Thiophene‐ and silarylene‐containing polyesters. Resonance effect on conductivity after polarization in an external electric field

Polyesters were synthesized by direct polycondensation of thiophene‐2,5‐dicarboxylic acid and five different silarylene‐containing diphenols using a tosyl chloride/pyridine/N,N‐dimethylformamide system as a condensing agent. Polymers were obtained in good yields and were characterized using Fourier transform infrared and NMR (¹H, ¹³C, 135‐DEPT and ²⁹Si) spectroscopy and elemental analysis. All polymers were completely soluble in aprotic organic polar solvents such as dimethylformamide, dimethylsulfoxide and N‐methyl‐2‐pyrrolidone. The range of effective mass of the polymers (m/z) was 1 × 10⁵–2 × 10⁵, determined using electrospray ionization mass spectrometry. Asymmetry and steric hindrance prevented dense packing of the polymeric chains, showing glass transition temperatures between ? 78 and ? 51 °C and loss of thermal stability at 177–199 °C (10% weight loss). Additionally, the melting points of the polyesters were found to be in the range 62–67 °C. Because of this, the samples were semi‐solid at room temperature. The optical band gaps of the polymers were observed between 4.54 and 4.48 eV, corresponding in all cases to insulator behavior. The molecular structure of the samples was studied using X‐ray diffraction, showing a degree of order that was associated with two monoclinic lattices. Additionally, the conductivity was studied using a two‐point method with contacts on top of polymer films. Prior to the electrical measurement, the samples were polarized in an external electric field of 0.8 to 6.4 V cm^?1, and the alignment of the dipoles increased the electrical conductivity. Copyright © 2012 Society of Chemical Industry     

Crude oil aggregation by microscopy and dynamic light scattering

This research is focused on establishing a methodology to evaluate the aggregation state of Mexican crude oil solutions from two different sources and SARA compositions, by using Dynamic Light Scattering (DLS). Different crude oil concentrations were established and monitored through time in order to determine their effects on the aggregation state. DLS results indicate that the aggregation state of the studied solutions is influenced by crude oil composition, specifically by the amount of resins. Particle size and elemental analysis of the aggregates were performed by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX), respectively. Results from these techniques reveal particulated low-porosity smooth surfaces due to the presence of resin, as well as the determination of the characteristic elements found in asphaltenes. High-Resolution Transmission Electron Microscopy (HTEM) indicated the presence of asphaltene aggregates constituted by nanometric particles and asphaltene stacking as well as ultrafine nanocrystalline-oriented structures.     

Nanoconfined mixed Li and Mg borohydrides as materials for solid state hydrogen storage

Several mixtures of LiBH₄ and Mg(BH₄)₂ borohydrides in different stoichiometric ratios (1:0, 2:1, 1:1, 1:2, 0:1), prepared by high energy ball milling, have been investigated with X-ray powder diffraction and thermal programmed desorption (TPD) volumetric analysis to test the dehydrogenation kinetics in correlation with the physical mixture composition. Afterwards mixed and unmixed borohydrides were dispersed on high specific surface area ball milled graphite by means of the solvent infiltration technique. BET and statistical thickness methods were used to characterize the support surface properties, and SEM micrographs gave a better understanding of the preparation techniques. It has been observed by TPD volumetric measurements that the confinement of the reactive borohydrides on the nanoporous supports leads to a lower dehydrogenation temperature compared to unsupported borohydrides. Moreover, a further decrease of the dehydrogenation temperature has been observed by increasing the specific surface area of the support and the pores volume and by using the prepared mixtures instead of pure materials. The dehydrogenation process seems to be favoured by the heterogeneous nucleation on the graphite surface of decomposition products or intermediate phases from melted liquid borohydrides.     

Combustion analysis of a spark ignition engine fueled with gaseous blends containing hydrogen

This paper presents the combustion characteristics of a naturally aspirated spark ignition engine, intended for installation in vehicles, fueled with different hydrogen and methane blends. The experimental tests were carried out in a wide range of speeds at equivalence ratios of 1, 0.8 and 0.7 and at full load. The ignition timing was maintained for each speed, independently of the equivalence ratio and blend used as fuel. Four methane-hydrogen blends were used. In-cylinder pressure, mass fraction burned, heat released and cycle-by-cycle variations were analyzed as representative indicators of the combustion quality. It was observed that hydrogen enrichment of the blend improve combustion for the ignition timing chosen. This improvement is more appreciable at low speeds, because at high speeds hydrogen effect is attenuated by the high turbulence. Also, hydrogen addition allowed the extension of the LOL, enabling the engine to run stable in points where methane could not be tested. The main inconvenience detected was the high NO_x emissions measured, especially at stoichiometric conditions, due mainly to the increment in the combustion temperature that hydrogen produces.     

Crisis response strategies in Finland and Spain

Crises are common in today's unpredictable environment rising the importance of crisis response strategies. Two societies in Europe are chosen: Finland, where trust in society is generalized to institutions, and Spain, where trust in society remains on the level of individuals. Using the results of the European Communication Monitor 2013 survey on crisis communication, we explored three hypotheses: “certain types of crises are often met with certain types of strategies,” “cultural context makes some crises more likely than others,” and “cultural context makes some response strategies more likely than others.” We find evidence for all three hypotheses and discuss our findings about perceived differences in the two societies. The results show that the cultural context plays an important role for crisis communication.     

Algorithms for computing triangular decomposition of polynomial systems

We discuss algorithmic advances which have extended the pioneer work of Wu on triangular decompositions. We start with an overview of the key ideas which have led to either better implementation techniques or a better understanding of the underlying theory. We then present new techniques that we regard as essential to the recent success and for future research directions in the development of triangular decomposition methods.     

N-(Anilinoethyl)amide Melatonergic Ligands with Improved Water Solubility and Metabolic Stability

The MT₂-selective melatonin receptor ligand UCM765 (N-(2-((3-methoxyphenyl)(phenyl)amino)ethyl)acetamide), showed interesting sleep inducing, analgesic and anxiolytic properties in rodents, but suffers from low water solubility and modest metabolic stability. To overcome these limitations, different strategies were investigated, including modification of metabolically liable sites, introduction of hydrophilic substituents and design of more basic derivatives. Thermodynamic solubility, microsomal stability and lipophilicity of new compounds were experimentally evaluated, together with their MT₁ and MT₂ binding affinities. Introduction of a m-hydroxymethyl substituent on the phenyl ring of UCM765 and replacement of the replacement of the N,N-diphenyl-amino scaffold with a N-methyl-N-phenyl-amino one led to highly soluble compounds with good microsomal stability and receptor binding affinity. Docking studies into the receptor crystal structure provided a rationale for their binding affinity. Pharmacokinetic characterization in rats highlighted higher plasma concentrations for the N-methyl-N-phenyl-amino derivative, consistent with its improved microsomal stability and makes this compound worthy of consideration for further pharmacological investigation.