Two-site jumps in dimethyl sulfone studied by one- and two-dimensional 17O NMR spectroscopy.

Polycrystalline dimethyl sulfone is studied using central-transition oxygen-17 exchange NMR. The quadrupolar and chemical shift tensors are determined by combining quantum chemical calculations with line shape analyses of rigid-lattice spectra measured for stationary and rotating samples at several external magnetic fields. Quantum chemical computations predict that the largest principal axes of the chemical shift anisotropy and electrical field gradient tensors enclose an angle of about 73°. This prediction is successfully tested by comparison with absorption spectra recorded at three different external magnetic fields. The experimental one-dimensional motionally narrowed spectra and the two-dimensional exchange spectrum are compatible with model calculations involving jumps of the molecules about their two-fold symmetry axis. This motion is additionally investigated by means of two-time stimulated-echo spectroscopy which allows for a determination of motional correlation functions over a wider temperature range than previously reported using carbon and deuteron NMR. On the basis of suitable second-order quadrupolar frequency distributions, sin-sin stimulated-echo amplitudes are calculated for a two-site model in the limit of vanishing evolution time and compared with experimental findings. The present study thus establishes oxygen-17 NMR as a powerful method that will be particularly useful for the study of solids and liquids devoid of nuclei governed by first-order anisotropies.

Four-time 7Li stimulated-echo spectroscopy for the study of dynamic heterogeneities: Application to lithium borate glass.

To study the nature of the nonexponential ionic hopping in solids a pulse sequence was developed that yields four-time stimulated-echo functions of previously inaccessible spin-3/2-nuclei such as 7Li. It exploits combined Zeeman and octupolar order as longitudinal carrier state. Higher-order correlation functions were successfully generated for natural-abundance and isotopically-enriched lithium diborate glasses. Four-time 7Li measurements are presented and compared with two-time correlation functions. The results are discussed with reference to approaches devised to quantify the degree of nonexponentiality in glass forming systems and evidence for the occurrence of dynamic heterogeneities and dynamic exchange were found. Additional experiments using the 6Li species illustrate the challenge posed by subensemble selection when the dipolar interactions are not very much smaller than the quadrupolar ones.

Submillimeter coils for stimulated-echo spectroscopy of a solid sodium ion conductor by nonselective excitation of MHz broad 23Na quadrupolar satellite spectra.

In solids the detection of ionic motion covering the time range of milliseconds and longer is often accomplished using stimulated-echo spectroscopy. For spectral line widths much below or much above 1MHz nonselective or fully selective radio-frequency pulse excitation, respectively, is typically applied in such experiments. To enable the study of samples with quadrupolarly broadened satellite spectra featuring intermediate widths (in the lower MHz range) the present work exploits microcoils. Using such coils, stimulated-echo spectroscopy can be performed under conditions of nonselective excitation for instance with 23Na as a nuclear probe. Nutation experiments carried out used to assess the coil performance. The impact of second-order quadrupolar interactions is studied using explicit density-matrix calculations. The applicability of the present approach is successfully tested for a sodium orthophosphate based solid ion conductor.

Quadrupolar transients, cosine correlation functions, and two-dimensional exchange spectra of non-selectively excited spin-3/2 nuclei: A (7)Li NMR study of the superionic conductor lithium indium phosphate.

Cos-cos stimulated echoes of non-selectively excited spin-3/2 nuclei were not exploited in studies of slow motional processes in solids and solid-like samples, so far. Based on a theoretical analysis of the quadrupolar transients which hitherto obviously precluded the application of such echoes, their utility is demonstrated for the example of (7)Li NMR on the polycrystalline fast ion conductor lithium indium phosphate. Quadrupolar transients can adversely affect the shape of two- and three-pulse echo spectra and strategies are successfully tested that mitigate their impact. Furthermore, by means of suitably adapted cos-cos echo sequences an effective suppression of central-line contributions to the NMR spectra is achieved. By combining cos-cos and sin-sin datasets static two-dimensional exchange spectra were recorded that display quadrupolarly modulated off-diagonal intensity indicative of ionic motion.

Two-dimensional second-order quadrupolar exchange powder spectra for nuclei with half-integer spins. Calculations and an experimental example using oxygen NMR.

Two-dimensional chemical exchange spectra are determined for powders containing half-integer quadrupolar nuclei that evolve under the second-order quadrupolar interaction. For simple exchange processes it is shown that the calculated exchange patterns depend sensitively on the jump angles, the tensor parameters, and the rotation axes characterizing the geometry of the underlying molecular motion. The inclusion of other interactions is discussed. To demonstrate the feasibility of the experimental method a two-dimensional second-order quadrupolar exchange spectrum was recorded for a clathrate hydrate using oxygen NMR. Simulations based on a motional model involving a six-site jump capture the essential features of the experimental results.

Molecular motions in supercooled and glassy ibuprofen: deuteron magnetic resonance and high-resolution rheology study.

Using deuteron nuclear magnetic resonance, the molecular motions of specifically isotope-labeled ibuprofen were probed at the carboxylic group and at the methin group next to it. Spin relaxometry revealed slight differences between the molecular motions of the two isotopomers that are rationalized with reference to the hydrogen bonding of the COOH moiety. In the glassy state, a small-angle jump process among about four sites, related to the so-called γ-process, was identified using stimulated-echo spectroscopy. Indications for a Debye-like process, previously found to leave a weak signature in the dielectric loss, could not unambiguously be detected in magnetic resonance or shear mechanical experiments carried out for supercooled liquid ibuprofen.

Dynamics of glass forming ammonia hydrates.

The dielectric relaxation of ammonia-water mixtures was studied for a range of NH3 mole fractions x. For 0.01 ≤ x < 0.33, the samples can be supercooled relatively easily. In this composition range, the relaxation strength is proportional to x. The dielectric relaxation times display a super-Arrhenius behavior, are independent of the NH3 content in the specified range, and, for T > 250 K, line up smoothly with those of pure water. The relaxation behavior of glass forming ammonia hydrates was also investigated using nuclear magnetic resonance techniques including deuteron relaxometry and stimulated-echo spectroscopy, as well as static field-gradient proton diffusometry. These experiments yielded additional insights into the rotational and translational dynamics of ammonia hydrates.

Modulation of expression of endothelial nitric oxide synthase by nordihydroguaiaretic acid, a phenolic antioxidant in cultured endothelial cells.

Retrospective epidemiological studies have suggested that antioxidant therapy may decrease cardiovascular morbidity and mortality rates, although the mechanisms for this effect remain unclear. In the present study, we demonstrate that selective antioxidants can enhance expression of endothelial nitric oxide synthase (eNOS). We found that the antioxidants nordihydroguaiaretic acid (NDGA), catechol, glutaryl probucol, and N-acetylcysteine increased eNOS expression in cultured bovine aortic endothelial cells (BAECs). NDGA seemed to be the most potent of the phenolic antioxidants, producing a 3-fold increase in eNOS mRNA. This effect of NDGA was enhanced by nonphenolic antioxidants such as N-acetylcysteine and ascorbic acid. Nuclear run-on studies indicated that NDGA increased eNOS transcription. A similar increase in eNOS protein content was observed with Western blot analysis after treating BAECs or human aortic endothelial cells with NDGA. Exposure of BAECs to NDGA enhanced NO production, as measured by electron paramagnetic resonance spin trapping and eNOS activity, as measured by [14C]arginine-to-[14C]citrulline assay. Methylation of the phenolic hydroxyl groups completely inhibited the NDGA effect on eNOS mRNA levels. This effect of NDGA was not due to inhibition of lipoxygenase because cis-5,8,11,14-eicosatetraynoic acid did not alter eNOS expression. We conclude that antioxidants may not only increase the bioactivity of nitric oxide but also enhance expression of the eNOS enzyme. Such an effect may prove useful in conditions such as hypertension and atherosclerosis, in which nitric oxide production and/or biological activity is impaired.