Effect of melt flow rate of polycarbonate and cobalt catalyst on properties of PET/PC (80/20 wt%) reactive blending

The influence of PC melt flow rate (MFR) on phase behavior, thermal and rheological properties of catalysed and non-catalysed poly(ethylene terephthalate)/polycarbonate (PET/PC) (80/20 wt%) reactive blending were investigated. Two types of PC named PC1 and PC2 with MFR 3.1 and 10.8 g/10 min, respectively, were used. Each PC and the catalyst showed significant influence on calorimetric properties, thermal stability and WAXS patterns of the blends. Regarding to TG/DTG, the blends degraded in two steps which were attributed to PET rich phase and PC one and permit to infer that a partially miscible blends were produced.     

Tin(IV) complexes with 2-pyridineformamide-derived thiosemicarbazones: Antimicrobial and potential antineoplasic activities

Reaction of tin tetrachloride with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph) derivatives gave [Sn(2Am4DH)Cl₃] (1), [Sn(2Am4Me)Cl₃] (2), [Sn(2Am4Et)Cl₃] (3) and [Sn(2Am4Ph)Cl₃] (4) as products, in which an anionic thiosemicarbazone coordinates to the metal centre along with three chloride ions. The crystal structures of 1 and 2 were determined. The thiosemicarbazones were moderately active against Candida albicans and Pseudomonas aeruginosa. Upon coordination to tin(IV) the antimicrobial activity of the thiosemicarbazones increases. The studied compounds proved to be toxic to Artemia salina, suggesting that they could present cytotoxic activity against solid tumors.     

Comparative study between a CMS membrane and a CMS adsorbent: Part I—Morphology, adsorption equilibrium and kinetics

This paper presents a comparative study between a carbon molecular sieve (CMS) membrane and a commercial CMS adsorbent; these materials are suited for selective gas permeation and adsorption-based gas separations, respectively. The purpose of this analysis is to better understand the mass transport mechanism in CMS membranes and how it is related to the material's structure. The structural characterization based on the adsorption of CO₂ at 0 °C revealed that the adsorbent has a greater micropore volume, a smaller mean pore width and a micropore size distribution shifted to the left, when compared to the membrane. This translates into a lower adsorption capacity of the membrane towards N₂, Ar, CO₂ and O₂ at 29.5 °C and 0–7 bar. The adsorption kinetics were also studied and the pressure-dependence of the apparent time constants established; different models were used to predict the experimental results, emphasizing the very important role of the ultramicroporosity on the properties of the materials. The CMS membrane exhibited a pore blockage effect when permeating O₂ and CO₂. Further morphologic characterization was performed by SEM, X-ray diffraction and mercury porosimetry.     

Sequential Injection Kinetic Flow Assay for Monitoring Glycerol in a Sugar Fermentation Process by <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>

A sequential injection system to monitor glycerol in a Saccharomyces cerevisiae fermentation process was developed. The method relies on the rate of formation of nicotinamide adenine dinucleotide in its reduced form (NADH, measured spectrophotometrically at 340 nm) from the reaction of glycerol with NAD⁺ cofactor, catalysed by the enzyme glycerol dehydrogenase present in solution. This procedure enables the determination of glycerol between 0.046 and 0.46 g/l, (corresponding to yeast fermentation samples with concentrations up to 50 g/l) with good repeatability (relative standard deviation for n = 10 lower than 2.2% for three different samples) at a sampling frequency of 25/h. The detection and quantification limits using a miniaturised spectrophotometer were 0.13 and 0.44 mM, respectively. Reagent consumption was of 0.45 μmol NAD⁺ and 1.8 μg enzyme per assay, and the waste production was 2.8 ml per determination. Results obtained for samples were in agreement with those obtained with a high-performance liquid chromatography method.     

Determination of eight fatty acid ethyl esters in meconium samples by headspace solid‐phase microextraction and gas chromatography–mass spectrometry

A number of fatty acid ethyl esters (FAEEs) have recently been detected in meconium samples. Several of these FAEEs have been evaluated as possible biomarkers for in utero ethanol exposure. In the present study, a method was optimized and validated for the simultaneous determination of eight FAEEs (ethyl laurate, ethyl myristate, ethyl palmitate, ethyl palmitoleate, ethyl stearate, ethyl oleate, ethyl linoleate and ethyl arachidonate) in meconium samples. FAEEs were extracted by headspace solid‐phase microextraction. Analyte detection and quantification were carried out using GC‐MS operated in chemical ionization mode. The corresponding D5‐ethyl esters were synthesized and used as internal standards. The LOQ and LOD for each analyte were <150 and <100 ng/g, respectively. The method showed good linearity (r²>0.98) in the concentration range studied (LOQ – 2000 ng/g). The intra‐ and interday imprecision, given by the RSD of the method, was lower than 15% for all FAEEs studied. The validated method was applied to 63 authentic specimens. FAEEs could be detected in alcohol‐exposed newborns (>600 ng/g cumulative concentration). Interestingly, FAEEs could also be detected in some non‐exposed newborns, although the concentrations were much lower than those measured in exposed cases.     

Metal oxalates in paints: a Raman investigation on the relative reactivities of different pigments to oxalic acid solutions

One degradation phenomenon that occurs in artworks is the formation of metal oxalates on their surfaces. In order to gain insight into the inclination of pigments to produce oxalates, nine pigments including Na, Ca, Fe, Pb and Cu cations were selected to react with oxalic acid solutions at different concentrations (1 M, 0.1 M, 0.01 M and 0.005 M). Micro-Raman spectroscopy was used to detect the different reaction products. Pigments containing calcium (calcite, gypsum and Volterra gypsum) showed a high tendency to form weddellite as well as whewellite, especially at high acidic concentrations; among copper-based pigments (malachite, azurite, verdigris), the formation of moolooite was observed for high concentrations of acid and down to the lowest concentration (0.005 M) in the case of verdigris. Lead oxalate was detected on lead white. No iron oxalates were observed for hematite; the formation of calcium oxalate crystals was observed instead. Ultramarine blue reacted to produce elemental sulfur. According to the results obtained, calcite and verdigris showed the highest reactivity in oxalic acid environments, resulting in a high tendency to form calcium and copper oxalates, even at very low acidic concentrations; this behavior seems to arise from the high solubilities of these pigments in acidic environments.     

Stable Gauss maps from a global viewpoint

We associate weighted graphs to stable Gauss maps on orientable closed surfaces immersed in 3-space and prove that any bipartite weighted graph can be associated to some stable Gauss map.     

Robust pair‐copula based forecasts of realized volatility

A useful application for copula functions is modeling the dynamics in the conditional moments of a time series. Using copulas, one can go beyond the traditional linear ARMA (p,q) modeling, which is solely based on the behavior of the autocorrelation function, and capture the entire dependence structure linking consecutive observations. This type of serial dependence is best represented by a canonical vine decomposition, and we illustrate this idea in the context of emerging stock markets, modeling linear and nonlinear temporal dependences of Brazilian series of realized volatilities. However, the analysis of intraday data collected from e‐markets poses some specific challenges. The large amount of real‐time information calls for heavy data manipulation, which may result in gross errors. Atypical points in high‐frequency intraday transaction prices may contaminate the series of daily realized volatilities, thus affecting classical statistical inference and leading to poor predictions. Therefore, in this paper, we propose to robustly estimate pair‐copula models using the weighted minimum distance and the weighted maximum likelihood estimates (WMLE). The excellent performance of these robust estimates for pair‐copula models are assessed through a comprehensive set of simulations, from which the WMLE emerged as the best option for members of the elliptical copula family. We evaluate and compare alternative volatility forecasts and show that the robustly estimated canonical vine‐based forecasts outperform the competitors. Copyright © 2013 John Wiley & Sons, Ltd.     

Gravity-driven azimuthal flow of a layer of thixotropic fluid on the inner surface of a horizontal tube

The gravity-driven azimuthal flow of a layer of thixotropic paint on the inner surface of a horizontal tube is studied, considering surface tension effects. Using the lubrication theory, it was shown that a non-linear, fourth-order partial differential equation governs the time evolution of the paint layer thickness distribution along the azimuthal coordinate. Three parameters arise in the analysis, namely, the Bond number and two rheology-related parameters. The governing equation is integrated via a second-order accurate finite-difference scheme. The results showed that, in situations where the capillary force dominates (Bo < 1), displacement of the paint after application is very slow. For situations where the gravity force dominates (Bo > 1), an undulation on the interface arises near the tube bottom at sufficiently large times.     

Statistical mechanics based on Renyi entropy

In this work we show that it is possible to obtain a generalized statistical mechanics (thermostatistics) based on Renyi entropy, to be maximized with adequate constraints. The equilibrium probability distribution thus obtained has a very interesting property. Indeed, it reminds us the statistical distribution proposed by Tsallis, known to conveniently describe a variety of phenomena in nonextensive systems. Moreover, some examples are worked out in order to illustrate the main features of the herein introduced formalism.