New pulse sequences for T1− and T1/T2−contrast enhancing in NMR imaging

Improved pulse sequences DIFN (abbreviation of the words: DIFferentiation by N pulses), 90° − τ₁ − 180° − τ₁ − … 180° − τ_n, with optimised time intervals τ₁ for T₁ measurement and contrast enhancing in NMR imaging are presented. The pulse sequences DIFN have a better sensitivity to T₁ than the well-known pulse sequence SR. In contrast to the IR pulse sequence, the information given by the DIFN pulse sequence is more reliable, because the NMR signal does not change its sign. For a given time interval τ₀ ≤ (0.1 − 0.3) T₁′ the DIFN pulse sequences serve as T₁-filters. They pass the signal components with relatively short T₁ < T₁′ and suppress the components with relatively long T₁ < T₁′. The effects of the radiofrequency field inhomogeneity and inaccurate adjusting of pulse lengths are also considered. It is also proposed in this work to use the joint T₁T₂-contrast in NMR imaging obtained as a result of applying the DIFN pulse sequences in combination with the well-known Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence. The region of interest, where the contrast should be especially enhanced, is specified by the two times at which measurements are performed, which allow the amplitudes of pixels to reach some defined levels by spin-lattice and spin-spin relaxation.     

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.     

Slow Dynamics Mapping of Large-Linewidth Solids by a MARF Spin-Lock Filter

A new method forT_1ρcontrast in solid-state imaging is presented. The method is based upon the addition of aT_1ρspin-lock pulse to the standard MARF pulse sequence and is able to provide relaxation contrast in dependence either on the lock time or on the intensity of the lock field, without having effects related to the line-narrowing procedure. The results on some large-linewidth solids show thatT_1ρvalues measured by the usual spin-lock pulse sequence agree with those measured on space-resolved lines.     

Nuclear spin-lattice relaxation in the triply rotating frame and ultraslow molecular motions in solids

A method for measuring nuclear magnetic spin-lattice relaxation in solids in the effective field H_e3 acting in the triply rotating frame (TRF) is described. The method advances the previously described techniques whereby nuclear magnetic resonance and relaxation in the rotating (RF) and doubly rotating frames (DRF) are measured directly. In the present work, the RF and DRF are employed for suppressing the secular part of nuclear dipole-dipole (DD) interactions in the first two orders. As a result, the higher-order DD interactions (four- and five-particle ones) were separated, and their contribution to the nuclear spin-lattice relaxation in the TRF was studied experimentally. The experiments were carried out on protons in polycrystalline benzene. With the introduced technique, an overall spin-lattice relaxation decay in the TRF was recorded continuously during a single radio-frequency pulse with a length not exceeding 1 s. The contribution of multiproton nonsecular DD interactions to the proton spin-lattice relaxation in the TRF was observed selectively as a pronounced local minimum in the temperature dependence of the relaxation timeT _1ϱϱϱ. This contribution corresponds to ultraslow motion of benzene molecules with a rate about γH_e3 ≈ 2π · (10¹-10³) s^-1 and is determined quantitatively by specific correlation functions corresponding to the multiparticle nonsecular DD interactions of protons. The prospects of using this method for studying ultraslow atomic and molecular dynamics in solids are discussed.     

7Li NMR study of the mobility of lithium ions in one-dimensional channels of Nb3Se4

The temperature dependence of the spin-lattice relaxation time T ₁ and the ⁷Li NMR spectra of the Li_0.7Nb₃Se₄ intercalation compound with one-dimensional channel structure have been studied. It is found that the temperature dependence of T ₁ exhibits two relaxation minima, and the quadrupole splitting in the Li NMR spectra shows an anomalous temperature behavior. The inference is drawn that the observed effects are associated with the high-rate diffusive motion of lithium ions along one-dimensional channels and the interchannel transitions.     

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.     

Critical slowing down of fluctuations in p-terphenyl and p-quaterphenyl observed by proton spin-lattice relaxation

The temperature evolution of the proton spin-lattice relaxation time T₁ in p-terphenyl and in p-quaterphenyl around their order-disorder phase transition has been measured. In both cases pretransitional collective fluctuations destroy the high temperature Arrhenius behaviour of the relaxation rate corresponding to a single reorientational jump motion. The spin-lattice relaxation times present then a drastic decrease until the transition temperature (T₀ = 193 K in p-terphenyl, T₀ = 238 K in p-quaterphenyl). This decrease is associated to the critical slowing down of fluctuations. In the low temperature phase the ordering phenomena lead to a sharp drop of the spin-lattice relaxation rate.     

Spin diffusion in multiple pulse spin-locking in solids containing paramagnetic impurities

Spin diffusion and spin-lattice relaxation in solids containing paramagnetic impurities under influence of a multiple-pulse spin-locking radio-frequency sequence are studied theoretically and experimentally. The diffusion equation obtained provides a clue for determination of the time dependent magnetization. The spin-lattice relaxation time is calculated as a function of the correlation time and multiple-pulse field parameters. From the experimental data the spin diffusion coefficient, the radius of the spin diffusion barrier, and the correlation time for very slow molecular motion in polycrystalline (C(2)F)(n) system are estimated and found to be D～7.1×10(-12)cm(2)/s, r(c)～4.8×10(-10)m, and τ(c)～10.2μs, respectively.     

Spin-lattice relaxation of the O2 − molecule-ion in the potassium halides

An experimental and theoretical study of the spin-lattice relaxation (SLR) of the O₂ ^? molecule-ion in the potassium halides has been made. The SLR rate was measured by several methods between 1.32°K and 36°K with a 3 cm. ESR spectrometer. The results indicate a one phonon process with a large anisotropy dominates forT<2°K.T ₁ is much longer for the magnetic field parallel to the molecular axis. Detailed theoretical calculations indicate a new SLR process, namely phonon-induced libration of the molecular axis, can probably explain the field parallel case. The Van Vleck SLR process can account for the field-perpendicular case.     

A field-cycling NMR study of nematic 4-pentyl-4′-cyanobiphenyl confined in porous glasses

The proton spin-lattice relaxation time T₁, in the nematic liquid crystal 4-pentyl-4′-cyanobiphenyl confined in a glassy porous matrix has been measured in a wide Larmor frequency range of 1 · 10²?2 · 10⁷ Hz employing the fast field-cycling NMR technique. A strong influence of the restricted geometry on the character of the T₁ dispersion was found. Our investigation clearly demonstrates the importance of the translationally induced molecular reorientations in inhomogeneous director field for the relaxation in the samples with 200 and 80 nm mean pore size. The experimental results are in a good agreement with the theoretical predictions. In the sample with 7 nm pore size the main contribution to the relaxation is ascribed to the slowing down of the molecular motion in the near-surface layer. Zero-field 1H NMR spectra of a microconfined liquid crystal are reported for the first time.     

T1 as a function of larmor frequency in solid CH4 at 4.2 K: An experiment on recent theories

The spin-lattice relaxation time T₁ has been measured in partially converted samples at NMR frequencies ranging from 4 to 55 MHz. Results allow to check in detail the existing models for relaxation in solid CH₄.     

Molecular dynamics in poly[(R)-3-hydroxybutyric acid] biopolymer as studied by NMR

Nuclear magnetic resonance line shapes and spin-lattice relaxation timesT ₁, of¹H and²H nuclei of poly[(R)-3-hydroxybutyric acid] have been measured in the temperature range 100–413 K. The results provide information on the local dynamics of the compound. Activation parameters of the revealed motion are determined.     

MRICOM–MRI COntrast Modelling using 2D T1–T2 correlation spectra and relaxation signatures

Image contrast is calculated by inputting experimental 2D T₁–T₂ relaxation spectra into the ODIN software interface. The method involves characterising a magnetic resonance imaging pulse sequence with a “relaxation signature” which describes the sensitivity of the sequence to relaxation and is independent of sample parameters. Maximising (or minimising) the overlap between the experimental 2D T₁–T₂ relaxation spectra and the relaxation signature can then be used to maximise image contrast. The concept is illustrated using relaxation signatures for the echo planar imaging and Turbo spin-echo imaging sequences, together with in-vitro 2D T₁–T₂ spectra for liver and cartilage.     

Proton NMR study of α-MnH0.06

Proton nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates for the solid solution α-MnH_0.06 have been measured over the temperature range 11-297 K and the resonance frequency range 20-90 MHz. A considerable shift and broadening of the proton NMR line and a sharp peak of the spin-lattice relaxation rate are observed near 130 K. These effects are attributed to the onset of antiferromagnetic ordering below the Néel temperature T_N≈130 K. The proton NMR line does not disappear in the antiferromagnetic phase; this suggests a small magnitude of the local magnetic fields at H-sites in α-MnH_0.06. The spin-lattice relaxation rate in the paramagnetic phase is dominated by the effects of spin fluctuations.     

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.     

What does NMR tell us about the electronic state of high-T c superconductors?

An introduction to the models which are usually applied, when interpreting the NMR (nuclear magnetic resonance) parameter Knight shift (K _s) and spin-lattice relaxation rate 1/T ₁ in the normal and the superconducting state of high-temperature superconductors, is given. The different hyperfine interaction parameters involved, as well as the static and dynamic susceptibility χ(q,ω) will be discussed. I will point at those highlights as antiferromagnetic correlations, spin gap and vortex lattice dynamics which have emerged from the analysis of the NMR data.     

Fluorine NMR and piezoelectricity in solid GeF4

Flourine NMR second moments and spin-lattice relaxation times were measured for solid GeF₄. The results indicate a hindered molecular motion and the piezolectricity of the solid GeF₄.     

H and C NMR studies of molecular orientation and dynamics in liquid crystal 6BA

The dynamics and orientation of dimers accompanying the formation and destruction of hydrogen bonds in the nematic phases of 4-n-hexylbenzoic acid (6BA) were studied by ¹³C and ²H NMR. The orientational order parameter S in the nematic phase was estimated from the quadrupole splitting of the ²H NMR spectrum. The intermolecular interaction energy for the molecular order in the nematic phase decreased with increasing temperature. The flexibility of dimers due to the destruction of the hydrogen bond is closely related to a decrease in the intermolecular interaction energy. The proportion of ²H NMR spin-lattice relaxation time (T₁) to S, which reveals the coupling of the orientational fluctuations with the hydrogen bonding processes, was observed.     

A rapid assessment of entrapment of nitroxyl radicals and lanthanide compounds by β-cyclodextrin using spin-lattice relaxation Measurements

Inclusion compounds of several tetramethylpiperidin-oxyl derivatives and gadolinium acetate, ytterbium acetate, praseodymium chloride, and praseodymium acetate with β-cyclodextrin were prepared. These compounds were compared, where appropriate (nitroxyls), by EPR spectroscopy, and by measurements of spin-lattice relaxation times (T ₁), of water protons with the corresponding uncomplexed radical and lanthanide species. It was shown that the spin-lattice relaxation measurements provide a viable, rapid method for the assessment of structures of these inclusion compounds. It is believed that the lanthanide-β-CD inclusion compounds could be of interest as potential contrast agents for MR imaging.     

Proton NMR relaxation study of the CsHSO4 solid acid system

At 141 °C the solid acid CsHSO₄ is known to undergo transition to a superprotonic phase that is characterized by dramatic (several-order-of-magnitude) increases in hydrogen ion conductivity. Proton NMR spin-spin relaxation time T₂ measurements reported here for CsHSO₄ also reveal substantial increases (factors of 20-30) in the vicinity of the transition temperature. In the temperature range just below the transition (70-136 °C), T₂ increases by a factor of order 10 relative to the rigid-lattice regime, suggesting motional narrowing of the NMR resonance line. In the regime of motional narrowing, the activation energy barrier to diffusion is 0.40 eV, as determined from the present T₂ results. NMR spin-lattice relaxation T₁ measurements also show behavior consistent with transition to a regime of rapid hydrogen motion. In particular, proton T₁'s decrease with temperature (from 80 to 120 °C), and then drop sharply near the transition temperature. Above the transition temperature, T₁ exhibits a minimum in which the correlation time is found to be ∼2 ns.