Synergistic effect of organoclay fillers based on fluorinated surfmers for preparation of polystyrene nanocomposites

Novel fluorinated reactive surfactants were used for the organic modification of monmorillonite clays. These organoclays were used for the preparation of polystyrene?clay nanocomposites by in‐situ free radical polymerization. Reference systems based on hydrocarbon homologous surfmer and nonpolymerizable surfactants were also used to deduce the effect of the fluorine moiety and the polymerizable function on the morphology and thermal stability of the prepared nanocomposites. Different structural parameters of the surfactants were investigated and modulated for the clay modification including: the nature of surfactant (surfmer/classical surfactant, fluorinated, or hydrocarbonated), the length of the fluorinated chain as well as the length of the hydrocarbon spacers linking the ammonium head to the fluorine chain or the polymerizable acrylic function. Wide angle‐X‐ray scattering (WAXD), thermogravimetric analysis (TGA), and electronic microcopies (TEM and SEM) were used to establish a structure‐morphology, thermal properties relationships, and to highlight the key parameters governing the exfoliation process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42347.     

Melanocytes Affect Nodal Expression and Signaling in Melanoma Cells: A Lesson from Pediatric Large Congenital Melanocytic Nevi

Expression of Nodal, a Transforming Growth Factor-beta (TGF-β) related growth factor, is associated with aggressive melanoma. Nodal expression in adult dysplastic nevi may predict the development of aggressive melanoma in some patients. A subset of pediatric patients diagnosed with giant or large congenital melanocytic nevi (LCMN) has shown increased risk for development of melanoma. Here, we investigate whether Nodal expression can help identify the rare cases of LCMN that develop melanoma and shed light on why the majority of these patients do not. Immunohistochemistry (IHC) staining results show varying degree of Nodal expression in pediatric dysplastic nevi and LCMN. Moreover, median scores from Nodal IHC expression analysis were not significantly different between these two groups. Additionally, none of the LCMN patients in this study developed melanoma, regardless of Nodal IHC levels. Co-culture experiments revealed reduced tumor growth and lower levels of Nodal and its signaling molecules P-SMAD2 and P-ERK1/2 when melanoma cells were grown in vivo or in vitro with normal melanocytes. The same was observed in melanoma cells cultured with melanocyte conditioned media containing pigmented melanocyte derived melanosomes (MDM). Since MDM contain molecules capable of inactivating radical oxygen species, to investigate potential anti-oxidant effect of MDM on Nodal expression and signaling in melanoma, melanoma cells were treated with either N-acetyl-l-cysteine (NAC), a component of the anti-oxidant glutathione or synthetic melanin, which in addition to providing pigmentation can also exert free radical scavenging activity. Melanoma cells treated with NAC or synthetic melanin showed reduced levels of Nodal, P-SMAD2 and P-ERK1/2 compared to untreated melanoma cells. Thus, the potential role for Nodal in melanoma development in LCMN is less evident than in adult dysplastic nevi possibly due to melanocyte cross-talk in LCMN capable of offsetting or delaying the pro-melanoma effects of Nodal via anti-oxidant effects of MDM.     

Particle Size of Whole Meal Rye Bread does not Affect the Digestibility of Macro-Nutrients and Non-Starch Polysaccharides and the Energy Value of Dietary Fibre in Humans

The effect of particle size of whole meal rye bread on the apparent digestibility of macro-nutrients, non-starch polysaccharides (NSP) and energy, the energy value of rye NSP and on faecal weight was studied in balance experiments in seven young women. The whole meal breads were prepared from one single batch of rye milled to two different particle sizes (coarse bread: 50% of particles >2 mm, 90% >1 mm; fine bread: 86% of particles <0·5 mm, 58% <0·2 mm). Two diets containing either coarse (350 g day⁻¹) or fine (377 g day⁻¹) whole meal bread and a low fibre control diet were consumed for 3 weeks each in a 3×3 cross-over design. Relative to the low fibre control diet, digestibility of protein, NSP and energy was significantly lower for the diets containing the whole meal breads. Digestibility of fat was the same for all diets. Partial digestible energy value for each g of NSP from coarse and fine whole meal rye bread was calculated to be −3±7 and 1±5 kJ, respectively. There were no differences between coarse and fine whole meal rye bread in the effects on the parameters measured with the exception on faecal wet weight, which was higher for the coarse bread diet.     

Sequencing analysis of a 40·2 kb fragment of yeast chromosome X reveals 19 open reading frames including URA2 (5′ end), TRK1, PBS2, SPT10, GCD14, RPE1, PHO86, NCA3, ASF1, CCT7, GZF3, two tRNA genes,three remnant delta elements and a Ty4 transposon

The complete sequence of a 40 247 bp DNA segment located on the left arm of chromosome X of Saccharomyces cerevisiae has been determined and analysed. The sequence encodes the 5′ coding region of the URA2 gene and 18 open reading frames of at least 100 amino acids. Ten of these correspond to known genes, whereas eight correspond to new genes. In addition, the sequence contains a tRNA-Ala gene, a tRNA-Asp gene, a Ty4 transposable element and three delta elements. The sequence has been deposited in the EMBL databank under Accession Numbers: Z49405, Z49404, Z49403, Z49402, Z49401, Z49400, Z49399, Z49398, Z49397, Z49396, Z49394, Z49392, Z49391, Z49390, Z49389, Z49387, Z49386, Z49385.     

Effect of cure temperature on the structure and water absorption of epoxy/amine thermosets

Dielectric and rheological measurements are reported on the effect of cure temperature on the water absorption of tris[(2,3-epoxypropoxy)phenyl] methane cured with a 1 : 1 stoichiometric ratio of 4,4′-diaminodiphenylsulphone. Analysis of the water absorption characteristics of these materials using a combination of dielectric and gravimetric measurements has indicated that water molecules can be found in two distinctly different types of environments. There are water molecules which are strongly interacting with polar groups and water molecules clustered together into sub-micro-scale cavities within the matrix structure. Changes in the final cure temperature have the effect of changing both the extent and distribution of the types of water molecules present in the matrix. Validation of the diffusion coefficients obtained from the dielectric analysis is based on a comparison with gravimetric data and the implications are discussed. Differences observed between these two different types of measurement are related to peculiarity in the dielectric method and its extreme sensitivity to interfacial phenomena.     

Comparative X-ray scattering,microscopical, and mechanical studies on rectangular plates injection molded from different types of isotactic polypropylene

Rectangular plates were injection molded from two grades of commercial polypropylene (PP) differing in the molar mass distribution. The mold was mechanically sealed when a desired pressure p_i,max (up to 1560 bar) was reached. Samples were taken from each plate at different distances from the gate and were investigated by applying various methods. In spatially resolved wide-angle X-ray studies, the cross section of the sample was scanned with a fine X-ray beam (collimated by a Kratky small-angle camera) and the intensity of scattering was registered by a linear detector as a function of position in the cross section. The evaluation of the scattering data delivered profiles of several parameters, describing the distribution of crystallite modification β-PP and γ-PP, the degree of orientation, the size of crystallites, and interplanar spacing, depending on the distance from surface. These results and those from measurements of birefringence and elongation at break, and from polarization microscopy and transmission electron microscopy, provided details of the layered structures in the plates, at different flow lengths, and allowed far-reaching statements about the influence of molecular properties and processing conditions on the development of texture in the plates.