Toward Production of Pure 13C Hyperpolarized Metabolites Using Heterogeneous Parahydrogen-Induced Polarization of Ethyl[1-13C]acetate.

Here, we report the production of 13C-hyperpolarized ethyl acetate via heterogeneously catalyzed pairwise addition of parahydrogen to vinyl acetate over TiO2-supported rhodium nanoparticles, followed by magnetic field cycling. Importantly, the hyperpolarization is demonstrated even at the natural abundance of 13C isotope (ca. 1.1%) along with the easiest separation of the catalyst from the hyperpolarized liquid.

Nasal aerodynamics protects brain and lung from inhaled dust in subterranean diggers, Ellobius talpinus.

Inhalation of air-dispersed sub-micrometre and nano-sized particles presents a risk factor for animal and human health. Here, we show that nasal aerodynamics plays a pivotal role in the protection of the subterranean mole vole Ellobius talpinus from an increased exposure to nano-aerosols. Quantitative simulation of particle flow has shown that their deposition on the total surface of the nasal cavity is higher in the mole vole than in a terrestrial rodent Mus musculus (mouse), but lower on the olfactory epithelium. In agreement with simulation results, we found a reduced accumulation of manganese in olfactory bulbs of mole voles in comparison with mice after the inhalation of nano-sized MnCl2 aerosols. We ruled out the possibility that this reduction is owing to a lower transportation from epithelium to brain in the mole vole as intranasal instillations of MnCl2 solution and hydrated nanoparticles of manganese oxide MnO · (H2O)x revealed similar uptake rates for both species. Together, we conclude that nasal geometry contributes to the protection of brain and lung from accumulation of air-dispersed particles in mole voles.

Conversion of nuclear spin isomers of ethylene.

A theoretical model of the nuclear spin isomer conversion in C2H4 induced by the intramolecular spin-spin interaction between hydrogen nuclei has been developed. In the ground electronic state, C2H4 has four nuclear spin isomers in contrast to two isomers in the molecules studied so far in this field of research. At the gas pressure of 1 Torr, the rate of conversion between isomers with the nuclear spin symmetries B1u and B2u was found to be 5.2 × 10(-4) s(-1), which coincides within experimental uncertainties with the rate recently measured by Sun et al. (Science 2005, 310, 1938). It was determined that at low gas pressures the conversion is induced mainly by the mixing of only one pair of rotational states. The calculated pressure dependence of the conversion rate predicts that conversion slows down with increasing pressure at pressures higher than 300 Torr.

The generating functions formalism for the analysis of spin response to the periodic trains of RF pulses. Echo sequences with arbitrary refocusing angles and resonance offsets.

The generating functions (GF) formalism was applied for calculation of spin density matrix evolution under the influence of periodic trains of RF pulses. It was shown that in a general case, closed expression for the generating function can be found that allows in many cases to derive analytical expressions for the generating function of spin density matrix (magnetization, coherences). This approach was shown to be particularly efficient for the analysis of multi-echo sequences, where one has to average over various frequency isochromats. The explicit analytical expressions for the generating function for echo amplitudes in a Carr-Purcell-Meiboom-Gill (CPMG) echo sequence, a multiecho sequence with incremental phase of refocusing pulse, a gradient echo sequence including transient period were obtained for an arbitrary flip angle and an arbitrary resonance offset. Comparison of the theory and the spin-echo experiments was done, demonstrating a good agreement.

The NMR microimaging studies of the interplay of mass transport and chemical reaction in porous media.

PFG NMR is employed to perform a comparative study of the filtration of water and propane through model porous media. It is shown that the dispersion coefficients for water are dominated by the holdup effects even in a bed of nonporous glass beads. It is demonstrated that correlation experiments such as VEXSY are applicable to gas flow despite the large diffusivity values of gases. The PFG NMR technique is applied to study the gravity driven flow of liquid-containing fine solid particles through a porous bed. The NMR imaging technique is employed to visualize the propagation of autocatalytic waves for the Belousov-Zhabotinsky reaction which is carried out in a model porous medium. It is demonstrated that the wave propagation velocity decreases as the wave crosses the boundary between the bulk liquid and the flooded bead pack. The images detected during the catalytic hydrogenation of alpha-methylstyrene on a single catalyst pellet at elevated temperatures have revealed that the reaction and the accompanying phase transition alter the distribution of the liquid phase within the pellet.

NMR imaging of mass transport and related phenomena in porous catalysts and sorbents.

NMR imaging is employed to study the preparation of supported catalysts and a number of mass transport processes in porous catalysts and sorbents. It is shown that, similar to Pt, adsorbed Pd leads to the increase of the relaxation times of liquids permeating porous alumina supports. A faster penetration of adsorbed water into the sorbent is observed when water vapor sorption by selective water sorbents is carried out under vacuum as compared to the sorption from moist air. An interruption of the capillary flow of water within the monolithic catalyst is shown to lead to a non-uniform drying along the monolith channels. Flow imaging of water inflowing into the monolith has revealed a complicated flow pattern characterized by the existence of counterflows in the entrance region.