Enantioselective epoxidations of alkenes catalyzed by (salen)Mn(III) in aqueous surfactant systems

An aqueous reaction medium, based on a surfactant solution of diethyltetradecylamine N-oxide (AOE-14), was developed for the enantioselective epoxidation of 1,2-dihydronaphthalene and of various cis-β-alkyl styrenes with increasing hydrophobicity, using bleach as oxidant and the Jacobsen chiral (salen)Mn(III) as catalyst. AOE-14 is able to both solubilize all reactants in water and bind the metal of the salen complex acting as coligand. Its use leads to good yields (>75%) and to ee values ranging from 75% up to 91% even in the case of cis-β-alkyl styrenes where lower cis/trans epoxide ratios are observed. The ratio of surfactant/substrate used is 1:1 or 4:1, much lower than those generally used in the literature.     

Monitoring of depth distribution of trace elements by GDMS

The depth distribution of B and Li have been studied in ZrO₂ layers by GDMS. Zr alloy has been corroded to ZrO₂ in an autoclave in solutions containing Li and B. Samples were collected at different reaction times and analyzed. The GDMS crater depth and the sputter rate could be determined by profilometry for the discharge conditions used. In the analyzed samples three zones could be identified: oxide, interface and zircaloy. The concentration of Li and B was followed in each of the three zones.     

On the problem of the elastic plate on one-sided foundation

Summary Solution existence, uniqueness and regularity are analyzed for the elastic plate on unilateral elastic foundation problem. Some results are also given for the one-sided rigid foundation case.

---

Sommario Si studiano l'esistenza, l'unicità e la regolarità delle soluzioni del problema della piastra elastica su fondazione elastica unilaterale. Sono anche dati alcuni risultati per il caso di fondazione rigida unilaterale.

     

Multivalued penalty method for evolution variational inequalities with <Emphasis Type="Italic">λ</Emphasis><Subscript>0</Subscript>-pseudomonotone multivalued maps

We consider evolution variational inequalities with λ ₀-pseudomonotone maps. The main properties of these maps are investigated. By using the finite-difference method, we prove the property of strong solvability for the class of evolution variational inequalities with λ ₀-pseudomonotone maps. Using the penalty method for multivalued maps, we show the existence of weak solutions of evolution variational inequalities on closed convex sets. The class of multivalued penalty operators is constructed. We also consider a model example to illustrate this theory.     

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.