Avaliação da crioinjúria em ovócitos imaturos e maturados in vitro e produção de embriões a partir de ovócitos bovinos vitrificados em Open Pulled Straw (OPS) e Cryotop

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Ciências Médicas, Programa de Pós-Graduação em Ciências Médicas, 2012.

Estrategias territoriales participativas como instrumentos de diagnóstico y prospectiva, en el contexto europeo de los Fondos de Cohesión 2014–2020: el caso de Villena (Alicante)

Las Estrategias Territoriales de carácter participado, se han convertido en el instrumento válido para diagnosticar las necesidades de un territorio. La Unión Europea obliga la aplicación de esta herramienta en el nuevo contexto del periodo 2014–2020. En el municipio de Villena (Alicante), se realizó una estrategia territorial integrada, desde hace dos años que ha derivado en un foro económico social, a través del proceso de abajo-arriba. El estudio de caso avala que la ciudadanía sí que es importante y ha participado activamente en una planificación estratégica ya que los nuevos tiempos, en el contexto del desarrollo local, así lo determinan. Se establecen las fases de aplicación, la metodología utilizada y también los resultados obtenidos.

Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids

The direct CO2 electrochemical reduction on model platinum single crystal electrodes Pt(hkl) is studied in [C2mim+][NTf2−], a suitable room temperature ionic liquid (RTIL) medium due to its moderate viscosity, high CO2 solubility and conductivity. Single crystal electrodes represent the most convenient type of surface structured electrodes for studying the impact of RTIL ion adsorption on relevant electrocatalytic reactions, such as surface sensitive electrochemical CO2 reduction. We propose here based on cyclic voltammetry and in situ electrolysis measurements, for the first time, the formation of a stable adduct [C2mimH–CO2−] by a radical–radical coupling after the simultaneous reduction of CO2 and [C2mim+]. It means between the CO2 radical anion and the radical formed from the reduction of the cation [C2mim+] before forming the corresponding electrogenerated carbene. This is confirmed by the voltammetric study of a model imidazolium-2-carboxylate compound formed following the carbene pathway. The formation of that stable adduct [C2mimH–CO2−] blocks CO2 reduction after a single electron transfer and inhibits CO2 and imidazolium dimerization reactions. However, the electrochemical reduction of CO2 under those conditions provokes the electrochemical cathodic degradation of the imidazolium based RTIL. This important limitation in CO2 recycling by direct electrochemical reduction is overcome by adding a strong acid, [H+][NTf2−], into solution. Then, protons become preferentially adsorbed on the electrode surface by displacing the imidazolium cations and inhibiting their electrochemical reduction. This fact allows the surface sensitive electro-synthesis of HCOOH from CO2 reduction in [C2mim+][NTf2−], with Pt(110) being the most active electrode studied.

Distance, evidentiality and counter-argumentation: Concessive future in Spanish

The aim of this paper is to examine the connection between Spanish concessive future and evidentiality. More specifically, it is argued that concessive future does not merely represent a contextual variant of conjectural future (Escandell, 2010) but a new use (Squartini, 2012) which is restricted by the activated status of the proposition ( Dryer, 1996). Unlike conjectural future, concessive future does not have an inferential purpose; instead, it plays a role within the (counter) argumentation process. It actually develops a déréalisant function ( Ducrot, 1995). Therefore, although conjectural use and concessive use share the deictic value of future, they are the projection of this value over different levels of meaning. More generally, this paper shows that future in Spanish may intersect with several semantic and discourse categories, including – but not limited to – evidentiality.

Improvement of carbon materials performance by nitrogen functional groups in electrochemical capacitors in organic electrolyte at severe conditions

N-doped activated carbon fibers have been synthesized by using chemically polymerized aniline as source of nitrogen. Commercial activated carbon fibers (A20) were chemically modified with a thin film of polyaniline (PANI) inside the microporosity of the carbon fibers. The modified activated carbon fibers were carbonized at 600 and 800 °C, respectively. In this way, activated carbon fibers modified with surface nitrogen species were prepared in order to analyze their influence in the performance of electrochemical capacitors in organic electrolyte. Symmetric capacitors were made of activated carbon fibers and N-doped activated carbon fibers and tested in a two-electrode cell configuration, using triethylmethylammonium tetrafluoroborate/propylene carbonate (TEMA-BF4/PC) as electrolyte. The effect of nitrogen species in the degradation or stabilization of the capacitor has been analyzed through floating durability tests using a high voltage charging (3.2 V). The results show higher stabilizing effect in carbonized samples (N-ACF) than in non-carbonized samples and pristine activated carbon fibers, which is attributed to the presence of aromatic nitrogen group, especially positively charged N-functional groups.

On Gruenhage spaces, separating σ-isolated families, and their relatives

We prove that, given a topological space X, the following conditions are equivalent. (α) X is a Gruenhage space. (β) X has a countable cover by sets of small local diameter (property SLD) by F∩G sets. (γ) X has a separating σ-isolated family M⊂F∩G. (δ) X has a one-to-one continuous map into a metric space which has a σ-isolated base of F∩G sets. Besides, we provide an example which shows Fragmentability ⇏ property SLD ⇏ the space to be Gruenhage.

A natural extension of the classical envelope theorem in vector differential programming

The aim of this paper is to extend the classical envelope theorem from scalar to vector differential programming. The obtained result allows us to measure the quantitative behaviour of a certain set of optimal values (not necessarily a singleton) characterized to become minimum when the objective function is composed with a positive function, according to changes of any of the parameters which appear in the constraints. We show that the sensitivity of the program depends on a Lagrange multiplier and its sensitivity.

Remote Substituent Effects on the Stereoselectivity and Organocatalytic Activity of Densely Substituted Unnatural Proline Esters in Aldol Reactions

The organocatalytic activities of highly substituted proline esters obtained through asymmetric [3+2] cycloadditions of azomethine ylides derived from glycine iminoesters have been analyzed by 19F NMR and through kinetic isotope effects. Kinetic rate constants have been determined for unnatural proline esters incorporating different substituents. It has been found that exo-L and endo-L unnatural proline methyl esters yield opposite enantiomers in aldol reactions between cyclic ketones and aromatic aldehydes. The combined results reported in this study show subtle and remote effects that determine the organocatalytic behavior of these synthetic but readily available amino acid derivatives. These data can be used as design criteria for the development of new pyrrolidine-based organocatalysts.

Cross-talk and regulatory interactions between the essential response regulator RpaB and cyanobacterial circadian clock output

The response regulator RpaB (regulator of phycobilisome associated B), part of an essential two-component system conserved in cyanobacteria that responds to multiple environmental signals, has recently been implicated in the control of cell dimensions and of circadian rhythms of gene expression in the model cyanobacterium Synechococcus elongatus PCC 7942. However, little is known of the molecular mechanisms that underlie RpaB functions. In this study we show that the regulation of phenotypes by RpaB is intimately connected with the activity of RpaA (regulator of phycobilisome associated A), the master regulator of circadian transcription patterns. RpaB affects RpaA activity both through control of gene expression, a function requiring an intact effector domain, and via altering RpaA phosphorylation, a function mediated through the N-terminal receiver domain of RpaB. Thus, both phosphorylation cross-talk and coregulation of target genes play a role in the genetic interactions between the RpaA and RpaB pathways. In addition, RpaB∼P levels appear critical for survival under light:dark cycles, conditions in which RpaB phosphorylation is environmentally driven independent of the circadian clock. We propose that the complex regulatory interactions between the essential and environmentally sensitive NblS-RpaB system and the SasA-RpaA clock output system integrate relevant extra- and intracellular signals to the circadian clock.