Picosecond acoustic transmission measurements. II. Probing high frequency structural relaxation in supercooled glycerol

The high frequency acoustic response of liquids is measured in a manner directly analogous to conventional ultrasonic measurements. Two thin metal films act as acoustic transducer and receiver for a liquid layer between them. Pulsed optical excitation generates high bandwidth wave packets in the transducer, and these are detected in the receiver after damping and dispersion by the liquid. This initial measurement probes structural relaxation dynamics of glycerol in the frequency range 2-20 GHz, for temperatures between 235 and 291 K. The analysis presented here demonstrates the presence of excess relaxation, not accounted for by either the alpha or beta relaxation of the mode-coupling theory, and suggests the presence of constant loss in the susceptibility spectrum of supercooled glycerol.     

Efficient Demethylation of Methyl Esters with Anhydrous Trifluoroacetic Acid

Trifluoroacetic acid (TFA) is an effective reagent for the demethylation of methyl esters under anhydrous conditions, affording the parent acids and methyl trifluoroacetate.     

Synthesis and carbon-13 nuclear magnetic resonance spectroscopy of 5,6-dihydro-2-methyl-1,4-oxathiin,trans-tetrahydro-1,4-benzoxathiin, 1,4-tetrahydro-[9,10]benzoxathiin,the 4-oxides, 4,4-dioxides and related acyclic compounds

The results of a ¹³C NMR spectral investigation involving 5,6-dihydro-1,4-oxathiins, 1,4-tetrahydro[9,10]benzoxathiin, trans-tetrahydro-1,4-benzoxathiin, and the corresponding sulfoxides and sulfones are reported. An interpretation involving a dipolar structure with (2p→2p)π conjugation as opposed to (2p→3d)π interactions with the vinyloxy sulfides seems consistent with trends in the ¹³C NMR shifts. For the sulfoxides and sulfones, the substitutent-induced chemical shift (SCS) effects at the β vinylic carbons (βSO and βSO₂ effects) are considerably less than those at sp³ carbons. The γSO and γSO₂ values at the sp²γ carbons indicate deshielding, in contrast to the shielding at the sp³ carbons.     

Bulk ablation of soft tissue with intense ultrasound: modeling and experiments

Methods for the bulk ablation of soft tissue using intense ultrasound, with potential applications in the thermal treatment of focal tumors, are presented. An approximate analytic model for bulk ablation predicts the progress of ablation based on tissue properties, spatially averaged ultrasonic heat deposition, and perfusion. The approximate model allows the prediction of threshold acoustic powers required for ablation in vivo as well as the comparison of cases with different starting temperatures and perfusion characteristics, such as typical in vivo and ex vivo experiments. In a full three-dimensional numerical model, heat deposition from array transducers is computed using the Fresnel approximation and heat transfer in tissue is computed by finite differences, accounting for heating changes caused by boiling and thermal dose-dependent absorption. Similar ablation trends due to perfusion effects are predicted by both the simple analytic model and the full numerical model. Comparisons with experimental results show the efficacy of both models in predicting tissue ablation effects. Phenomena illustrated by the simulations and experiments include power thresholds for in vivo ablation, differences between in vivo and ex vivo lesioning for comparable source conditions, the effect of tissue boiling and absorption changes on ablation depth, and the performance of a continuous rotational scanning method suitable for interstitial bulk ablation of soft tissue.     

Os(VIII)-catalysed oxidation of sulfides by sodium salt of N-chlorobenzenesulfonamide

Catalytic activity of Os(VIII) in the oxidation of some twenty organic sulfides with sodium salt of N-chlorobenzenesulfonamide (CAB) has been investigated in alkaline (pH8.7) t-butanol–water (1:1 v/v) medium. Significant retarding influence of [OH⁻] on the reactivity is exhibited. The catalysed reaction is strongly accelerated in the presence of Hg(II). Imperfections are observed in the linear Hammett relationship in the case of –NO₂ substituents.     

Raman spectroscopic investigation on the microenvironment of the liver tissues of Zebrafish (Danio rerio) due to titanium dioxide exposure

Nano titanium dioxide (nTiO₂), generally considered to be toxicologically inert, is manufactured in large quantities and extensively applied in consumer products. The small size and large surface area endow them with an active group or intrinsic toxicity. Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of (bio) chemical applications. One of the great advantages of this technique is its ability to provide information on the concentration, structure and interaction of biochemical molecules in their microenvironments within intact cells and tissues, non-destructively. Zebrafish (Danio rerio), one of the most important vertebrate model organisms used in developmental biology, are increasingly used in biomedical research, particularly as a model of human disease. In the present work, an attempt is made to study the effect of titanium dioxide, both nano and bulk, on the microenvironment of the liver tissues of Zebrafish using FT-Raman spectroscopy. The results of the present study suggest that TiO₂ exposure demonstrate a marked influence on the microenvironments of the liver tissues of Zebrafish. A shift to a higher wavenumber and an increase in the intensity of the band at ∼1087 cm⁻¹ in the TiO₂ exposed tissues suggest that some of the conformational changes resulting from the alkali recovery process takes place due to TiO₂ exposure. The decreased intensity ratio (I₃₂₂₀/I₃₄₀₀) observed in the titanium-exposed tissues suggests a decreased water domain size, which could be interpreted in terms of weaker hydrogen-bonded molecular species of water in the TiO₂ exposed tissues. The observed shift of COO⁻ bands to higher frequencies shows the disruption of salt bridges as a result of a change in the oppositely charged partners and due to the enhanced random coil conformation. The variation in the intensity ratio of the tyrosyl doublet (I₈₅₈/I₈₂₅) indicates variation in the hydrogen bonding of the phenolic hydroxyl group due to TiO₂ exposure. The results further suggest that the microenvironments are greatly altered due to titanium nano exposure when compared to titanium bulk. In conclusion, the results indicate that FT-Raman spectroscopy might be a useful tool for rapid assessment of nano particle biological interactions.     

Direct equilibration of soil water for delta(18)O analysis and its application to tracer studies

Current methods for stable oxygen isotopic (delta (18)O) analysis of soil water rely on separation of water from the soil matrix before analysis. These separation procedures are not only time consuming and require relatively large samples of soil, but also have been shown to introduce a large potential source of error. Current research at Queen's University Belfast is focused on using direct equilibration of CO(2) with the pore water to eliminate this extraction step using the automated Multiprep system and a Micromass Prism III isotope ratio mass spectrometer (IRMS). The findings of this research indicate the method is less time consuming, more reliable, and reproducible to within accepted limits (+/-0.1% per thousand delta (18)O). In this study the direct equilibration method is used to analyse delta (18)O tracer profiles in the unsaturated zone of field soils, concurrently with chloride tracer profiles, which can be used to assess infiltration rates and mechanisms through the unsaturated zone. Copyright 1999 John Wiley & Sons, Ltd.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

The study of the changes in the thermal properties of <Emphasis Type="Italic">Labeo rohita</Emphasis> bones due to arsenic exposure

The paper presents the changes in the thermal properties of control, arsenic exposed and DMSA treated Labeo rohita bones by using thermo analytical techniques. The result shows that the mass loss due to the thermal decomposition occurs in three distinct steps due to loss of water, organic and inorganic materials. The arsenic exposed bones present a different thermal behaviour compared to the control bones. The residue masses are increased due to arsenic exposure, while the DMSA treatment reduces the residue mass level. These thermal characteristics can be used as a qualitative method to check the metal accumulation in samples.