Molecular motions in chloramphenicol studied by35Cl nuclear quadrupole and1H nuclear magnetic resonance spectroscopy

The³⁵Cl nuclear quadrupole resonance (NQR) frequency (v_Q), nuclear quadrupole spinlattice relaxation time (T_1Q),¹H nuclear magnetic resonance second moment (M₂) and nuclear magnetic spin-lattice relaxation timeT ₁) were measured for polycrystalline chloramphenicol (drug) as a function of temperature. Hindered rotation of the CHC1₂ group and the phenyl ring was detected, the relevant activation energies were determined. The rotations are discussed in detail.     

Phase transition and ferroelastic property studied by using the Cs nuclear magnetic resonance in a CsHSO4 single crystal

The ¹³³Cs spin-lattice relaxation time in a CsHSO₄ single crystal was measured in the temperature range from 300 to 450 K. The changes in the ¹³³Cs spin-lattice relaxation rate near T_c1 (=333 K) and T_c2 (=415 K) correspond to phase transitions in the crystal. The small change in the spin-lattice relaxation time across the phase transition from II to III is due to the fact that during the phase transition, the crystal lattice does not change very much; thus, this transition is a second-order phase transition. The abrupt change of T₁ around T_c2 (II-I phase transition) is due to a structural phase transition from the monoclinic to the tetragonal phase; this transition is a first-order transition. The temperature dependences of the relaxation rates in phases I, II, and III are indicative of a single-phonon process and can be represented by T₁⁻¹=A+BT. In addition, from the stress-strain hysteresis loop and the ¹³³Cs nuclear magnetic resonance, we know that the CsHSO₄ crystal has ferroelastic characteristics in phases II and III.     

Temperature dependence of the spin-lattice relaxation time for quadrupole nuclei under conditions of NMR line saturation

The contributions of different mechanisms of nuclear spin-lattice relaxation are experimentally separated for ⁶⁹Ga and ⁷¹Ga nuclei in GaAs crystals (nominally pure and doped with copper and chromium), ²³Na nuclei in a nominally pure NaCl crystal, and ²⁷Al nuclei in nominally pure and lightly chromium-doped Al₂O₃ crystals in the temperature range 80–300 K. The contribution of impurities to spin-lattice relaxation is separated under the condition of additional stationary saturation of the nuclear magnetic resonance (NMR) line in magnetic and electric resonance fields. It is demonstrated that, upon suppression of the impurity mechanism of spin-lattice relaxation, the temperature dependence of the spin-lattice relaxation time T₁ for GaAs and NaCl crystals is described within the model of two-phonon Raman processes in the Debye approximation, whereas the temperature dependence of T₁ for corundum crystals deviates from the theoretical curve for relaxation due to the spin-phonon interaction.     

La NMR and As NQR study of the As-based filled skutterudite LaOs4As12

We report experimental results of nuclear magnetic resonance (NMR) at the La site and nuclear quadrupole resonance (NQR) at the As site in the normal state of the superconducting compound LaOs₄As₁₂. Measurements have been performed on powder sample obtained from high quality single crystals. The temperature dependences of the nuclear spin-lattice relaxation rates, 1/T₁, of ⁷⁵As and ¹³⁹La nuclei were measured. No scaling between them was found indicating a local character of relaxation processes. The relaxation of ⁷⁵As nuclei can consistently be understood in terms of antiferromagnetic spin fluctuations, as deduced from the T-dependence of (1/T₁T)=C/(T−θ)^1/2.     

DTA and NQR studies of polymorphism in p-chlorofluorobenzene

Differential thermal analysis, and the ³⁵Cl Nuclear Quadrupole Resonance frequency (ν_Q) and spin-lattice relaxation time (T₁) were measured as a function of temperature in p-chlorofluorobenzene. Three different phases were found according to the thermal history of the sample and only one was stable up to the melting point. In one of the phases, the presence of molecular reorientations can be inferred from T₁ data with activation energy of 3.7 kcal/mol. A value of 13.9 kJ/mol for the fusion heat of this compound has been obtained.     

NMR observation of critical dynamics in the (TMTSF)2PF6 organic superconductor

We have studied the organic superconductor (TMTSF)₂PF₆ using ¹H nuclear magnetic resonance. The spin-lattice (T₁) and the spin-spin relaxation time (T₂) measurements manifested a divergence associated with a structural phase transition at 160 K.     

The ratio of the quadrupole moments of the isotopes95Mo and97Mo

The spin-lattice relaxation timesT ₁ of the NMR signals of⁹⁵Mo and⁹⁷Mo in aqueous K₂MoO₄ solutions were determined by the inversion recovery technique. To separate the relaxation rates due to electric quadrupole interaction and due to magnetic dipole interaction, pure H₂O and mixtures of H₂O and D₂O were used as solvent. No dependence of the ratio of the relaxation ratesT ₁(⁹⁵Mo)/T ₁(⁹⁷Mo) on the composition of the solvent was to be detected, i.e. the relaxation due to magnetic dipole interaction may be neglected. From the ratio of the relaxation rates the absolute value of the ratio of the quadrupole moments of the molybdenum isotopes was evaluated: ¦Q(⁹⁷Mo)/Q(⁹⁵Mo)¦ = 11.4 ±0.3.     

31P and 11B NMR in amorphous NiPB alloys near the paramagnetic-ferromagnetic transition

Knight-shift and nuclear spin-lattice relaxation time measurements have been performed between 4.2°K and room temperature on ¹¹B and ³¹P in amorphous NiPB alloys near the para-ferromagnetic transition. The EFG parameters on ¹¹B were found to be ν_Q=200(±20)kHz and η = 0.35 (±0.10). Knight-shift and Korringa spin-lattice relaxation are mainly due to mechanisms involving p electrons. The effect of Ni magnetic clouds results in a broadening of the linewidth. We observed also the occurence of a Giovannini-Heeger-like contribution to the spin-lattice relaxation rate.     

Low temperature 93Nb nuclear spin-lattice relaxation in Nb and NbMo alloys

High accuracy ⁹³Nb nuclear spin-lattice relaxation data are presented for Nb, Nb_0.75Mo_0.25, and Nb_0.70Mo_0.30 between 1.7 and 4.2 K. (T₁T)^?1 is independent of temperature and scales as the square of the density of states at the Fermi level.     

199Hg and63,65Cu NMR studies of mercury based high-T c superconductors

Hg-oxide ceramic high temperature superconductors were studied by¹⁹⁹Hg and^63,65Cu NMR spectroscopy. Room temperature spectra, spin-spin and spin-lattice relaxation times of samples with different superconducting transition temperatures are presented. A spin-lattice relaxation time ofT ₁=35 msec and a spin-spin relaxation time ofT ₂=1.6 msec were found for the¹⁹⁹Hg NMR. All samples exhibit similar characteristic powder spectra caused by an axially symmetric¹⁹⁹Hg spin interaction. The isotropic value and the anisotropy of the tensor relative to solid HgCl₂ as a standard substance is estimated. Furthermore, results of^63,65Cu NMR measurements at a temperature of 4.2 K which exhibit a typical powder line shape (forI=3/2) are presented.     

H NMR study of the phase transitions of trissarcosine calcium chloride single crystals at low temperature

The ¹H NMR line-width and spin-lattice relaxation time T₁ of TSCC single crystals were studied. Variations in the temperature dependence of the spin-lattice relaxation time were observed near 65 and 130 K, indicating drastic alterations of the spin dynamics at the phase transition temperatures. The changes in the temperature dependence of T₁ near 65 and 130 K correspond to phase transitions of the crystal. The anomalous decrease in T₁ around 130 K is due to the critical slowing down of the soft mode. The abrupt change in relaxation time at 65 K is associated with a structural phase transition. The proton spin-lattice relaxation time of this crystal also has a minimum value in the vicinity of 185 K, which is governed by the reorientation of the CH₃ groups of the sarcosine molecules. From this result, we conclude that the two phase transitions at 65 and 130 K can be discerned from abrupt variations in the ¹H NMR relaxation behavior, and that ¹H nuclei play important roles in the phase transitions of the TSCC single crystal.     

Isotope ratio of Cl NQR spin-lattice relaxation times in 1D hydrogen-bonding system of tetramethylpyrazine-chloranilic acid at high temperatures

The temperature dependences of spin-lattice relaxation time T ₁ of ³⁵Cl and ³⁷Cl NQR were studied for the co-crystal of tetramethylpyrazine (TMP) with chloranilic acid (H₂ca), TMP-H₂ca, in which one-dimensional hydrogen bonding is formed by alternate arrangement of TMP and H₂ca. The isotope ratio ³⁷Cl T ₁ / ³⁵Cl T ₁ was determined to be 1.0 ± 0.1 above ca. 290 K where a steep decrease of spin-lattice relaxation time T ₁ with increasing temperature was observed. In this temperature range it is suggested that the relaxation is originated from the slow fluctuation of electric field gradient (EFG). Beside EFG fluctuation due to the external-charge-density fluctuation, the small angle reorientation of the quantization axis triggered by a proton transfer motion between N...H-O and N-H...O hydrogen bonding states is proposed.     

The “corset effect” of spin-lattice relaxation in polymer melts confined in nanoporous media

Linear polyethylene oxides with molecular weightsM _w of 1665 and 10170 confined in pores with variable diameters in a solid methacrylate matrix were studied by proton field-cycling nuclear magnetic resonance relaxometry. The pore diameter was varied in the range of 9–57 nm. In all cases, the spin-lattice relaxation time shows a frequency dependence close toT ₁∞ v^3/4 in the range ofv=3·10^?1-2·10¹ MHz as predicted by the tube-reptation model. This protonT ₁ dispersion essentially reproduces that found in a previous deuteron study (R. Kimmich, R.-O. Seitter, U. Beginn, M. Möller, N. Fatkullin: Chem. Phys. Lett. 307, 147, 1999). As a feature particularly characteristic for reptation, this finding suggests that reptation is the dominating chain dynamics mechanism under pore confinement in the corresponding time range. The absolute values of the spin-lattice relaxation times indicate that the diameter of the effective tubes in which reptation occurs is much smaller than the pore diameters on the time scale of spin-lattice relaxation experimens. An estimation leads to a valued ^*～0.5 nm. The impenetrability of the solid pore walls, the uncrossability of polymer chains (“excluded volume”) and the low value of the compressibility in polymer melts create the “corset effect” which reduces the lateral motions of polymer chains to a microscopic scale of only a few tenths of a nanometer.     

Nuclear Quadrupole spin-lattice relaxation in Rhombohedral Arsenic

The temperature dependence of the spin-lattice relaxation time T₁ in rhombohedral arsenic has been measured by nuclear quadrupole resonance. The relaxation time is inversely proportional to the temperature and of a magnitude which indicates that the relaxation results from the Fermi contact interaction of the conduction electrons and holes and the arsenic nuclei. The density of electrons and holes at the site of the nucleus, averaged over the Fermi surface is approximately 2.6 × 10²¹ carriers cm^?3.     

H and K spin-lattice relaxation, ionic motion and Raman processes in the proton conducting KHSeO4 single crystal

The spin-lattice relaxation rates of ¹H and ³⁹K nuclei in KHSeO₄ crystals were studied in the temperature range 160-400 K. The spin-lattice relaxation recovery of ¹H nucleus in this crystal can be represented with a single exponential function, and the relaxation T₁⁻¹ curve of ¹H can be represented with the Bloembergen-Purcell-Pound (BPP) function. The relaxation process of ³⁹K with dominant quadrupole relaxation can be described by a linear combination of two exponential functions. T₁⁻¹ for the ³⁹K nucleus was found to have a very strong temperature dependence, T₁⁻¹=βT⁷. Rapid variations in relaxation rates are associated with critical fluctuations in the electronic spin system. The T⁷ temperature dependence of the Raman relaxation rate is shown here to be due to phonon-magnon coupling.     

Distinction between normal and leukemic bone marrow by water protons nuclear magnetic resonance relaxation times

Pulsed nuclear magnetic resonance studies have been carried out on bone marrow of normal human subjects and patients with leukemia: chronic myeloid leukemia (CML) and acute myeloid leukemia (AML). It was observed that the proton spin-lattice relaxation time (T₁) value was discriminatory in the normal and leukemic cases with a statistical significance of (p < 0.01). Ouabain treatment of cells did not show any perceptible change of T₁ value when compared with the nontreated cells, indicating that the concomitant cation effluxes do not affect spin-lattice relaxation time. The water contents of normal, leukemic, and ouabain treated cells were in the range 60%–80%. Higher Fe levels were encountered in the normal than the leukemic samples, while levels of Zn, Cu, Mn, Co, and Ni were elevated in the leukemic samples compared with the normals. Despite the T₁ differences observed, the multiparameter studies do not uniquely pinpoint factors responsible for the elevation of T₁ in the malignant state.     

Frequency-dependent spin-lattice relaxation study of transport processes in superionic conductors

The sensitivity of the¹⁹F spin-lattice relaxation dispersion, T₁,(ω), to motional disorder in crystalline superionic conductors of the type La_1?xSr_xF_3?x (x = 0; 0.03) is shown. T₁ times are measured in the frequency range from 90 kHz to 370 MHz using standard techniques in combination with field-cycling. The relaxation dispersion shows qualitative differences from the standard Bloembergen-Purcell-Pound behavior. At low frequencies a relaxation model using a distribution of correlation times for diffusing ions is found to be consistent with the experimental results. At frequencies higher than 50 MHz another process of the Debye type which is not induced by ionic hopping dominates the relaxation.     

Nuclear spin-lattice relaxation due to non-linear excitations in magnetic chains

A simple classical model for nuclear spin-lattice relaxation due to solitons in XY one-dimensional magnetic chains in an external magnetic field is discussed. The results show that one should expect opposite behavior for the H/T dependence of T^-1₁ for the ferromagnetic and the antiferromagnetic case.     

Spin gap, phase separation and d-wave pairing as revealed by electron spin-lattice relaxation in 123 and 124 YBaCuO systems doped with Gd3+

With an original modulation technique, the Gd³⁺ electron spin-lattice relaxation has been investigated in normal and superconducting states of YBa₂Cu₃O_6+x (123) and YBa₂Cu₄O₈ (124) compounds doped with 1% Gd. In the 123 sample withx = 0.9T _c = 90 K), theT ₁ behavior within 50 <T< 200 K reveals the [1 ? tanh²(Δ/2kT)]/T dependence typical of a spin gap opening with Δ ≈ 240 K. Below 50 K, the exponential slowing down ofT ₁ is limited by the Korringa-like behaviorT ₁ T = const); the same Korringa-like law is found in the 123 sample withx = 0.59 (T _c = 56 K) within the total 4.2–200 K temperature range. This is interpreted in terms of microscopic separation of the normal and superconducting phases allowing for the electron spin cross-relaxation between them. In the 124 sample (T _c = 82 K), the Gd³⁺ relaxation rate below 60 K is found to obey a power lawT _n with an exponentn ≈ 3. Such a behavior (previously reported for nuclear spin relaxation) is indicative of the d-wave superconducting pairing. Additional paramagnetic centers characterized by relatively slow spin-lattice relaxation are found in both 123 and 124 systems. A well-pronounced change in theT ₁ temperature dependence atTT* ≈ 180–200 K is observed for these slowly relaxing centers as well as for the conventional, fast-relaxing Gd³⁺ ions, suggesting microscopic phase separation and a change in the relaxation mechanism due to electronic crossover related with the opening of the spin gap. This hypothesis is supported by some “180 K anomalies” previously reported by other authors.     

Nuclear quadrupole spin-lattice relaxation in Bi4Ge3O12 single crystals doped with atoms of d or f elements. Crystal field effects in compounds exhibiting anomalous magnetic properties

The nuclear quadrupole spin-lattice relaxation was studied in the range 4.2–300 K for single crystals of Bi₄Ge₃O₁₂ doped with minor amounts (the tenth fractions of mol%) of paramagnetic atoms of Cr, Nd, and Gd. Unusual spin dynamic features were recently found for these crystals at room temperature: a dramatic (up to 8-fold) increase in the effective nuclear quadrupole spin-spin relaxation time T ₂* occurred upon doping the pure Bi₄Ge₃O₁₂ sample. Unlike T ₂*, the effective spin-lattice relaxation time T ₁* at room temperature differs insignificantly for both doped and pure samples. But at lower temperatures, the samples exhibit considerably different behavior of the spin-lattice relaxation with temperature, which is caused by different contributions to the relaxation process of the dopant paramagnetic atoms. The distinctive maximum in the temperature dependence of the spin-lattice relaxation time for the Nd-doped crystal is shown to result from the crystal electric field effects.