Selective Complexation and Membrane Transport of Guanidinium Salts by Calix[6]arene Amides

The p-tert-butylcalix[6]arene hexamide 2 and syn-1,3,5–trimethoxy-2,4,6-triamide 4 were synthesized by reaction of α-chloro-N,N-diethylacetamide and the corresponding calix[6]arenes 1 and 3 , respectively. ¹H NMR spectroscopy shows that 2 is a mixture of different conformations whereas 4 is fixed in a cone conformation. Extraction experiments, (S-L) and (H₂O–CDCl₃) with picrate salts, indicate that 2 complexes both alkali metal (1:2 complex) and guanidinium salts (1:1 complex) but 4 complexes only guanidinium (1:1 complex). Incorporated in supported liquid membranes (Accurel^® / o-nitrophenyl n-octyl ether) the calixarenes 2 and 4 transport guanidinium salts. The hexamide 2 is a more efficient carrier of guanidinium but the syn-1,3,5-trimethoxy-2,4,6-triamide 4 is much more selective. Both 2 and 4 are sufficiently lipophilic to give membranes that are stable over longer periods (weeks).     

Effect of poly(ethylene terephthalate) morphology on thermal cis-trans isomerization and photofading of some azo dyes: A kinetic study

Three poly(ethylene terephthalate) films were prepared having the same crystallinity but different morphology. They were colored with azo dyes XC₆H₄N = NC₆H₄N(C₂H₅)₂ (where X is H, OCH₃, CN, and COOC₂H₅). The kinetics of the thermal cis-trans isomerization of these dyes has been studied below the glass transition temperature in the range 25–56°C. The isomerization process was found to be the result of a multiplicity of first-order reactions. The kinetic parameters have been correlated with the order degree at molecular level of the polymer. Lightfastness of the dyes in the polymer matrices has been also investigated: it appeared to be in relation with the supermolecular structure of the film.     

Genetic analysis of avoidance, maze, and wheel-running behaviors in the mouse.

Conducted a genetic analysis of avoidance, maze learning, and wheel-running activity in 1,573 SEC/1ReJ, DBA/2J, and C57BL/6J strain mice and their F1, F2, and F3 progenies. Results show that the mode of inheritance in a given behavioral measure depends on the crosses considered. Thus, a given allele may be dominant in a given hybrid combination and recessive in another combination. The significant genetic correlations between these 3 behavioral measures suggest that these traits could be influenced by some of the same genes. The estimates of heritability are larger for avoidance than for activity, suggesting that the latter trait is more related to fitness. (36 ref.) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The clock model and its relationship with the Allan and related variances

The clock errors are modeled by stochastic differential equations (SDE) and the relationships between the diffusion coefficients used in SDE and the Allan variance, a typical tool used to estimate clock noise, are derived. This relationship is fundamental when a mathematical clock model is used, for example in Kalman filter, noise estimation, and clock prediction activities.     

Heterogeneity of subunit composition in lupin globulins. Comparison of proteins from a single seed and from a number of seeds

The subunit compositions of a legumin-like (globulin 8) and a vicilin-like protein (globulin 4) extracted from a plurality of seeds and from a single seed both in commercial and in a selected cultivar of Lupinus albus were studied. In the case of globulin 4, a very similar number of bands were observed in SDS-PAGE, in the protein extracted from a batch of seed and in the same globulin isolated from a single seed. For globulin 8 the SDS-PAGE pattern showed fewer subunits in the protein from the batch of seeds than in that from a single seed. This is more pronounced in the single seed and in the plurality of seeds of a selected cultivar. Reasons for this behaviour are discussed.     

Advances in anodic alumina membranes thin film fuel cell: CsH2PO4 pore-filler as proton conductor at room temperature

Anodic alumina membranes (AAM) filled with cesium hydrogen phosphate proton conductor have been tested as inorganic composite electrolyte for hydrogen–oxygen thin film (≤50 μm) fuel cell (TFFC) working at low temperatures (25 °C), low humidity (T_gas = 25 °C) and low Pt loading (1 mg cm⁻²). Single module TFFC delivering a peak power of around 15–27 mW cm⁻², with open circuit voltage (OCV) of about 0.9 V and short circuit current density in the range 80–160 mA cm⁻² have been fabricated. At variance with pure solid acid electrolytes showing reproducibility problems due to the scarce mechanical resistance, the presence of porous alumina support allowed to replicate similar fuel cell performances over numerous AAM/CsH₂PO₄ assemblies. A scale-up process of the electrodic area has been optimized in order to increase the delivered peak power of AAM thin film fuel cell. Morphological, chemical and electrochemical studies on the alumina composite electrolyte have been carried out by means of scanning electron microscopy, X-ray diffractometry, Micro-Raman spectroscopy, DTA/DTG analysis, ac impedance spectroscopy and single fuel cell tests.     

Monitoring of perfluorinated compounds in edible fish from the Mediterranean Sea

Perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS) are environmental contaminants belonging to a chemical group known as perfluorinated compounds (PCFs). The United States Environmental Protection Agency (US EPA) considers both compounds to be carcinogenic. The goal of the present study was to evaluate the contamination levels of PFOS and PFOA in edible fish of the Mediterranean Sea. Twenty six fish muscles, 17 fish livers, five series of cephalopods (each composed of ten specimens) and thirteen series of bivalves (each composed of about 50 specimens) were used for the investigation. A fast sample treatment, followed by an LC–ESI–MS/MS method is described for the identification, and quantification of PFOA and PFOS in fish. The method was in-house-validated through the determination of precision, accuracy, specificity, calibration curve, decision limit (CCα), and detection capability (CCβ). The results showed PFOA and PFOS levels in fishes and molluscs lower than those reported for analogue matrices in different geographic areas. Therefore, our biomonitoring results did not show that the Mediterranean Sea had any particularly alarming pollution by PFCs, although it is located in a semi-closed basin with scarce water change. Nonetheless, a worrying element is that a few fish showed extremely high contamination by PFOA and PFOS. This finding needs further clarification in order to assess whether such unusual contamination is linked to “dot-like” pollutant release, which could explain the anomaly.     

Exploitation of Polyphenolic Extracts from Grape Marc as Natural Antioxidants by Encapsulation in Lipid-Based Nanodelivery Systems

Phenolic compounds were extracted from grape marc by means of high pressure and temperature extraction. In order to increase their dispersability in the aqueous phase, the polyphenolic extracts were encapsulated at a final concentration of 0.1 % (w/w) in nanoemulsion-based delivery systems, which were formulated with natural ingredients, using either a liquid (sunflower oil) or a solid (palm oil) lipid phase, as well as the combination of a hydrophilic and hydrophobic emulsifier, and were produced by high-pressure homogenization. The delivery systems were characterized in terms of physicochemical stability under accelerated ageing (storage at 4 °C, 30 °C, and 55 °C for 14 days), by recording the evolution of the mean droplet size, the creaming index as well as the UV–vis absorption spectra of the encapsulated polyphenols. The antioxidant activity of the encapsulated extracts was measured with two different chemical assays (FRAP and ORAC) and a cellular antioxidant assay. Sunflower oil-based nanoemulsions resulted to be the most physically and chemically stable, with no significant variation of the mean droplet size and no degradation of the encapsulated compounds under the different conditions tested. The FRAP and ORAC assays showed that the antioxidant compounds, when encapsulated, are as available as unencapsulated polyphenols in scavenging the peroxyl radicals (ORAC), but are less available in reducing the ferric tripyridyltriazine complexes (FRAP). Remarkably, the cellular antioxidant activity was significantly higher for the encapsulated grape marc polyphenols than for the unencapsulated ones, suggesting the fundamental role of the nanoemulsions in favoring the delivery through the biological membranes.