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.     

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.     

Adaptive Immune Responses in a Multiple Sclerosis Patient with Acute Varicella-Zoster Virus Reactivation during Treatment with Fingolimod

Fingolimod, an oral sphingosine 1-phosphate (S1P) receptor modulator, is approved for the treatment of relapsing forms of multiple sclerosis (MS). The interference with S1P signaling leads to retention particularly of chemokine receptor-7 (CCR7) expressing T cells in lymph nodes. The immunological basis of varicella zoster virus (VZV) infections during fingolimod treatment is unclear. Here, we studied the dynamics of systemic and intrathecal immune responses associated with symptomatic VZV reactivation including cessation of fingolimod and initiation of antiviral therapy. Key features in peripheral blood were an about two-fold increase of VZV-specific IgG at diagnosis of VZV reactivation as compared to the previous months, a relative enrichment of effector CD4+ T cells (36% versus mean 12% in controls), and an accelerated reconstitution of absolute lymphocytes counts including a normalized CD4+/CD8+ ratio and reappearance of CCR7+ T cells. In cerebrospinal fluid (CSF) the lymphocytic pleocytosis and CD4+/CD8+ ratios at diagnosis of reactivation and after nine days of fingolimod discontinuation remained unchanged. During this time CCR7+ T cells were not observed in CSF. Further research into fingolimod-associated VZV reactivation and immune reconstitution is mandatory to prevent morbidity and mortality associated with this potentially life-threatening condition.     

Stability of rare‐earth‐doped spherical yttria‐stabilized zirconia synthesized by ultrasonic spray pyrolysis

Phase stability is one of the crucial requirements for any material that can be used at elevated temperature applications such as thermal barrier coating (TBC). The most traditional TBC material, partially stabilized zirconia, limits the operating temperature due to its phase transformation. Conversely, the low thermal conductivity of fully stabilized zirconia (YSZ) may enable effective reduction in the surface temperature on the coated component, while avoiding deleterious phase transitions, although still being subjected to sintering and grain growth. It has been reported that addition of rare‐earths as dopants to YSZ can significantly increase resistance to grain growth at high temperature. Keeping this under consideration, this work investigates the role of rare‐earths (lanthanum and gadolinium) in increasing thermal stability of YSZ microspheres, the building blocks for high‐temperature photonics for reflective TBC. The spheres were produced by ultrasonic spray pyrolysis, and the doping led to significant improvement of stability by significant inhibition of grain growth. While the individual dopants showed significant growth and sintering inhibition up to 900°C, co‐doping with 4% (in mol) of each (Gd and La) led to coarsening resistance up to 1000°C for 3 hours, when particles retained reasonable spherical features with nanometric crystallite sizes.     

The Importance of Crosslinking and Glass Transition Temperature for the Mechanical Strength of Nanofibers Obtained by Green Electrospinning

Crosslinked particles containing butyl acrylate, methyl methacrylate, and allyl methacrylate are prepared by free‐radical emulsion polymerization. The glass transition temperatures of the polymers are varied by the crosslinking densities in the latex particles. Aqueous acrylate dispersions with polymers of different glass transition temperatures are electrospun with PVA as the matrix polymer. The effects of crosslinking density and T_g on the structure and mechanical properties of the fibers are studied. Crosslinking of unreacted allyl groups is induced by UV irradiation to stabilize the fibers by interparticle crosslinking. Both the ability to undergo interparticle crosslinking and the E modulus depend on the merging of the particles during the electrospinning process.

     

Optimized Growth of Heteroepitaxial (111) NiFe2O4 Thin Films on (0001) Sapphire with Two In‐Plane Variants via Chemical Solution Deposition

(111)‐oriented epitaxial thin films of nickel ferrite (NFO) are grown on c‐plane sapphire [α‐Al₂O₃(0001)] substrates using a chemical solution deposition technique. The processing conditions, including pyrolysis and annealing temperatures, are varied to achieve a film that shows maximum texture and epitaxy. It is shown that increasing the pyrolysis temperature to 400°C and decreasing the annealing temperature to 750°C for 10 min result in the highest degree of texture in the films. Lower film thickness also leads to a higher degree of texture. Microstructural studies confirm an in‐plane epitaxial relationship between the (111) NFO film and the (0001) Al₂O₃ substrate in two variants, [110]_NFO || or .     

A Method for Evaluating Lignin Mobility Distributions Obtained by Capillary Zone Electrophoresis

Abstract

The profile of the mobility distribution of lignin-containing samples depends on type of sample. To facilitate comparison, a procedure for determining the average mobility (μ_av), i.e. the average charge density, of lignin is presented. The procedure is applied to black liquor (Sb), isolated dissolved lignin (Sd) and isolated residual (Sr) lignin samples, obtained from flow-through kraft cooks of softwood. The μ_av of the isolated lignin samples is compared with the concentration of phenol and carboxyl groups and relative molecular size. As the cook proceeds the μ_av for a particular type of lignin sample increases, reflecting an increase in average charge density. The μ_av, measured at pH 12, decreases in the order Sd>Sb>Sr, except at the end of the cook, when the average charge densities of the Sb and Sr samples are similar. Associations between lignin and carbohydrate fragments are proposed to cause the lower mobility of black liquor compared to isolated dissolved lignin. Characterisations performed at pH 10 indicate that the isolated dissolved lignin samples may have a higher pK_a in the middle of the cook than the other samples.     

Homogeneous dispersion of SiO2 nanoparticles in an hydrosoluble polymeric network

The main difficulty still encountered in the elaboration of polymer/silica nanocomposites is the control of the nanoparticles dispersion homogeneity and the stability of the nanoparticle dispersion in the surrounding substance. The innovative point of this work is the elaboration of hybrid networks in aqueous solution performed with ASE (alkali swellable emulsion) thickeners grafted with silica nanoparticles. The thickening ability of the polymer should favour silica nanoparticles dispersion in fluid matrices. Two ASE copolymers were realised by copolymerisation in emulsion of MA (methacrylic acid) and EA (ethyl acrylate) and/or TFEM (trifluoroethyl methacrylate). The substitution of a part of EA by TFEM gave fluorinated ASE copolymers. Their free acid functions were then coupled with different ratio of amine functionalized silica nanoparticles to afford nanocomposites. The amounts of silica nanoparticles in the copolymers were determined by thermogravimetric experiments. Depending on the silica nanoparticles/copolymer ratio in basic aqueous solutions we achieved stable translucent gel like aqueous suspensions of silica nanoparticles containing 1 wt.% of the polymer/SiO₂ nanocomposite.