(Z)-3-p-tolylsulfinylacrylonitriles as chiral dipolarophiles: reactions with diazoalkanes

[reaction: see text] The dipolarophilic reactivity of enantiopure (Z)-3-p-tolylsulfinylacrylonitriles (1) has been evaluated with diazoalkanes. 3-Cyanopyrazoles are obtained when R = H, but with R = alkyl (Bn, n-Bu, and t-Bu) only one cycloadduct (4 or 5) is formed in high yield under mild conditions, therefore evidencing a complete control of the regioselectivity and the endo/exo and pi-facial selectivities. These reactions are a new straightforward entry to the synthesis of pyrazolines and related structures and reveal the excellent dipolarophilic features of (Z)-sulfinylacrylonitriles.     

Cosmological Two-Fluid Thermodynamics

We reveal unifying thermodynamic aspects of so different phenomena as the cosmological electron-positron annihilation, the evaporation of primordial black holes with a narrow mass range, and the "deflationary" transition from an initial de Sitter phase to a subsequent standard Friedmann–Lemaître–Robertson–Walker (FLRW) behavior.     

Multiresolution information measures applied to speech recognition

Considerable advances in automatic speech recognition have been made in the last decades, thanks specially to the use of hidden Markov models. In the field of speech signal analysis, different techniques have been developed. However, deterioration in the performance of the speech recognizers has been observed when they are trained with clean signal and tested with noisy signals. This is still an open problem in this field. Continuous multiresolution entropy has been shown to be robust to additive noise in applications to different physiological signals. In previous works we have included Shannon and Tsallis entropies, and their corresponding divergences, in different speech analysis and recognition systems. In this paper we present an extension of the continuous multiresolution entropy to different divergences and we propose them as new dimensions for the pre-processing stage of a speech recognition system. This approach takes into account information about changes in the dynamics of speech signal at different scales. The methods proposed here are tested with speech signals corrupted with babble and white noise. Their performance is compared with classical mel cepstral parametrization. The results suggest that these continuous multiresolution entropy related measures provide valuable information to the speech recognition system and that they could be considered to be included as an extra component in the pre-processing stage.     

Fractional diffusion models of option prices in markets with jumps

Most of the recent literature dealing with the modeling of financial assets assumes that the underlying dynamics of equity prices follow a jump process or a Lévy process. This is done to incorporate rare or extreme events not captured by Gaussian models. Of those financial models proposed, the most interesting include the CGMY, KoBoL and FMLS. All of these capture some of the most important characteristics of the dynamics of stock prices. In this article we show that for these particular Lévy processes, the prices of financial derivatives, such as European-style options, satisfy a fractional partial differential equation (FPDE). As an application, we use numerical techniques to price exotic options, in particular barrier options, by solving the corresponding FPDEs derived.     

Cohomogeneity One Einstein-Sasaki 5-Manifolds

We consider hypersurfaces in Einstein-Sasaki 5-manifolds which are tangent to the characteristic vector field. We introduce evolution equations that can be used to reconstruct the 5-dimensional metric from such a hypersurface, analogous to the (nearly) hypo and half-flat evolution equations in higher dimensions. We use these equations to classify Einstein-Sasaki 5-manifolds of cohomogeneity one.     

Catalyst-free synthesis of benzodiazepines and benzimidazoles using glycerol as recyclable solvent

We described herein the use of glycerol as solvent in the catalyst-free synthesis of benzodiazepines and benzimidazoles. This simple and efficient method furnishes the corresponding 1-H-1,5-benzodiazepines and 1,2-disubstituted benzimidazoles in good yields by the condensation of o-phenylenediamine with several ketones and aldehydes, respectively. In addition, glycerol can be easily re-utilized for further condensation reactions up to four times without lost of activity.     

Nafion/tetraruthenated porphyrin glassy carbon-modified electrode: characterization and voltammetric studies of sulfite oxidation in water–ethanol solutions

In this work, the modification of a glassy carbon electrode with tetraruthenated porphyrins electrostatically assembled onto a Nafion film, previously adsorbed on the electrode surface, is reported. This modified electrode was characterized by scanning electron microscopy–energy-dispersive X-ray, Raman spectroscopy, UV-Vis spectroelectrochemistry, and cyclic voltammetry. The Nafion film onto the glassy carbon electrode shows a smooth disposition; when the tetraruthenated porphyrin is incorporated on the Nafion film, the complex is adsorbed in a homogeneous way. The modified electrode catalyzes HSO₃⁻ oxidation in water–ethanol solutions and shows an enhanced stability compared with the electrode modified with the dip coating method. Rotating disk electrode experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film. I/E curves show a Tafel slope of 120 mV/decade corresponding to a first electron-transfer reaction, depending on the potential, as the determining step. Spectroelectrochemical experiments demonstrated that Ru(II) is the active site for the electrocatalysis.