Synthesis of semiconducting polyphenylacetylene catalyzed by Ni(MeCN)6(BF4)2/AlEt2Cl

Summary Phenylacetylene (PhA) is polymerized by the dicationic nickel complex Ni(MeCN)₆(BF₄)₂ associated with AlEt₂Cl as co-catalyst. The production of 200g of polymer per gram of nickel per hour represents a typical activity of this system. Under our experimental conditions, the polymer displays an exclusive trans structure. The molecular weight distribution of the polymer is polymodal (5000 g.mol⁻¹ and 200 g.mol⁻¹). The highest average molecular weight fraction (5000 g. mol⁻¹) represents the highest published value for polyphenylacetylene (PPA) where a nickel catalyst is employed. The electrical conductivities vary between 10⁻⁷ and 10⁻¹⁶ S.cm⁻¹, and are characteristic of a semi-conductor polymer. Equivalent values are cited in the literature only in the case of doped PPA. Experimental observations enabled us to propose a mechanism for the formation of the active species through the reaction of Ni(MeCN)₆(BF₄)₂ with AlEt₂Cl. Received: 13 September 2001/Revised version: 10 January 2002/ Accepted: 11 January 2002     

Antioxidant activity in leaves of some mediterranean plants

Hexane and methanol leaf extracts of sixteen Mediterranean plant species were obtained by percolation. Higher yields were observed for methanol (16.4–47.8%) than for hexane extracts (1.3–13%). Antioxidant activity of these extracts was determined by a rapid spectrophotometric method involving the combined oxidation of beta-carotene and linoleic acid. Leaf extracts were thus characterized by an Antioxidant Activity Coefficient (AAC) ranging from 0 to 1000. Hexane extracts gave much higher AAC values than the corresponding methanol extracts. In both cases, myrtle (Myrtus communis) showed the best antioxidant effectiveness.     

Stress Heterogeneity Effect on the Strength of Silicon Nitride

The experiments reported in this paper demonstrate the causes of the failure of monolithic ceramics. The specimens are made of silicon nitride and tested at room temperature. The stress field within the specimen is different for each of four series of tests that have been conducted. Fractographic observations have also been made to identify the causes of the failures. A size effect analysis is performed.     

Molders' perceptions of vinyl injection molding compounds

As a result of advances in such properties as processability and thermal stability, vinyl may now compete with ABS and many engineering resins in a broad number of injection molding applications. However, do past experiences with PVC compounds prevent molders from quoting on new vinyl jobs? What do molders think of vinyl's physical properties and molding characteristics versus other resins? Independent research conducted in 1989 questioned a broad range of molders in the United States regarding their perception of vinyl versus other resins as an injection molding material. The results highlight the fact that molders are aware of the benefits of vinyl in finished part applications, but require training to overcome the perceptions of past molding experiences. This paper shares the results of this survey.     

Improved methods for evaluating the molar mass distributions of cellulose in kraft pulp

Multi‐angle laser light scattering (MALLS) was used to characterize birch kraft pulps with respect to their absolute molecular mass distributions (MMDs). The pulps were dissolved in lithium chloride/N,N‐dimethylacetamide and separated by size exclusion chromatography (SEC). The weight‐average and number‐average molecular masses of the cellulose fractions of the pulps obtained from the absolute MALLS measurements were compared with the molar masses obtained by direct‐standard‐calibration relative pullulan standards. Discrepancies between the two detection methods were found, and two ways of correlating the relative pullulan molar masses to the absolute molar masses were examined. In the first method, the correlation was made over a large range of molecular masses. The second method correlated the molecular masses of the standards to the molecular masses of samples by the calculation of fictitious, cellulose‐equivalent molar masses of the standards. With the preferred second method, a more correct MMD of kraft pulp samples could, therefore, be obtained from an SEC system calibrated with narrow standards. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1170–1179, 2003     

Dissolution of softwood kraft pulps by direct derivatization in lithium chloride/N,N‐dimethylacetamide

A method for the characterization of the molar mass distributions (MMDs) of softwood kraft pulps dissolved in 0.5% lithium chloride (LiCl)/N,N‐dimethylacetamide (DMAc) by size exclusion chromatography is presented. The method is based on derivatization with ethyl isocyanate and the dissolution of samples in 8% LiCl/DMAc. In this study, the derivatization of hardwood kraft pulps did not influence the MMD. In the case of softwood pulps, however, the derivatization decreased the proportion of the high‐molecular‐mass material and increased the proportion of the low‐molecular‐mass material, which resulted in a distribution similar to the MMD of a hardwood kraft pulp. The results suggest that associations between hemicellulose and cellulose in the softwood kraft pulp were ruptured during derivatization. This led to a more correct estimation of the MMD of derivatized softwood kraft pulps than obtained by the dissolution of nonderivatized samples. This new method offers several advantages over derivatization with phenyl isocyanate: a precipitation step is not necessary, it is possible to follow the lignin distribution in the samples, and the method allows very high levels of dissolution of softwood kraft pulps up to a κ number of around 50. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 424–431, 2004     

Characterisation of electrodeposited nanocrystalline Ni–Mo alloys

Ni–Mo nanocrystalline layers were electrodeposited using direct current from citrate–ammonia solutions. The quartz crystal microbalance investigation confirms that the discharge process starts with hydrogen evolution before the onset of the alloy deposition. The grain size was estimated from X-ray line broadening. It decreases when the molybdenum content is increased. It is smaller for layers deposited at pH 9.5 than 8.5. The microhardness exhibits a maximum close to 800 Vickers for _Mo around 17 wt%. For higher _Mo a softening is observed showing a deviation from Hall-Petch behaviour due to small grain size. In deaerated hydrochloric solutions, the layers show a large passivation domain without any pitting. The corrosion currents as well as the passivation currents, higher than for the bulk Hastelloy B alloy, decrease when _Mo is increased.     

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.     

Melamine salts as hardeners for urea formaldehyde resins

Various salts derived from melamine and organic acids were prepared and used as melamine substitutes for melamine urea formaldehyde (MUF) resins. The synthesis of these melamine salts and a detailed characterization of their stoichiometry are described. All salts form 1 : 1 or 1 : 2 stoichiometries in a homogeneous reaction. They crystallize during cooling of the hot and diluted reaction mixture. Both ¹³C–NMR and ¹⁵N–NMR data are reported and point toward the formation of real ionic structures. Most salts have higher water solubility than that of pure melamine and are tested for their ability to substitute melamine in MUF resins. The mechanical and chemical properties of plywood panels made up of traditional MUF resins and mixtures of UF resins with melamine salts are investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1654–1661, 2001     

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.