Structural modifications and fibre processing of hydroxy-functionalised mesogenic polyazomethines

A number of semiflexible homopolyazomethines and copolyazomethines based on hydroxy-functionalised mesogenic cores have been synthesised and characterised. The reported polymers include structural modifications such as an alteration of the coaxiality, shortening of the flexible spacers or copolymerisation to attain materials with reduced melting temperatures and suitable processability. These structural alterations have been introduced by condensing different ,ω-bis-[(4-formyl-3-hydroxyphenyl)oxy]alkanes with 2-methyl-1,4-phenylenediamine and/or 4-methyl-1,3-phenylenediamine. Fibres have been melt extruded from those nematic polyazomethines with the most favourable thermal properties. As-spun and tension-annealed fibres have been investigated by thermal analysis (TGA and DSC), X-ray diffraction and SEM microscopy in an attempt to infer a relationship between microstructure and tensile properties. From the results presented here, copolymerisation incorporating flexible spacers of different lengths seems to be the best strategy to balance ease of processing and tensile properties. Some of the fibres have improved mechanical properties compared with those previously reported for this class of semiflexible polyazomethine. A nematic polyazomethine with a decamethylenic spacer has also been modified with low percentages of several metal ions [Fe(III), Zn(II), V(IV) and Ni(II)] in order to establish a comparison with previously reported Cu(II)-modified fibres.     

Cardiac tamponade as a presentation of primary hypothyroidism in a young woman

Pericardial effusion (PE) as a hypothyroidism associated sign, is something that can be found with relative frequency; nevertheless, cardiac tamponade (CT) as the first sign of this disease may be considered exceptional especially in young patients. We report a 31 years old woman with clinical symptoms and signs of CT that in the forward workshop was diagnosed of primary hypothyroidism as cause of the CT. We shortly describe the case and review the literature, emphasizing the importance of the knowledge of CT trigger factors in myxedematous PE, as well as its usual benign evolution with hormonal treatment, without recurrences of the CT after pericardiocentesis is performed. This justify a conservative approach, in spite of the slow resolution of the PE what can take as long as 1.5 years.     

A noncompetitive peptide inhibitor of the nicotinic acetylcholine receptor from Conus purpurascens venom

A paralytic peptide, psi-conotoxin Piiie has been purified and characterized from Conus purpurascens venom. Electrophysiological studies indicate that the peptide inhibits the nicotinic acetylcholine receptor (nAChR). However, the peptide does not block the binding of alpha-bungarotoxin, a competitive nAChR antagonist. Thus, psi-conotoxin Piiie appears to inhibit the receptor at a site other than the acetylcholine-binding site. As ascertained by sequence analysis, mass spectrometry, and chemical synthesis, the peptide has the following covalent structure: HOOCCLYGKCRRYOGCSSASCCQR* (O = 4-trans hydroxyproline; * indicates an amidated C-terminus). The disulfide connectivity of the toxin is unrelated to the alpha- or the alphaA-conotoxins, the Conus peptide families that are competitive inhibitors of the nAChR, but shows homology to the mu-conotoxins (which are Na+ channel blockers).     

A magnetic resonance imaging study of planum temporale asymmetry in men with developmental dyslexia

The influence of ionic strength and composition on the binding and inhibition of human leukocyte elastase by glycosaminoglycans with variable degree and position of sulfation was investigated. The kinetic mechanism of inhibition had a hyperbolic, mixed-type character with a competitive component that was promoted by low ionic strength, reduced by phosphate ions, and which also depended on the substrate and glycosaminoglycan structure. Enzyme binding was a cooperative phenomenon that varied with ionic strength and composition. The inhibition patterns correlated with the cationic character of elastase and with the distribution of arginines on its molecular surface, most notably with residues located in the vicinity of the substrate binding region. The order of affinity for elastase binding was chondroitin 4-sulfate < chondroitin 6-sulfate < dermatan sulfate, iduronate-containing derivatives being superior with respect to the glucuronate-containing counterparts. Additional sulfation at both the 4- and 6- positions or at the N- and 4-positions of the N-acetylgalactosamine moiety decidedly improved the inhibitory efficiency. The results highlight a fundamental physiological role of enzyme-glycosaminoglycan interactions. In the azurophil granule of the human polymorphonuclear neutrophil, elastase and other enzymes are bound to a matrix of chondroitin 4-sulfate because this is the only glycosaminoglycan that simultaneously offers good binding for enzyme compartmentalization together with prompt release from the bound state at the onset of phagocytosis.     

Reaction scheme and kinetic modelling for the MTO process over a SAPO-18 catalyst

A kinetic model for simulation of the MTO process over SAPO-18 catalyst in a wide range of operating conditions has been proposed. The kinetic model predicts the experimental evolution of reaction products with time on stream, which follows three consecutive periods: initiation (where olefin production increases), a period of maximum olefin production and a period in which this production decreases. The kinetic scheme takes into account these three steps that evolve with time on stream: formation of active intermediate compounds, an step where olefins are formed by reaction of oxygenates (methanol/DME) with these intermediates and deactivation of intermediates by degradation to coke. The presence of water in the reaction medium attenuates the reaction rate of these steps. Discrimination of kinetic equations and calculation of the parameters of best fit have been carried out by solving the mass conservation equations of the individual components of the kinetic scheme together with the kinetic equation for deactivation and taking into account the effect of water on the kinetics of each step.     

A time series bootstrap procedure for interpolation intervals

A sieve bootstrap procedure for constructing interpolation intervals for a general class of linear processes is proposed. This sieve bootstrap provides consistent estimators of the conditional distribution of the missing values, given the observed data. A Monte Carlo experiment is used to show the finite sample properties of the sieve bootstrap and finally, the performance of the proposed method is illustrated with a real data example.