Evaluation of unsteady pressure fields and forces in rotating airfoils from time-resolved PIV

The final stages of transitional phenomena in laminar separation bubbles play a key role in their reattachment process, and they condition the boundary layer properties and flow structure after reattachment. In this experimental study, the evolution of the perturbation velocity spectra found in this zone is first presented, showing the nonlinear growth of instabilities in their path to develop fully turbulent spectra. The study of the average flow field allows the scaling of the reattachment region, both in its extension and in the characterization of the integral boundary layer magnitudes. Experimental laws are proposed for the evolution of the momentum thickness and of the shape factor. In addition, a universal, wake-like mean velocity profile is found shortly after the reattachment station. The phase-locked characterization technique allows measurements conditioned to the presence of a fluid event. This technique is used to track the evolution of large-scale structures, whose dynamics is seen to dominate the fluid behavior in the reattachment zone. The simultaneous existence of two vortex blobs is found to characterize this flow region, with the longest lived one being convected toward the wall and stretched. This process results in the fast breakdown of the large-scale vorticity structure and the sudden formation of 3-D, small scales that promote the rapid flow evolution toward a fully developed turbulent state.     

Organocatalyzed Enantioselective Desymmetrization of Diols in the Preparation of Chiral Building Blocks

Desymmetrization of diols is a powerful tool to the synthesis of chiral building blocks. Among the different approaches to perform discrimination between both enantiotopic hydroxyl groups, the organocatalytic approach has gained importance in the last years. A diverse range of organocatalysts has been used to efficiently promote this enantioselective transformation and this Minireview examines the different contributions in this field.     

The Keto–Enol Tautomerism of Biliverdin in Bacteriophytochrome: Could it Explain the Bathochromic Shift in the Pfr Form?†

Phytochromes are ubiquitous photoreceptors found in plants, eukaryotic algae, bacteria and fungi. Particularly, when bacteriophytochrome is irradiated with light, a Z‐to‐E (photo)isomerization takes place in the biliverdin chromophore as part of the Pr‐to‐Pfr conversion. This photoisomerization is concomitant with a bathochromic shift in the Q‐band. Based on experimental evidence, we studied a possible keto–enol tautomerization of BV, as an alternative reaction channel after its photoisomerization. In this contribution, the noncatalyzed and water‐assisted reaction pathways for the lactam–lactim interconversion through consecutive keto–enol tautomerization of a model BV species were studied deeply. It was found that in the absence of water molecules, the proton transfer reaction is unable to take place at normal conditions, due to large activation energies, and the endothermic formation of lactim derivatives prevents its occurrence. However, when a water molecule assists the process by catalyzing the proton transfer reaction, the activation free energy lowers considerably. The drastic lowering in the activation energy for the keto–enol tautomerism is due to the stabilization of the water moiety through hydrogen bonds along the reaction coordinate. The absorption spectra were computed for all tautomers. It was found that the UV–visible absorption bands are in reasonable agreement with the experimental data. Our results suggest that although the keto–enol equilibrium is likely favoring the lactam tautomer, the equilibrium could eventually be shifted in favor of the lactim, as it has been reported to occur in the dark reversion mechanism of bathy phytochromes.     

Optical spectroscopy of silver ion-exchanged As-doped glass

Soda-lime-silicate glass containing arsenic oxide and undoped soda-lime-silicate glass (blank) are prepared by melting from pure sand (iron concentration lower than 0.01 wt%). The effect of arsenic on the optical properties of the glass with and without silver ion exchange at 325 °C for various times is investigated by optical absorption and photoluminescence spectroscopy. Emission/excitation spectra of silver ion exchanged glass allow differentiation of three stages in the silver incorporation into the glass network. First and second stages are only observed in the undoped glass ion exchanged for short times. Such stages are associated with the presence of isolated Ag⁺-ions and Ag⁺-Ag⁺ pairs, respectively. The third stage appears in the undoped glass ion exchanged for times longer than 10 min and in the arsenic-doped glass even for exchange times as short as 1 min. Then, this stage is characterised by molecular mixed species formed with Ag⁺ and Ag⁰, which coexist with nanoparticles of metallic silver. The presence of those Ag⁰-aggregates gives a yellow colour to the glasses, which show the well-know absorption band at about 400 nm due to surface plasmon resonance.     

Cobalt‐Catalyzed Aminocarbonylation of Alkyl Tosylates: Stereospecific Synthesis of Amides

Metal‐catalyzed aminocarbonylation is a standard approach for installing amide functionality in chemical synthesis. Despite broad application of this transformation using aryl or vinyl electrophiles, there are few examples involving unactivated aliphatic substrates. Furthermore, there are no stereocontrolled aminocarbonylations of alkyl electrophiles known. Herein, we report a stereospecific aminocarbonylation of unactivated alkyl tosylates for the synthesis of enantioenriched amides. This cobalt‐catalyzed transformation uses a remarkably broad range of amines and proceeds with excellent stereospecificity and chemoselectivity.     

Solution methods for the bi-objective (cost-coverage) unconstrained facility location problem with an illustrative example

The Colombian coffee supply network, managed by the Federación Nacional de Cafeteros de Colombia (Colombian National Coffee-Growers Federation), requires slimming down operational costs while continuing to provide a high level of service in terms of coverage to its affiliated coffee growers. We model this problem as a biobjective (cost-coverage) uncapacitated facility location problem (BOUFLP). We designed and implemented three different algorithms for the BOUFLP that are able to obtain a good approximation of the Pareto frontier. We designed an algorithm based on the Nondominated Sorting Genetic Algorithm; an algorithm based on the Pareto Archive Evolution Strategy; and an algorithm based on mathematical programming. We developed a random problem generator for testing and comparison using as reference the Colombian coffee supply network with 29 depots and 47 purchasing centers. We compared the algorithms based on the quality of the approximation to the Pareto frontier using a nondominated space metric inspired on Zitzler and Thiele's. We used the mathematical programming-based algorithm to identify unique tradeoff opportunities for the reconfiguration of the Colombian coffee supply network. Finally, we illustrate an extension of the mathematical programming-based algorithm to perform scenario analysis for a set of uncapacitated location problems found in the literature.