Cis–trans isomerization of olefinic alcohols promoted by Rh(I) complexes

Homogeneous hydrogenation and isomerization reaction of cis-2-butene-1,4-diol has been investigated in ethanol by using tris(triphenylphosphine)chlororhodium(I), RhCl(PPh₃)₃, and triethylamine at 303 K and 0.01–0.1 MPa partial hydrogen pressure. Under reduced H₂ pressure, the geometric isomerization reaction occurs, to a high extent, leading to trans-2-butene-1,4-diol up to 93% selectivity at 90% conversion of the cis analogous. Effects of H₂ partial pressure as well as triethylamine, added phosphine and olefin concentrations on the rate of reaction and on the products distribution were also investigated. The results obtained can be interpreted on the basis of a proposed mechanism in which RhH(PPh₃)₃ is the active species. The high selectivity towards cis-trans isomerization of cis-2-butene-1,4-diol is attributed to steric factors of the Rh(I) coordinated triphenylphosphine groups.     

K- and Cs-FeV/Al2O3soot combustion catalysts for diesel exhaust treatment

Alkali-doped FeV oxide catalysts supported on -alumina were prepared and their catalytic activity in the combustion of diesel soot is reported. The catalysts were characterized by XRD, TPR and SEM–EDX analysis. The influence of the nature of the alkali metal (K and Cs), the temperature of treatment of the catalysts and the stability to sulfur poisoning have been investigated.

Catalysts doped with Cs were the most active and stable also after several combustion cycles and in the presence of sulfur in the stream. The activity measurements and microstructural results suggest that the combustion of soot is favored on catalysts where amorphous phases and/or mixed Fe---V---O phases, ensuring an intimate contact between iron and vanadium, are present. A reaction mechanism involving the participation of the redox couple Fe(II)–Fe(III) in the activation of the vanadium combustion sites, is proposed.     

Is Melanoma Progression Affected by Thyroid Diseases?

Clinical and epidemiological evidence indicate a relationship between thyroid diseases and melanoma. In particular, the hypothyroidism condition appears to promote melanoma spread, which suggests a protective role of thyroid hormones against disease progression. In addition, experimental data suggest that, in addition to thyroid hormones, other hormonal players of the hypothalamic–pituitary–thyroid (HPT) axis, namely the thyrotropin releasing hormone and the thyrotropin, are likely to affect melanoma cells behavior. This information warrants further clinical and experimental studies in order to build a precise pattern of action of the HPT hormones on melanoma cells. An improved knowledge of the involved molecular mechanism(s) could lead to a better and possibly personalized clinical management of these patients.     

Hydrogen sorption properties of V85Ni15

An alloy with nominal composition V₈₅Ni₁₅ was prepared in a vacuum induction melting apparatus. The chemical analysis of the sample showed a V (Ni) content of 82.63 (15.68) at% and small contaminations by carbon and aluminum. XRD measurements confirmed that the bcc Ni-V solid solution phase is the main constituent of the sample. However, a minor impurity (approximately 6.5 wt%) due to the precipitation of the sigma NiV_3-x phase is present in the sample.Hydrogen sorption measurements extending from 150 °C up to 400 °C in a wide pressure range (up to 90 bar) were performed. Upon hydrogenation below 250 °C, one observes the subsequent presence of an α phase and of two hydride phases with different values of dehydrogenation enthalpy: ΔH_dehydr = 21 ± 1 kJ/mol for 0.15 ≤ H/M ≤ 0.30 and ΔH_dehydr = 26 ± 2 kJ/mol for 0.53 ≤ H/M ≤ 0.59. Above 300 °C, there is no evidence of the formation of hydrides and only an α phase is present up to the maximum measured composition, with a hydrogenation enthalpy ΔH_hydr = 10.0 ± 0.5 kJ/mol.     

Aging and inhibition processes: The case of metaphor treatment.

The inhibitory deficit hypothesis has often been cited as a possible explanation for cognitive changes related to age. The aim of this study was to develop a new procedure for evaluating effortful inhibition on the basis of the comprehension of metaphors. Our experiment was carried out on younger and older adults, in whom we also measured inhibitory capacity, working memory, and processing speed. The results show that older participants required a longer time and made more frequent errors in rejecting metaphors versus literally false statements. The interference effect was predicted by the psychometric tests designed to evaluate inhibition. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Approximate Analytic Estimate of Axial Fluid Conduction in Laminar Forced Convection Tube Flows with Zero-to-Uniform Step Wall Heat Fluxes

The influence of axial fluid conduction on low Péclet number flows in the thermal entrance region of long circular tubes is investigated in this theoretical study. The convective heat transport of viscous fluids relates to a specific condition under which the first part of the tube ( x h 0) is insulated and the second part of the tube ( x > 0) receives a heat flux of uniform intensity. A conjugate one-dimensional lumped model produces a solution of compressed algebraic form that is able to deliver dependable mean bulk temperatures that are in perfect agreement with those obtained numerically by the formal conjugate two-dimensional distributed model. As a by-product of the succession of algebraic calculations within the platform of the lumped model, the critical Péclet number Pe cr has been easily quantified. This number is a figure-of-merit of remarkable importance in the modeling of forced heat convection in tubes because it establishes the threshold between two contrasting situations: one embracing axial fluid conduction (finite Pe) and the other implicating negligible axial fluid conduction (Pe M X ). In addition, the local wall temperatures were calculated with an approximate engineering procedure, showing good agreement with those determined numerically by the formal conjugate two-dimensional distributed model.