Single Drop Dynamics under Shearing Flow in Systems with a Viscoelastic Phase

In this article, we discuss the dynamics of a single drop immersed in an immiscible liquid, under an imposed shear flow. The two situations of a viscoelastic matrix with a Newtonian drop and of a viscoelastic drop in a Newtonian matrix are considered, both systems being characterized by a viscosity ratio equal to one, and by the same elasticity parameter. Experimental data are taken with a rheo-optical computer-assisted shearing device, allowing for drop observation from the vorticity direction of the shear flow. Data favourably compare with predictions of the recently proposed Maffettone-Greco model, where the drop is described as a deforming ellipsoid.     

Pd nanoparticles as efficient catalysts for Suzuki and Stille coupling reactions of aryl halides in ionic liquids

Pd-catalyzed Suzuki and Stille cross-couplings of aryl bromides and chlorides were carried out in quaternary ammonium salts as solvents under mild conditions and with the recycling of the catalyst.     

EPR and kinetic investigation of free cyanide oxidation by photocatalysis and ozonation

Oxidation of free cyanide in aqueous suspensions of three commercial TiO₂ specimens, with different anatase crystal size, has been carried out in a batch photoreactor by simultaneously applying ozonation and photocatalysis. Dissolved ozone participates both in homogeneous and catalytic reactions with cyanide; the extents of these two processes are comparable to that of the photodegradation with oxygen. The reactivity results are well described by the Langmuir-Hinshelwood kinetic model, providing the values of the kinetic and equilibrium adsorption constants for the catalytic and photocatalytic reactions contributing to cyanide oxidation. The cyanide concentration decreases faster with time for catalysts with increasing anatase crystal size, being more marked under UV irradiation. EPR studies on gaseous ozone adsorption on the three samples in the dark have shown stronger ozone interactions with Ti⁴⁺ and O^2? ions of the samples with largest anatase crystal size, leading to the formation of significant signals of Ti³⁺ and _s O^??O₂ radicals than with the anatase with the lowest crystal size, where ozone was mainly adsorbed on water molecular arrangements covering its surface. The hampering of the ozone and/or cyanide adsorption by the water molecular arrangements covering the surface of the catalyst with the lowest crystal size would justify the low cyanide degradation rate observed for this sample.     

Sequence and phosphorylation level determination of two donkey β‐caseins by mass spectrometry

Two coeluting components, with experimentally measured M_r values of 25529 and 24606 Da, were identified by reversed‐phase high‐performance liquid chromatography (RP‐HPLC) and mass spectrometric analysis in the dephosphorylated casein fraction of a milk sample collected from an individual donkey belonging to the Ragusano breed of the east of Sicily. By coupling enzymatic digestions, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) and RP‐HPLC/nano‐electrospray ionization tandem mass spectrometry (nESI‐MS/MS) analysis, the two proteins were identified as donkey β‐CNs and their sequences characterized completely, using the two known β‐CNs from mare as references. The two donkey β‐CNs, showing a mass difference of 923 Da, differ by the presence of the domain E²⁷SITHINK³⁴ in the full‐length component (M_r 25529 Da). In comparison with the mare's β‐CNs used as reference, they present nine amino acid substitutions: L→S³⁷, R→H⁵², S→N⁸¹, P→V⁸⁴, L→V⁹¹, R→Q²⁰³, P→L/I²⁰⁶, L→F²¹⁰ and A→P²¹⁹. Together, these substitutions account for the increase of 18 Da in the M_r of the donkey β‐CNs with respect to the counterparts from the mare. The molecular mass determination by ESI‐MS for the phosphorylated proteins showed that the full‐length component was composed of highly multi‐phosphorylated isoforms with five to seven phosphate groups. By analogy with the homologous mare's β‐CNs, the full‐length (226 amino acids) β‐CN was termed variant A, whereas the shorter (218 amino acids) β‐CN was termed variant A^Δ5. Copyright © 2009 John Wiley & Sons, Ltd.     

Dielectric properties of two phases of crystalline lutetium oxide

High-dielectric constant oxides are the focus of intense current research. As a contribution to the rationalization of the search for candidate materials, we compare the dielectric properties obtained from first-principles linear-response calculations for two phases—the ground state bixbyite and the competing hexagonal structures—of the crystalline oxide Lu₂O₃. The dielectric constants of bixbyite is about 12 and that of hexagonal is about 19 (the electronic constant being about 4.5 in both cases). This difference is due almost exclusively to the vibrational properties, with minor or no influence of charge anomaly differences; as these are related mainly to oxygen vibrations, we argue that the dielectric properties of sesquioxides will be determined mostly by their preferred structure, i.e. they will be poorer for bixbyite (e.g. Y₂O₃) than for hexagonal (e.g. La₂O₃) sesquioxides.     

The play operator on the rectifiable curves in a Hilbert space

The vector play operator is the solution operator of a class of evolution variational inequalities arising in continuum mechanics. For regular data, the existence of solutions is easily obtained from general results on maximal monotone operators. If the datum is a continuous function of bounded variation, then the existence of a weak solution is usually proved by means of a time discretization procedure. In this paper we give a short proof of the existence of the play operator on rectifiable curves making use of basic facts of measure theory. We also drop the separability assumptions usually made by other authors. Copyright © 2007 John Wiley & Sons, Ltd.     

Enhanced Electrocatalytic Oxygen Evolution in Au–Fe Nanoalloys

Oxygen evolution reaction (OER) is the most critical step in water splitting, still limiting the development of efficient alkaline water electrolyzers. Here we investigate the OER activity of Au–Fe nanoalloys obtained by laser-ablation synthesis in solution. This method allows a high amount of iron (up to 11 at %) to be incorporated into the gold lattice, which is not possible in Au–Fe alloys synthesized by other routes, due to thermodynamic constraints. The Au_0.89Fe_0.11 nanoalloys exhibit strongly enhanced OER in comparison to the individual pure metal nanoparticles, lowering the onset of OER and increasing up to 20 times the current density in alkaline aqueous solutions. Such a remarkable electrocatalytic activity is associated to nanoalloying, as demonstrated by comparative examples with physical mixtures of gold and iron nanoparticles. These results open attractive scenarios to the use of kinetically stable nanoalloys for catalysis and energy conversion.