Kinetics and mechanism of the thermal gas‐phase oxidation of perfluorobutene‐2 in presence of trifluoromethyl hypofluorite

The oxidation of perfluorobutene‐2 (C₄F₈) initiated by trifluoromethyl hypofluorite (CF₃OF) in presence of O₂ has been studied at 323.1, 332.6, 342.5, and 352.0 K, using a conventional static system. The initial pressure of CF₃OF was varied between 4.8 and 23.6 Torr, that of C₄F₈ between 48.7 and 302.4 Torr, and that of O₂ between 51.5 and 270.4 Torr. Several runs were made in presence of 325.5–451.2 Torr of N₂. The main products were COF₂, CF₃C(O)F, and CF₃OC(O)F. Small amounts of compound containing ? CF(CF₃)? O? C(O)CF₃ group were also formed, as detected by ¹³C NMR spectroscopy. The oxidation is a homogeneous short‐chain reaction, attaining, at the pressure of O₂ used, the pseudo‐zero‐order condition with respect to O₂ as reactant. The reaction is independent of the total pressure. Its basic steps are as follows: the thermal generation of CF₃O^? radicals by the abstraction of fluorine atom of CF₃OF by C₄F₈, the addition of CF₃O^? to the alkene, the formation of perfluoroalkoxy radicals RO^? in presence of O₂, and the decomposition of these radicals via the C? C bond scission, giving products containing ? C(O)F end group and reforming RO^? and CF₃O^? radicals. The mechanism consistent with experimental results is postulated. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 532–541, 2003     

Transport properties of a single-quantum dot Aharonov-Bohm interferometer

We consider a two-terminal Aharonov-Bohm (AB) interferometer with a quantum dot inserted in one path of the AB ring. We investigate the transport properties of this system in and out of the Kondo regime. We utilize perturbation theory to calculate the electron self-energy of the quantum dot with respect to the intradot Coulomb interaction. We show the expression of the Kondo temperature as a function of the AB phase together with its dependence on other characteristics such as the linewidth of the ring and the finite Coulomb interaction and the energy levels of the quantum dot. The current oscillates periodically as a function of the AB phase. The amplitude of the current oscillation decreases with increasing Coulomb interaction. For a given temperature, the electron transport through the AB interferometer can be selected to be in or out of the Kondo regime by changing the magnetic flux threading perpendicular to the AB ring of the system.     

Investigation on time scales in a low Reynolds number jet flow using particle-tracking velocimetry

The near flow field of an axisymmetric water jet at Reynolds numbers between 2000 and 5000 is investigated using Particle-Tracking Velocimetry. Measurements are taken in the longitudinal section (along the mean flow) and in cross-sections (orthogonal to the mean flow). From the former, correlation coefficients of the two in-plane velocity components in a Lagrangian framework are obtained: thus Lagrangian integral scales can be computed. Those of the streamwise velocity (axial) component increase on moving away from the centreline, whereas the opposite happens for the vertical velocity (radial) component: integral time scales of the two components are almost equal at the interface between jet and ambient fluids. On the other hand, integral scales are almost constant or increase slightly with the axial direction. In cross-sections, fluid ejection and injection from the jet centreline are observed to be connected to counter-rotating vortices (mushroom): their number and size change with Reynolds number in agreement with results from other authors. The maximum ejection velocity (orthogonal to the mean jet flow), at 3 nozzle diameters downstream of the outlet, is found to be one half of the mean outlet velocity.     

“Green Electrodes” Modified with Au Nanoparticles Synthesized in Glycerol,as Electrochemical Nitrite Sensor

A new environmentally friendly Au nanoparticles (Au NPs) synthesis in glycerol by using ultraviolet irradiation and without extra‐added stabilizers is described. The synthesis proposed in this work may impact on the non‐polluting production of noble nanoparticles with simple chemicals normally found in standard laboratories. These Au NPs were used to modify a carbon paste electrode (CPE) without having to separate them from the reaction medium. This green electrode was used as an electrochemical sensor for the nitrite detection in water. At the optimum conditions the green sensor presented a linear response in the 2.0×10^?7–1.5×10^?5 M concentration range, a good detection sensitivity (0.268 A L mol^?1), and a low detection limit of 2.0×10^?7 M of nitrite. The proposed modified green CPE was used to determine nitrite in tap water samples.     

A comparison between parallelization approaches in molecular dynamics simulations on GPUs

We test the relative performances of two different approaches to the computation of forces for molecular dynamics simulations on graphics processing units. A “vertex‐based” approach, where a computing thread is started per particle, is compared to an “edge‐based” approach, where a thread is started per each potentially non‐zero interaction. We find that the former is more efficient for systems with many simple interactions per particle while the latter is more efficient if the system has more complicated interactions or fewer of them. By comparing computation times on more and less recent graphics processing unit technology, we predict that, if the current trend of increasing the number of processing cores—as opposed to their computing power—remains, the “edge‐based” approach will gradually become the most efficient choice in an increasing number of cases. © 2014 Wiley Periodicals, Inc.     

The effect of boundary conditions by the side of the nozzle of a low Reynolds number jet

The near flow field of an axially symmetric water jet at Reynolds numbers from about 1,000 to 10,000 is investigated using laser-induced fluorescence (LIF), laser Doppler anemometry and particle tracking velocimetry. Spanwise and streamwise vortices are detected on the longitudinal plane and on cross-sections. Attention is focused onto the effects of rigid or free boundaries sideways to the nozzle outlet (no-slip or free-slip conditions), and particularly on the start up, growth and interaction of large vortical structures. On average, for the free-slip jet these structures develop more gradually and closer to the nozzle than for the no-slip jet; the local mixedness (derived from LIF measurements) is also higher for the free-slip case. Moreover, the measured velocity field decreases more slowly, with a longer potential core and a higher shear layer (momentum) thickness for the free-slip rather than for the no-slip conditions. The relation between spanwise and streamwise large-scale vortices is clarified by the observation that the ejection of fluid in cross-sections through streamwise vortices is coupled to the pairing of spanwise vortices on the longitudinal section.     

On Leon's criterion

Summary The theory of limit surfaces of resistance for isotropic materials in the space of the principal stress components is recalled. This resistance is viewed in terms of the phenomena of ductile or brittle failure that may arise in alternation for a given material, depending on the type of stress state. A transformation of coordinates is introduced that proves to be very useful for comparing the various limit conditions with that deriving from intrinsic curve theory. Reference is made to the criterion of Stassi, certainly the most reliable of the criteria that allow for dependence of the limit condition on the value of the principal intermediate stress. The theory of the intrinsic curve is generalised by means of Leon's modification, which interprets the phenomenon of tensile fracture. It is shown how Griffith's theory of brittle fracture leads to a limit condition that may be regarded as a special case of the one deriving from Leon's theory. Comparison with some experimental data shows that Leon's theory is well suitable for the study of brittle fracture. A generalisation that takes account of the influence of the principal intermediate stress and so permits good agreement with the experimental data in the field of ductile failure too, whilst conserving the characteristics of Leon's theory in brittle fracture, is proposed.

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Sommario Si richiama la teoria delle superfici limiti di resistenza per materiali isotropi nello spazio delle componenti principali di tensione. Tale resistenza è intesa nei riguardi dei fenomeni di rottura duttile o fragile che possono intervenire in alternativa per uno stesso materiale in dipendenza dei diversi tipi di stato tensionale. Si introduce una trasformazione di coordinate che risulta particolarmente utile per il confronto delle varie condizioni limiti con quella derivante dalla teoria della curva intrinseca. In particolare si fa riferimento al criterio di Stassi, certo il più attendibile fra quelli che prendono in considerazione la dipendenza della condizione limite dal valore della tensione principale intermedia. La teoria della curva intrinseca viene generalizzata attraverso la modifica di Leon, che interpreta il fenomeno della crisi per distacco. Si mostra come la teoria di Griffith della rottura fragile conduca ad una condizione limite che si può considerare un caso particolare di quella derivante dalla teoria di Leon. Per confronto con alcuni dati sperimentali si verifica che questa ultima teoria bene si presta allo studio dei fenomeni di rottura fragile. Si propone una generalizzazione che, tenendo conto dell'influenza della tensione principale intermedia, consente di ottenere un buon accordo con l'esperienza anche nel campo di rottura duttile, pur conservando le caratteristiche della teoria di Leon in quello della rottura fragile.

     

Single cell 3-D platform to study ligand mobility in cell-cell contact

Lateral mobility and dimensionality have both been shown to influence cellular behavior, but have yet to be combined and applied in a single in vitro platform to address, e.g., cell adhesion in a setting mimicking the three-dimensional environment of neighboring cells in a reductionist way. To study the effect of the lateral mobility of cell adhesive ligands in three dimensions we present and characterize a platform, which enables patterning of single cells into microwells presenting a cell membrane mimetic interface pre-patterned to its walls. Soluble E-cadherin extracellular domains coupled through an optimized streptavidin-antibody linkage to lipids in a supported lipid bilayer (SPB) were presented on the microwell walls as either laterally mobile or immobile ligands. The fluidity was controlled through a small change in temperature by choosing phospholipids for the SPB with a lipid phase transition temperature around 30 °C. The platform thus enabled the investigation of cell adhesion to either laterally immobile or mobile E-cadherin ligands presented on the same cell membrane mimetic surface. Chinese hamster ovary (CHO) cells engineered to express E-cadherin that were cultured on the platform demonstrated that enhanced cadherin lateral mobility significantly decreased the formation of actin bundles and resulted in more diffuse actin organization, while constraining the cell shape to that of the microwell. This example highlights the potential to use in vitro cell culture platforms to mimic direct cell-cell interaction in a controlled environment that nevertheless captures the dynamic nature of the native cell environment.