much weaker or even reverse trend. This is attributed in part to a change of radical concentration on the pore surface upon coverage of the native rock surface by bitumen as well as by the change of surface chemistry and roughness. EPR and DNP measurements quantify the change of volume vs surface radical concentration in the rocks, and an improved understanding of the role of relaxation via paramagnetic centers is obtained. By means of comparing different fluids and nuclei in combination with a defined wettability change of natural rocks, a refined model for molecular dynamics in conjunction with NMR relaxation dispersion is proposed.

In Vivo Partial Oxygen Pressure Assessment in Subcutaneous and Intraperitoneal Sites Using Imaging of Solid Oxygen Probe.

The purpose of this study was to assess the natural partial oxygen pressure (pO2) of subcutaneous (SC) and intraperitoneal (IP) sites in mice to determine their relative suitability as sites for placement of implants. The pO2 measurements were performed using oxygen imaging of solid probes using lithium phthalocyanine (LiPc) as the oxygen sensitive material. LiPc is a water-insoluble crystalline probe whose spin-lattice and spin-spin relaxation rates (R1 and R2) are sensitive to the local oxygen concentration. To facilitate direct in vivo oxygen imaging, we prepared a solid probe containing encapsulated LiPc crystals in polydimethylsiloxane (PDMS), an oxygen-permeable and bioinert polymer. Although LiPc-PDMS or similar probes have been used in repeated spectroscopic or average oxygen measurements using continuous wave electron paramagnetic resonance (EPR) since the late 1990s and now have advanced to clinical applications, they have not been used for pulse EPR oxygen imaging. One LiPc-PDMS probe of 2 mm diameter and 10 mm length was implanted in SC or IP sites (left or right side) in each animal. The pO2 imaging of implanted LiPc-PDMS probes was performed weekly for 6 weeks using O2M preclinical 25 mT oxygen imager, JIVA-25™, using the pulse inversion recovery electron spin echo method. At week 6, the probes were recovered, and histological examinations were performed. We report in this study, first-ever solid probe oxygen imaging of implanted devices and pO2 assessment of SC and IP sites.

Possible quadrupole-order-driven commensurate-incommensurate phase transition in B20 CoGe

The B20-type cobalt germanide CoGe was investigated by measuring the specific heat, resistivity, and $^{59}$Co nuclear magnetic resonance (NMR). We observed a phase transition at $T_Q=13.7$ K, evidenced by a very narrow peak of the specific heat and sharp changes of the nuclear spin-spin ($T_2^{-1}$) and spin-lattice ($T_1^{-1}$) relaxation rates. The fact that the entropy release is extremely small and the Knight shift is almost independent of temperature down to low temperatures as anticipated in a paramagnetic metal indicates that the $T_Q$ transition is of non-magnetic origin. In addition, we detected a crossover scale $T_0\sim30$ K below which the resistivity and the NMR linewidth increase, and $T_1^{-1}$ is progressively distributed in space, that is, a static and dynamical spatial inhomogeneity develops. While the order parameter for the $T_Q$ transition remains an open question, a group-theoretical analysis suggests that the finite electric quadrupole density arising from the low local site symmetry at cobalt sites could drive the crystal symmetry lowering from the P2$_1$3 symmetry that is commensurate to the R3 symmetry with an incommensurate wavevector, which fairly well accounts for the $T_Q$ transition. The quadrupole-order-driven commensurate-incommensurate phase transition may be another remarkable phenomenon arising from the structural chirality inherent in the noncentrosymmetric B20 family.

Nuclear Spin Relaxation in Viscous Liquids: Relaxation Stretching of Single-Particle Probes.

Spin-lattice relaxation rates R1(ω,T), probed via high-field and field-cycling nuclear magnetic resonance (NMR), are used to test the validity of frequency-temperature superposition (FTS) for the reorientation dynamics in viscous liquids. For several liquids, FTS is found to apply so that master curves can be generated. The susceptibility spectra are highly similar to those obtained from depolarized light scattering (DLS) and reveal an excess wing. Where FTS works, two approaches are suggested to access the susceptibility: (i) a plot of deuteron R1(T) vs the spin-spin relaxation rate R2(T) and (ii) a plot of R1(T) vs an independently measured reference time τref(T). Using single-frequency scans, (i) allows one to extract the relaxation stretching as well as the NMR coupling constant. Surveying 26 data sets, we find Kohlrausch functions with exponents 0.39 < βK ≤ 0.67. Plots of the spin-spin relaxation rate R2─rescaled by the NMR coupling constant─as a function of temperature allow one to test how well site-specific NMR relaxations couple to a given reference process. Upon cooling of flexible molecule liquids, the site-specific dynamics is found to merge, suggesting that near Tg the molecules reorient essentially as a rigid entity. This presents a possible resolution for the much lower stretching parameters reported here at high temperatures that contrast with the ones that were reported to be universal in a recent DLS study close to Tg. Our analysis underlines that deuteron relaxation is a uniquely powerful tool to probe single-particle reorientation.

Local evidence for collective spin excitations in the distorted kagome antiferromagnet Pr3BWO9

We report the local probe investigation of a frustrated antiferromagnet Pr$_3$BWO$_9$ with the distorted kagome lattice. Absence of magnetic order or spin freezing is indicated by the spectral analysis down to 0.3 K and specific heat measurements down to 0.09 K. The Knight shifts show an upturn behavior with the sample cooling down, which is further suppressed by external field. For the spin dynamics, gapped spin excitation is observed from the temperature dependence of spin-lattice relaxation rates, with the gap size proportional to the applied magnetic field intensity. Comparatively, an unexpected sharp peak is observed in the nuclear spin-spin relaxation rate data at $T^*\sim 4-5$ K. These results indicate an unconventional persistent fluctuating paramagnetic ground state with antiferromagnetic collective spin excitations in the strongly frustrated spin system.

Proton $T_1$ and $T_2$ Relaxivities for $CH_2$ and $CH_3$ Peaks in Crude Oil Measured by 400 MHz NMR

Petroleum fluid has been extensively studied at low magnetic fields by Nuclear Magnetic Resonance (NMR) Spectroscopy, but high field NMR studies are rarely found in this area. The aim of this study is to determine the proton spin-lattice relaxation rate (1/T1), T1 relaxivity (R1), proton spin-spin relaxation rate (1/T2) and T2 relaxivity (R2) of paraffinic CH2 and gamma CH3 peaks. For this purpose, crude oil samples were taken from 3 separate wells in the Batman region. Using these samples, 3 different sets were prepared from a mixture of deuterated chloroform (CDCl3) and crude oil. The total volume of each prepared mixture was 1 mL. The crude oil content in each set was changed from 0.05 mL to 0.20 mL in 0.05 mL steps.. Special care has been taken to ensure the best shimming of the NMR spectrometer operating at 400 MHz. T1 measurements were performed using an inversion recovery (IR) pulse sequence. 1/T2 values were determined from the half-height line widths of CH2 and CH3 peaks. 1/T1 and 1/T2 rates and all relaxivities were found to vary from well to well. This change is due to the fluid composition of the wells. The 1/T2 rates and R2 relaxivities were found to be considerably greater than the 1/T1 rates and R1 relaxivities. R2 relaxivities for CH3 were also 2-5 times greater than for CH2.The higher 1/T2 and R2 relaxivities compared with 1/T1 and R1 were attributed to the additional CDCl3-mediated relaxation mechanisms. In conclusion, available data show that high 1/T2 rates and R2 relaxivities measured in the high field NMR laboratory can be applied to separate crude oil from other fluids in the oil field.

Temperature-linear spin-spin relaxation rates of one-dimensional He3 fluid formed in nanochannels

We have made systematic nuclear magnetic resonance measurements for $^{3}\mathrm{He}$ fluid formed in $^{4}\mathrm{He}$-coated nanochannels including the quantum-mechanically one-dimensional (1D) region, which is a possible candidate for a different type of Tomonaga-Luttinger (TL) liquid. Corresponding to the previous heat capacity measurements, a dimensional crossover into the 1D state at low temperatures was observed by the susceptibility. In the 1D region, increases of the spin-spin relaxation time inversely proportional to temperature were found, which is apparently similar to $T$-linear electron spin resonance linewidths for 1D spin chains. While the relevance for TL liquids is still controversial since the behavior is observed in both degenerate and nondegenerate fluids, increases of the spin-spin relaxation time were confirmed to be observed only when 1D conditions for $^{3}\mathrm{He}$ fluid are satisfied, indicating that it is a characteristic property of the 1D $^{3}\mathrm{He}$ fluid.

Systematic differences in the relaxation stretching of polar molecular liquids probed by dielectric vs magnetic resonance and photon correlation spectroscopy.

Relaxation spectra of molecular glass formers devoid of secondary relaxation maxima, as measured by dielectric spectroscopy (DS), nuclear magnetic resonance (NMR) relaxometry, photon correlation spectroscopy (PCS), and Fabry-Perot interferometry, are quantitatively compared in terms of the Kohlrausch stretching parameter βK. For a reliable estimate of βK, the excess wing contribution has to be included in the spectral analysis. The relaxation stretching probed by PCS and NMR varies only weakly among the liquids (βK = 0.58 ± 0.06). It is similar to that found in DS, provided that the liquid is sufficiently nonpolar (relaxation strength Δε≲6). For larger strengths, larger βK DS (narrowed relaxation spectra) are found when compared to those reported from NMR and PCS. Frequency-temperature superposition (FTS) holds for PCS and NMR. This is demonstrated by data scaling and, for the few glass formers for which results are available, by the equivalence of the susceptibilities χPCS ″ωτ∝χNMR ″τ∝χNMR ″ω, i.e., measuring at a constant frequency is equivalent to measuring at a constant temperature or constant correlation time. In this context, a plot of the spin-lattice relaxation rate R1(T) as a function of the spin-spin relaxation rate R2(T) is suggested to reveal the stretching parameter without the need to perform frequency-dependent investigations. Dielectrically, we identify a trend of increasing deviations from FTS with increasing Δε. Depending on the technique and glass former, the relative relaxation strength of the excess wing varies, whereas its exponent appears to be method independent for a given substance. For polar liquids, we discuss possible reasons for the discrepancy between the results from PCS and NMR as compared to those from DS.

NMR Studies of Bicontinuous Liquid Crystalline Phases of Cubic Symmetry: Interpretation of Frequency-Dependent Relaxation Rates.

Extensive deuterium NMR relaxation data are presented for two specifically deuterium labeled surfactants forming bicontinuous cubic phases with water. 2H spin-lattice (R1) and spin-spin (R2) relaxation rates were measured over an extended frequency range from 2 to 60 MHz. The data are interpreted with an existing theoretical framework for spin relaxation in bicontinuous cubic phases, which takes its starting point in the description of bicontinuous phases using periodic minimal surfaces. We show that the theory succeeds in accounting for the data and that the defining parameters of the theory, correlation times and order parameters, are in agreement with related data in other surfactant phase situations. Specifically, we obtain the surfactant self-diffusion coefficient over the minimal surface in one unit cell and show that it is in agreement with the corresponding macroscopic NMR diffusion data. By measuring two additional NMR relaxation parameters for each carbon on the surfactant hydrocarbon tail, we demonstrate how order parameter and correlation time profiles can be obtained. Finally, we analyze published molecular dynamics trajectories for a bicontinuous cubic phase. The analysis provides further support for the theoretical framework used to interpret relaxation data.

End-to-end delivery quality assurance of computed tomography–based high-dose-rate brachytherapy using a gel dosimeter

PurposeThe purpose of this study was to develop a novel quality assurance (QA) program to check the entire treatment chain of image-guided brachytherapy with dose distribution evaluation in a single setup and irradiation using a gel dosimeter. Methods and MaterialsA polymer gel was used, and the readout was performed by magnetic resonance scanning. A CT-based treatment plan was generated using the Oncentra planning system (Elekta, Sweden), and irradiation was performed three times using an afterloading device with an Ir-192 source. The dose-response curve of the gel was created using 6-MV X-ray, which is independent of the source beams. Planar gamma images on a coronal plane along the source transport axis were calculated using the measured dose as a reference, and the calculated doses were used in several error simulations (no error; 2.0 or 2.5 mm systematic and random source dwell mispositioning; and dose error of 2%, 5%, 10%, and 20%). ResultsThe dose-R2 (spin-spin relaxation rate) conversion table revealed that the uncertainty and dose resolution of 6-MV X-ray were better than those of Ir-192 and also constant between the three measurements. With the 3%/1 mm criteria, there were statistically significant differences between each pair of settings except dose error of 2% and 5%. ConclusionThis work depicts a simple and efficient end-to-end test that can provide a clinically useful tool for QA of image-guided brachytherapy. In this QA program, air kerma strength and dwell position setting could also be verified. This test can also distinguish between different types of error.

A new approach to determining the structure of lanthanide complexes in solution according to the Curie-spin contribution to the paramagnetic spin-spin relaxation rate enhancements: Ho-DOTA

In this work, we propose for the first time a new type of NMR method for obtaining structural information on Ln complexes in solutions based on the analysis of the Curie-spin contribution to the paramagnetic spin-spin relaxation rate enhancements on the ligand nuclei. The application of the proposed methodology was carried out in this work by the example of studying the structure of the complex anion [Ho(DOTA)(H2O)]− (I) in D2O. Earlier we carried out the assignment of signals [S.P. Babailov, P.V. Dubovskii, E.N. Zapolotsky, Polyhedron 79 (2014) 277], investigated the molecular conformational dynamics and the dependence of the spin-spin relaxation rate on the magnetic field of complex I. Actually, the Curie spin contribution to the paramagnetic spin-spin relaxation rate enhancements on the ligand nuclei of this complex was determined by varying the constant magnetic field and temperature. As a result, it was found that the structure of the complex in solution is identical to its structure in the crystalline phase (found by the X-ray diffraction).

Unified phase diagram of F-doped LaFeAsO by means of NMR and NQR parameters

We present $^{75}$As Nuclear Magnetic and Quadrupole Resonance results (NMR, NQR) on a new set of LaFeAsO$_{1-x}$F$_x$ polycrystalline samples. Improved synthesis conditions led to more homogenized samples with better control of the fluorine content. The structural$\equiv$nematic, magnetic, and superconducting transition temperatures have been determined by NMR spin-lattice relaxation rate and AC susceptibility measurements. The so-determined phase diagram deviates from the published one especially for low F-doping concentrations. However, if the doping level is determined from the NQR spectra, both phase diagrams can be reconciled. The absence of bulk coexistence of magnetism and superconductivity and a nanoscale separation into low-doping-like and high-doping-like regions have been confirmed. Additional frequency dependent intensity, spin-spin, and spin-lattice relaxation rate measurements on underdoped samples at the boundary of magnetism and superconductivity indicate that orthorhombicity and magnetism originate from the low-doping-like regions, and superconductivity develops at first in the high-doping-like regions.

125Te-NMR Study on a Single Crystal of Heavy Fermion Superconductor UTe2

We report 125Te-NMR studies on a newly discovered heavy fermion superconductor UTe2. Using a single crystal, we have measured the 125Te-NMR Knight shift K and spin-lattice relaxation rate 1/T1 for fields along the three orthorhombic crystal axes. The data confirm a moderate Ising anisotropy for both the static (K) and dynamical susceptibilities (1/T1) in the paramagnetic state above about 20 K. Around 20 K, however, we have observed a sudden loss of NMR spin-echo signal due to sudden enhancement of the NMR spin-spin relaxation rate 1/T2, when the field is applied along the easy axis of magnetization (=a axis). This behavior suggests the development of longitudinal magnetic fluctuations along the a axis at very low frequencies below 20 K.