Study of the Ternary Mixture of Methanol/Formamide/Acetonitrile via Solvatochromic Probes.

Following previous studies, the ternary mixture of methanol/formamide/acetonitrile (MeOH/Formamide/MeCN) was studied using the UV-Vis absorption spectra at 298.15 K with a set of five probes, 4-nitroaniline, 4-nitroanisole, 4-nitrophenol, N,N-dimethyl-4-nitroaniline and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio)phenolate (Reichardt betaine dye), for a total of 22 mole ternary fractions. In addition, nine mole fractions of the underling binary mixtures, MeOH/Formamide and Formamide/MeCN were also tested. Spectroscopic results were used to model the preferential solvation order for each probe in the mixtures. The Kamlet-Taft solvatochromic solvent parameters, α, ß, and π*, were also computed through the use of the solvatochromic shifts of the five probe indicators. Moreover, discrepancies in the spectroscopic behavior of 4-nitrophenol in formamide-rich mixtures were observed and analyzed.

Hierarchical Zeolites Prepared Using a Surfactant-Mediated Strategy: ZSM-5 vs. Y as Catalysts for Friedel-Crafts Acylation Reaction.

Hierarchical ZSM5 and Y zeolites were prepared through a surfactant-mediated strategy with NH4OH changing the duration of the treatment and the amount of CTAB surfactant and taking as reference multiples of the critical micellar concentration (CMC). The materials were characterized using powder X-ray diffraction, N2 adsorption isotherms at -196 °C, and SEM and TEM microscopy. The catalytic performance was evaluated in Friedel-Crafts acylation of furan with acetic anhydride at 80 °C. The alkaline surfactant-mediated treatment had different effects on the two zeolites. For ZSM5, the CTAB molecular aggregates can hardly diffuse inside the medium-size pores, leading mainly to intercrystalline mesoporosity and increased external surface area, with no positive catalytic impact. On the other hand, for large-pore Y zeolite, the CTAB molecular aggregates can easily diffuse and promote the rearrangement of crystal units around micelles, causing the enlargement of the pores, i.e., intracrystalline porosity. The optimized Y-based sample, treated for 12 h with a CTAB amount 32 times the CMC, shows an increase in product yield and rate constant that was not observed when a higher amount of surfactant was added. The reuse of spent catalysts upon thermal treatment at 400 °C shows a regeneration efficiency around 90%, showing good potentialities for the modified catalysts.

Probing Substrate/Catalyst Effects Using QSPR Analysis on Friedel-Crafts Acylation Reactions over Hierarchical BEA Zeolites.

Attempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates' molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media.

Cosmology and Fundamental Physics with the Euclid Satellite.

Euclid is a European Space Agency medium-class mission selected for launch in 2019 within the Cosmic Vision 2015-2025 program. The main goal of Euclid is to understand the origin of the accelerated expansion of the universe. Euclid will explore the expansion history of the universe and the evolution of cosmic structures by measuring shapes and red-shifts of galaxies as well as the distribution of clusters of galaxies over a large fraction of the sky. Although the main driver for Euclid is the nature of dark energy, Euclid science covers a vast range of topics, from cosmology to galaxy evolution to planetary research. In this review we focus on cosmology and fundamental physics, with a strong emphasis on science beyond the current standard models. We discuss five broad topics: dark energy and modified gravity, dark matter, initial conditions, basic assumptions and questions of methodology in the data analysis. This review has been planned and carried out within Euclid's Theory Working Group and is meant to provide a guide to the scientific themes that will underlie the activity of the group during the preparation of the Euclid mission.

Modeling preferential solvation in ternary solvent systems.

The theoretical solvent exchange model of Bosch and Rosés for binary solvents was extended to ternary solvent mixtures. The model was applied to ENT values for the mixture methanol/1-propanol/acetonitrile, in terms of 48 new values in a total of 79, measured at 25 degrees C over the whole range of solvent compositions. It was also applied to the mixture methanollethanol/acetone at the same temperature using 93 E(N)T values obtained from literature. Very good fits between experimental and calculated values, substantiated by external validation methods, were achieved for both sets of data. The use of the developed extended model allowed the interpretation of measured solvatochromic shifts in terms of solute-solvent and solvent-solvent interactions in the local environment of the solute's dye for the two ternary systems and the underlying binary mixtures. It also provided the identification of various complex solvent entities and the quantification of their relative concentrations in the probe's cybotactic region, thus leading to new and significant physicochemical insights at a molecular level, regardless of the nonconsideration of the formation of solvent complexes in the bulk. Results clearly showed a different solvent composition in the vicinity of the solute. The further extension of the model to four and five components is also presented.

The face-to-face encounter in indigenous health care: a perspective in Lévinas.

OBJECTIVE: To reflect on the sensitive behaviors of indigenous healthcare professionals based on the philosophy of Emmanuel Lévinas, to ratify completeness, equity, and humanity. METHOD: reflective study. REFLECTION: Studies have identified inadequacies in meeting the indigenous singularities. In the hospital and outpatient settings, they are diluted in the search for care. The difficulty of the professionals to admit them generates conflicts and non-adherence of indigenous individuals to treatments that disregard their care practices. In Lévinas, consciousness requires, "a priori," sensitivity to access the Infinity on the Face of the Other, which in the face-to-face encounters is presented to the Self as radical Alterity, proposing an Ethical relationship through transcendence. The freedom of the Self as to the Other is finite, as the Self cannot possess the Other, and infinite for its responsibility for the Other. FINAL CONSIDERATIONS: The Self builds essence and existence in responsibility. In the Ethics of Alterity, in Lévinas, reflections are proposed that influence sensitive behaviors.

UV-Vis spectroscopic study of preferential solvation and intermolecular interactions in methanol/1-propanol/acetonitrile by means of solvatochromic probes.

Solvatochromic UV-Vis shifts of four indicators (4-nitroaniline, 4-nitroanisole, 4-nitrophenol and N,N-dimethyl-4-nitroaniline) have been measured at 298.15K in the ternary mixture methanol/1-propanol/acetonitrile (MeOH/1-PrOH/MeCN) in a total of 22 mole fractions, along with 18 additional mole fractions for each of the corresponding binary mixtures, MeOH/1-PrOH, 1-PrOH/MeCN and MeOH/MeCN. These values, combined with our previous experimental results for 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (Reichardt's betaine dye) in the same mixtures, permitted the computation of the Kamlet-Taft solvent parameters, α, ß, and π(*). The rationalization of the spectroscopic behavior of each probe within each mixture's whole mole fraction range was achieved through the use of the Bosch and Rosés preferential solvation model. The applied model allowed the identification of synergistic behaviors in MeCN/alcohol mixtures and thus to infer the existence of solvent complexes in solution. Also, the addition of small amounts of MeCN to the binary mixtures was seen to cause a significant variation in π(*), whereas the addition of alcohol to MeCN mixtures always lead to a sudden change in α and ß. The behavior of these parameters in the ternary mixture was shown to be mainly determined by the contributions of the underlying binary mixtures.

The face-to-face encounter in indigenous health care: a perspective in Lévinas / El encuentro frente a frente en el cuidado en la salud indígena: una perspectiva en Lévinas / O encontro face a face no cuidado em saúde indígena: uma perspectiva em Lévinas

ABSTRACT Objective: To reflect on the sensitive behaviors of indigenous healthcare professionals based on the philosophy of Emmanuel Lévinas, to ratify completeness, equity, and humanity. Method: reflective study. Reflection: Studies have identified inadequacies in meeting the indigenous singularities. In the hospital and outpatient settings, they are diluted in the search for care. The difficulty of the professionals to admit them generates conflicts and non-adherence of indigenous individuals to treatments that disregard their care practices. In Lévinas, consciousness requires, "a priori," sensitivity to access the Infinity on the Face of the Other, which in the face-to-face encounters is presented to the Self as radical Alterity, proposing an Ethical relationship through transcendence. The freedom of the Self as to the Other is finite, as the Self cannot possess the Other, and infinite for its responsibility for the Other. Final considerations: The Self builds essence and existence in responsibility. In the Ethics of Alterity, in Lévinas, reflections are proposed that influence sensitive behaviors.

RESUMEN Objetivo: Reflejar sobre los comportamientos sensibles de los profesionales en salud indígena desde la filosofía de Emmanuel Lévinas, para ratificar la integralidad, la equidad y la humanidad. Método: Estudio reflexivo. Reflejo: Estudios están identificando inadecuaciones en la atención a las singularidades indígenas. En los escenarios hospitalarios y de ambulatorios, ellas se diluyen en la búsqueda por cuidados. La dificultad de los profesionales en admitirlas genera conflictos y no aceptación de los indígenas a tratamientos que no consideran sus prácticas de cuidado. En Lévinas, la consciencia requiere, "a priori," sensibilidad para acceder el Infinito en el Rostro del Otro, que en los encuentros frente a frente se presenta al Yo como Alteridad radical, proponiendo una relación Ética por la transcendencia. La libertad del Yo cuanto al Otro es finita, porque de él no puede apropiarse, e infinita por su responsabilidad por el Otro. Consideraciones finales: El Yo construye la esencia y la existencia en la responsabilidad. En la Ética de la Alteridad, en Lévinas, se proponen reflejos que influencien los comportamientos sensibles.

RESUMO Objetivo: Refletir sobre os comportamentos sensíveis dos profissionais em saúde indígena a partir da filosofia de Emmanuel Lévinas, para ratificar a integralidade, a equidade e a humanidade. Método: estudo reflexivo. Reflexão: Estudos têm identificado inadequações no atendimento às singularidades indígenas. Nos cenários hospitalar e ambulatorial, elas se diluem na busca por cuidados. A dificuldade dos profissionais em admiti-las gera conflitos e não adesão dos indígenas a tratamentos que desconsideram suas práticas de cuidado. Em Lévinas, a consciência requer,"a priori," sensibilidade para acessar o Infinito no Rosto do Outro, que nos encontros face a face se apresenta ao Eu como Alteridade radical, propondo uma relação Ética pela transcendência. A liberdade do Eu quanto ao Outro é finita, porque dele não pode se apossar, e infinita pela sua responsabilidade pelo Outro. Considerações finais: O Eu constrói essência e existência na responsabilidade. Na Ética da Alteridade, em Lévinas, propõem-se reflexões que influenciem comportamentos sensíveis.