Effect of temperature on the photobehavior of Rose Bengal associated with dipalmitoylphosphatidyl choline liposomes

The association and photobehavior of Rose Bengal (RB) in the presence of dipalmitoylphosphatidyl choline (DPPC) small unilamellar liposomes is determined by the temperature. At temperatures above the main phase transition of the bilayer, the incorporation of the dye is ca. 2.5 times more efficient than that taking place when the bilayer is in the gel state. In both temperature ranges, adsorption isotherms show a noticeable anti-cooperativity that can be related to electrostatic repulsion between bound molecules. The photophysics and the photochemistry of the bound dye molecules also depend on the bilayer status. In particular, in the liquid crystalline state the surrounding of the dye is more polar and production of singlet oxygen is less efficient (Φ∼0.1). This reduced singlet oxygen production is partially due to a low triplet yield (Φ_T=0.35) and triplet self-quenching due to a high local RB concentration. In spite of these, tryptophan is efficiently photobleached when RB is associated to liposomes in the liquid crystalline state, probably due to a Type I mechanism favored by its high local concentration in the sensitized surroundings.     

Synthesis and characterization of silicon-doped gallium oxide nanowires for optoelectronic UV applications

Silicon-doped gallium oxide nanowires have been synthesized by thermal methods using either a mixture of gallium oxide and silicon powders or metallic gallium with silicon powder as precursor materials. The growth mechanism has been found to be a vapour–liquid–solid (VLS) or vapour–solid (VS) process, respectively, depending on the precursor used. In the former case, silicon oxide droplets at the end of the nanowires have been observed. Their possible role during the growth of the nanostructures is discussed. Structural and morphological characterization of the doped nanowires has been performed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results show a high crystalline quality and a uniform distribution of silicon along the nanowires. Room temperature cathodoluminescence (CL) in the SEM shows that slight variations in the composed UV–blue emission band appear due to the influence of Si impurities in the oxygen vacancy defect structure.     

Energy efficiency and risk management in public buildings: strategic model for robust planning

Due to deregulations of the energy sector and the setting of targets such as the 20/20/20 in the EU, operators of public buildings are now more exposed to instantaneous (short-term) market conditions. On the other hand, they have gained the opportunity to play a more active role in securing long-term supply, managing demand, and hedging against risk while improving existing buildings’ infrastructures. Therefore, there are incentives for the operators to develop and use a Decision Support System to manage their energy sub-systems in a more robust energy-efficient and cost-effective manner. In this paper, a two-stage stochastic model is proposed, where some decisions (so-called first-stage decisions) regarding investments in new energy technologies have to be taken before uncertainties are resolved, and some others (so-called second-stage decisions) on how to use the installed technologies will be taken once values for uncertain parameters become known, thereby providing a trade-off between long- and short-term decisions.     

THE EFFECT OF ALCOHOLS WITH DIFFERENT STRUCTURES ON THE FORMATION OF WARM O/W MICROEMULSIONS

The influence of twenty five different alcohols on the formation of warm oil-in-water (O/W) microemulsions was investigated. Selected concentrations of each alcohol were added to fixed amounts of stearic acid, Tween 20 and water at 65 ° C. Fifteen alcohols formed microemulsions, at least at one of the concentrations. A pattern recognition study was performed to elucidate the activities of the alcohols by Principal Component Analysis (PCA). Linear Discriminant Analysis (LDA) was used to classify them. Two classification functions, obtained for alcohols forming / not forming microemulsions, suggest that the formation of warm O/W microemulsion is linked to the nature and the dimension/lipophilicity of the alcohol.     

Catalytic Asymmetric Reactions of 4‐Substituted Indoles with Nitroethene: A Direct Entry to Ergot Alkaloid Structures

A domino Friedel–Crafts/nitro‐Michael reaction between 4‐substituted indoles and nitroethene is presented. The reaction is catalyzed by BINOL‐derived phosphoric acid catalysts, and delivers the corresponding 3,4‐ring‐fused indoles with very good results in terms of yields and diastereo‐ and enantioselectivities. The tricyclic benzo[cd]indole products bear a nitro group at the right position to serve as precursors of ergot alkaloids, as demonstrated by the formal synthesis of 6,7‐secoagroclavine from one of the adducts. DFT calculations suggest that the outcome of the reaction stems from the preferential evolution of a key nitronic acid intermediate through a nucleophilic addition pathway, rather than to the expected “quenching” through protonation.     

A combined treatment of hydration and dynamical effects for the modeling of host–guest binding thermodynamics: the SAMPL5 blinded challenge

As part of the SAMPL5 blinded experiment, we computed the absolute binding free energies of 22 host–guest complexes employing a novel approach based on the BEDAM single-decoupling alchemical free energy protocol with parallel replica exchange conformational sampling and the AGBNP2 implicit solvation model specifically customized to treat the effect of water displacement as modeled by the Hydration Site Analysis method with explicit solvation. Initial predictions were affected by the lack of treatment of ionic charge screening, which is very significant for these highly charged hosts, and resulted in poor relative ranking of negatively versus positively charged guests. Binding free energies obtained with Debye–Hückel treatment of salt effects were in good agreement with experimental measurements. Water displacement effects contributed favorably and very significantly to the observed binding affinities; without it, the modeling predictions would have grossly underestimated binding. The work validates the implicit/explicit solvation approach employed here and it shows that comprehensive physical models can be effective at predicting binding affinities of molecular complexes requiring accurate treatment of conformational dynamics and hydration.     

Regularity Results for a Class of Functionals with Non-Standard Growth

We consider the integral functional

Force–displacement relationship in micro-metric pantographs: Experiments and numerical simulations

In this paper, we reveal that the mathematical discrete model of Hencky type, introduced in [1], is appropriate for describing the mechanical behavior of micro-metric pantographic elementary modules. This behavior does not differ remarkably from what has been observed for milli-metric modules, as we prove with suitably designed experiments. Therefore, we conclude that the concept of pantographic microstructure seems feasible for micro-metrically architected microstructured (meta)materials as well. These results are particularly indicative of the possibility of fabricating materials that can have an underlying pantographic microstructure at micrometric scale, so that its unique behavior can be exploited in a larger range of technological applications.