Tortuosity measurement and the effects of finite pulse widths on xenon gas diffusion NMR studies of porous media.

We have extended the utility of NMR as a technique to probe porous media structure over length scales of approximately 100-2000 microm by using the spin 1/2 noble gas 129Xe imbibed into the system's pore space. Such length scales are much greater than can be probed with NMR diffusion studies of water-saturated porous media. We utilized Pulsed Gradient Spin Echo NMR measurements of the time-dependent diffusion coefficient, D(t), of the xenon gas filling the pore space to study further the measurements of both the pore surface-area-to-volume ratio, S/V(p), and the tortuosity (pore connectivity) of the medium. In uniform-size glass bead packs, we observed D(t) decreasing with increasing t, reaching an observed asymptote of approximately 0.62-0.65D(0), that could be measured over diffusion distances extending over multiple bead diameters. Measurements of D(t)/D(0) at differing gas pressures showed this tortuosity limit was not affected by changing the characteristic diffusion length of the spins during the diffusion encoding gradient pulse. This was not the case at the short time limit, where D(t)/D(0) was noticeably affected by the gas pressure in the sample. Increasing the gas pressure, and hence reducing D(0) and the diffusion during the gradient pulse served to reduce the previously observed deviation of D(t)/D(0) from the S/V(p) relation. The Pade approximation is used to interpolate between the long and short time limits in D(t). While the short time D(t) points lay above the interpolation line in the case of small beads, due to diffusion during the gradient pulse on the order of the pore size, it was also noted that the experimental D(t) data fell below the Pade line in the case of large beads, most likely due to finite size effects.     

Wine Storage at Cellar vs. Room Conditions: Changes in the Aroma Composition of Riesling Wine

Storage temperature is one of the most important factors affecting wine aging. Along with bottling parameters (type of stopper, SO₂ level and dissolved O₂ in wine), they determine how fast wine will evolve, reach its optimum and decline in sensory quality. At the same time, lowering of the SO₂ level in wine has been a hot topic in recent years. In the current work, we investigated how Riesling wine evolved on the molecular level in warm (~25 °C) and cool (~15 °C) conditions depending on the SO₂ level in the wine (low, medium and high), flushing of the bottle’s headspace with CO₂ and three types of stoppers (Diam 30, Diam 30 origin and Diam 5) with different OIR levels (0.8–1.3 mg) and OTR levels (0.3–0.4 mg/year). It was demonstrated that the evolution of primary and secondary aromas, wine color and low molecular weight sulfur compounds (LMWSCs) during the two years of aging mainly depended on the storage temperature. Variation in the SO₂ level and CO₂ in the headspace affected mostly certain LMWSCs (H₂S, MeSH) and β-damascenone. New aspects of C₁₃-norisprenoids and monoterpenoids behavior in Riesling wine with different levels of SO₂ and O₂ were discussed. All three types of stoppers showed very close wine preservation properties during the two years of storage. The sensory analysis revealed that, after only six months, the warm stored wines with a low SO₂ level were more oxidized and different from the samples with medium and high SO₂ levels. A similar tendency was also observed for the cool stored samples.     

Partial halogenation of cyclic and branched perhydropentasilanes

The perhydropentasilanes (H(3)Si)(4)Si and Si(5)H(10) were chlorinated with SnCl(4) to give chlorohydropentasilanes without destruction of the Si-Si backbone. Tetrachloroneopentasilane (ClH(2)Si)(4)Si (2) was prepared in high yield from (H(3)Si)(4)Si and 3.5 equiv of SnCl(4), while Si(5)H(10) and an equimolar amount of SnCl(4) afforded a mixture of ～60% of ClSi(5)H(9) (1) with polychlorinated cyclopentasilanes and unreacted starting material, which could not be separated by distillation. The selective monochlorination of Si(5)H(10) was achieved starting from MesSi(5)Cl(9) (3; Mes = 2,4,6-trimethylphenyl) or TBDMP-Si(5)Cl(9) (4; TBDMP = 4-tert-butyl-2,6-dimethylphenyl). 3 or 4 was successfully hydrogenated with LiAlH(4) to give MesSi(5)H(9) (6) or TBDMP-Si(5)H(9) (7), which finally gave 1 along with aryl-H and Si(5)H(10) after treatment with an excess of liquid anhydrous HCl. All compounds were characterized by standard spectroscopic techniques. For Si-H derivatives, the coupled (29)Si NMR spectra were analyzed in detail to obtain an unequivocal structural assignment. The molecular structures of 2-4 were further confirmed by X-ray crystallography.     

UTILIZATION OF TOOLS FOR SUCCESSFUL. TROUBLESHOOTING OF STRUCTURAL PROBLEMS

A structural failure problem was solved using an integrated and iterative program of testing and analysis. The steps taken in solving the problem were: analytical calculations; operational testing; qualifications of analytical results; problem identification; design of corrective action; and confirmatory testing.     

The narrow pulse approximation and long length scale determination in xenon gas diffusion NMR studies of model porous media

We report a systematic study of xenon gas diffusion NMR in simple model porous media, random packs of mono-sized glass beads, and focus on three specific areas peculiar to gas-phase diffusion. These topics are: (i) diffusion of spins on the order of the pore dimensions during the application of the diffusion encoding gradient pulses in a PGSE experiment (breakdown of the narrow pulse approximation and imperfect background gradient cancellation), (ii) the ability to derive long length scale structural information, and (iii) effects of finite sample size. We find that the time-dependent diffusion coefficient, D(t), of the imbibed xenon gas at short diffusion times in small beads is significantly affected by the gas pressure. In particular, as expected, we find smaller deviations between measured D(t) and theoretical predictions as the gas pressure is increased, resulting from reduced diffusion during the application of the gradient pulse. The deviations are then completely removed when water D(t) is observed in the same samples. The use of gas also allows us to probe D(t) over a wide range of length scales and observe the long time asymptotic limit which is proportional to the inverse tortuosity of the sample, as well as the diffusion distance where this limit takes effect (approximately 1-1.5 bead diameters). The Padé approximation can be used as a reference for expected xenon D(t) data between the short and the long time limits, allowing us to explore deviations from the expected behavior at intermediate times as a result of finite sample size effects. Finally, the application of the Padé interpolation between the long and the short time asymptotic limits yields a fitted length scale (the Padé length), which is found to be approximately 0.13b for all bead packs, where b is the bead diameter.