Mechanism of aluminium and oxygen ions transport in the barrier layer of porous anodic alumina films

Aluminium was anodised in oxalic acid electrolyte at concentrations 0.125–0.5?M, current densities 25–100?A?m^?2 and low temperatures 0 and 5?°C. The efficiencies of Al consumption and oxide production in the metal|oxide interface and the transport numbers of Al³⁺ and O^2? in the barrier layer of porous anodic alumina films were determined. The Al consumption efficiency essentially coincides with that by Faraday’s law while that of oxygen evolution, visually detected at these temperatures, is negligible. The oxide production efficiency and O^2? transport number decrease with temperature, increase with current density and are almost independent of electrolyte concentration. The transport numbers combined with literature ones for oxalate and sulphuric acid electrolytes were treated by high field kinetic equations describing independent Al³⁺ and O^2? transport to penetrate its mechanism. The half jump activation distances were found comparable to ions radii. This mechanism embraces two steps, equilibrium established between ordinary oxide lattice hardly allowing transport and locally emerging transformed structure dispersed in barrier layer consisting of pairs of Al³⁺ and O^2? clusters enabling transport and the rate-controlling step of actual ion transport within clusters. The transformed structure then returns to ordinary while it emerges at other sites. The real activation energy of Al³⁺ transport is higher than that of O^2?, e.g. by ≈?19?kJ?mol^?1 at low current densities, but the fraction of really mobile Al³⁺ is ≈?10³–10⁴ times larger than that of O^2? justifying the not excessively different values of O^2? and Al³⁺ transport numbers.     

Operational risk: Emerging markets,sectors and measurement

The role of decision support systems in mitigating operational risks in firms is well established. However, there is a lack of investment in decision support systems in emerging markets, even though inadequate operational risk management is a key cause of discouraging external investment. This has also been exacerbated by insufficient understanding of operational risk in emerging markets, which can be attributed to past operational risk measurement techniques, limited studies on emerging markets and inadequate data.     

Newtonian plane Couette flow with dynamic wall slip

Meccanica - The occurrence of slip complicates the estimation of the viscosity in rheometric flows. Thus, special analyses and experimental protocols are needed in order to obtain reliable...     

Enhancement of the Anti-Inflammatory Activity of NSAIDs by Their Conjugation with 3,4,5-Trimethoxybenzyl Alcohol

The synthesis of derivatives of three nonspecific COX-1 and COX-2 inhibitors, ibuprofen, ketoprofen, naproxen is presented. These acids were connected via an amide bond with an amino acid (L-proline, L-tyrosine, and beta-alanine) used as a linker. The amino acid carboxylic group was esterified with 3,4,5 trimethoxybenzyl alcohol. The activity of the novel derivatives was examined in vivo on carrageenan-induced inflammation, and in vitro, as cyclooxygenase and lipoxygenase inhibitors. It was found that the new compounds were more potent anti-inflammatory agents than the parent drugs. Thus, the ibuprofen (21) and ketoprofen (16) derivatives reduced rat paw edema by 67 and 91% (the reduction by the relevant NSAIDs was 36 and 47%, respectively). They inhibited COX-2 more than the starting drugs (21 by 67%, ibuprofen 46%, 19 by 94%, ketoprofen 49%). Docking of compounds on the active sites of COX-1 and COX-2 reflects their in vitro activity. Thus, 19 adopts an unfavorable orientation for COX-1 inhibition, but it binds effectively in the binding pocket of COX-2, in agreement with the absence of activity for COX-1 and the high inhibition of COX-2. In conclusion, the performed structural modifications result in the enhancement of the anti-inflammatory activity, compared with the parent NSAIDs.     

On the limiting distribution of sample central moments

We investigate the limiting behavior of sample central moments, examining the special cases where the limiting (as the sample size tends to infinity) distribution is degenerate. Parent (non-degenerate) distributions with this property are called singular, and we show in this article that the singular distributions contain at most three supporting points. Moreover, using the delta-method, we show that the (second-order) limiting distribution of sample central moments from a singular distribution is either a multiple, or a difference of two multiples of independent Chi-square random variables with one degree of freedom. Finally, we present a new characterization of normality through the asymptotic independence of the sample mean and all sample central moments.

     

Bragg scattering as a probe of atomic wave functions and quantum phase transitions in optical lattices

We have observed Bragg scattering of photons from quantum degenerate ^{87}Rb atoms in a three-dimensional optical lattice. Bragg scattered light directly probes the microscopic crystal structure and atomic wave function whose position and momentum width is Heisenberg limited. The spatial coherence of the wave function leads to revivals in the Bragg scattered light due to the atomic Talbot effect. The decay of revivals across the superfluid to Mott insulator transition indicates the loss of superfluid coherence.     

A study of properties of adaptive quadratic grids for three-dimensional near-surface field computations

Curved geometries and the corresponding near-surface fields typically require a large number of linear computational elements. High-order numerical solvers have been primarily used with low-order meshes. There is a need for curved, high-order computational elements. Typical near-surface meshes consist of hexahedral and/or prismatic elements. The present work studies the employment of quadratic meshes that are relatively coarse for field simulations. Directionally quadratic high-order elements are proposed for the near-surface field regions. The quadratic meshes are compared with the conventional low-order ones in terms of accuracy and efficiency. The cases considered include closed surface volume calculations, as well as computation of gradients of several analytic fields. A special method of adaptive local quadratic meshes is proposed and evaluated. Truncation error analysis for quadratic grids yields comparison with the conventional linear hexahedral/prismatic meshes, which are subject to typical distortions such as stretching, skewness, and torsion.     

Employing (half-)titanocene complexes as initiators for the synthesis of end-functionalized polylactides by coordination polymerization

Seven (half-)titanocene alkoxide complexes, [Cp₂TiCl(OEt)], [Cp₂TiCl(O-2-Bu)], [Cp₂TiCl(OCH₂CF₂CF₂H)], [CpTiCl₂(OEt)], [CpTiCl₂(O-(S)-2-Bu)], [CpTiCl₂(OCH₂CF₃)], and [Cp₂TiCl(OCH₂CF₃)], were synthesized and employed in lactide coordination polymerization. These organotitanium (IV) compounds proved to be very efficient initiators for the ring-opening polymerization of enantiomeric l -lactide and racemic mixture of rac-lactide, leading to end-functionalized polymers. Kinetic studies illustrated that these compounds produce well-defined polymers in a controlled manner. This was further demonstrated by synthesizing poly(l -lactide-b-hexyl isocyanate) diblock copolymer. The effect of the alkoxy end groups on the thermal behavior of the polymers was also studied by thermogravimetric analysis and differential scanning calorimetry. The polymers were characterized using size exclusion chromatography and proton nuclear magnetic resonance spectroscopy. The optical properties of the diblock copolymer were also investigated. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2192–2202