Solid acid (superacid) catalyzed regioselective adamantylation of substituted benzenes

Adamantylation of substituted benzenes with 1-bromo-adamantane was catalyzed by solid acids including acidic ion exchange and ionomer resins, HY zeolite, sulfated zirconia and supported superacids on HY zeolite and SiO₂. Adamantylation generally takes place in excellent yield giving predominantly para products without formation of byproducts. The reactions did not require the usual workup of Friedel-Crafts reactions as catalysts were simply filtered of. Cross-linked polystyrene resin sulfonic acid (Amberlyst) was found particularly suitable as besides its high catalytic activity, high regioselectivity was observed with almost exclusive formation ofp-adamantylated benzenes. AMI, PM3 and MNDO semiempirical calculations of heats of formation showed that of all regioisomers, the para isomer is the most stable. The temperature dependence of adamantylation was also investigated allowing the optimization ofp-substituted product in high yield and excellent selectivity. Lack of isomerization of 1-p-tolyla-damantane using solid (Amberlyst, Nafion-H) and liquid acids (neat and modified trifluoromethanesulfonic acid) indicates absence of product isomerization, while the intramolecular rearrangement of the intermediate arenium complex is still possible.Catalysis by solid superacids, Part 30. For part 29, see ref.[1A].     

The effects of clay dispersion on the mechanical,physical, and flame‐retarding properties of wood fiber/polyethylene/clay nanocomposites

In this study, nanosized clay particles were introduced into wood fiber/plastic composites (WPCs) to improve their mechanical properties and flame retardancy, which are especially important in various automotive and construction applications. A high degree of exfoliation for nanoclay in the wood fiber/high density polyethylene (HDPE) composites was successfully achieved with the aid of maleated HDPE (PE‐g‐MAn), through a melt blending masterbatch process. The structures and morphologies of the composites were determined using X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. This article presents the effects of clay content and degree of clay dispersion on the mechanical and physical properties and flame retardancy of wood fiber/HDPE composites that contained a small amount of clay, in the range of 3–5 wt %. We concluded that achieving a higher degree of dispersion for the nanosized clay particles is critical to enhance the mechanical properties and the flame retardancy of WPCs when small amounts of clay are used. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Production of H<Subscript>2</Subscript>S and properties of sulfite reductase from selected strains of wine-producing yeasts

Correlation between H₂S productivity (p) and sulfite reductase activity (A) was estimated for seven wine-producing yeasts. It was described by a linear function p=f(A), the slope of which depended on the yeast strain. The most intensive H₂S synthesis by all the examined yeasts was observed within the early logarithmic growth phase, either in nitrogen abundance and SO₂ presence, or in nitrogen deficient and SO₂-free medium. Sulfite reductase from all the strains was optimally active at pH close to 7.4. The enzyme from cryophilic yeasts displayed maximum activity at approximately 16 °C, and from mesophiles at 22–26 °C. The preparations showed different affinities toward sulfite (K_m of 16.7–67.5 M). Values of activation energy in sulfite reduction depended on the yeast, and ranged from 14.07 to 67.04 kJ mol^–1.     

Steam hydration-reactivation of FBC ashes for enhanced in situ desulphurization

Bed and fly ashes originating from industrial-scale fluidized bed combustors (FBCs) were steam hydrated to produce sorbents suitable for further in situ desulphurization. Samples of the hydrated ash were characterized by X-ray diffraction analysis, scanning electron microscopy and porosimetry. Bed ashes were hydrated in a pressure bomb for 30 and 60 min at 200 °C and 250 °C. Fly ash was hydrated in an electrically heated tubular reactor for 10 and 60 min at 200 °C and 300 °C. The results were interpreted by considering the hydration process and the related development of accessible porosity suitable for resulphation. The performance of the reactivated bed ash as sulphur sorbent improved with a decrease of both the hydration temperature and time. For reactivated fly ash, more favourable porosimetric features were observed at longer treatment times and lower hydration temperatures. Finally, it was shown that an ashing treatment (at 850 °C for 20 min) promoted a speeding up of the hydration process and an increase in the accessible porosity.     

In situ X-ray diffraction study of self-forming barriers from a Cu-Mn alloy in 100 nm Cu/low-k damascene interconnects using synchrotron radiation

An in situ study of self-forming barriers from a Cu-Mn alloy was performed to investigate the barrier growth using X-ray diffraction on damascene lines. The associated evolution in interconnect texture and Cu stress was also observed. The shift in Cu diffraction peak position was used to determine the change in Mn concentration and hence, estimate the thickness of the MnSi_xO_y barrier. The observed peak shift followed a log(t) behaviour and is described well by metal oxidation kinetics, following the field enhanced diffusion model. We used multiple anneal temperatures to study the activation of the formation process, demonstrating a faster barrier formation with higher ion excitation. A strong [1 1 1] Cu texture was shown to develop during the anneal in contrast to traditional PVD barrier systems. Finally, the stress in the 100 nm Cu lines was calculated, observing a large in-plane relaxation when using a self-forming barrier due to reduced confinement.     

Antioxidant and lipoxygenase inhibitory activities of pumpkin seed extracts

Pumpkin seeds have been implicated in providing health benefits. However their antioxidant or anti-inflammatory activity of their extracts has never been studied. Therefore, four commercially available pumpkin seeds were treated with two different extraction methodologies in order to obtain fractions with different content. The extracts were screened for their antioxidant activity using 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay and for their inhibitory activity against lipid peroxidation catalyzed by soybean lipoxygenase.Most extracts tested have demonstrated radical scavenging activity, which depends on their total phenolic content, with fractions rich in phenolics showing the strongest activity. On the other hand, the phenolic content of extracts does not determine their activity against lipoxygenase, as acetone and polar lipid fractions are its strongest inhibitors. The presence of molecules being able to scavenge radicals and inhibit lipoxygenase in pumpkin seeds may in part explain the health benefits attributed to them.     

Solution process of suspension poly(vinyl chloride) in cyclohexanone by means of a viscometer

To study the structure of grains of suspension poly(vinyl chloride) (PVC), the authors applied a capillary viscometer for cyclic measurements of viscosity of the PVC–cyclohexanone solution during dissolution of the polymer. Final concentration of the solution was 0.5–1.0 g/100 cm³ and the measurements were made at temperatures of 313, 333, 353, and 373 K. It was found that at 353 K, a temperature close to the glass transition temperature of PVC, the curve describing changes of viscosity vs. the dissolution time has a pronounced maximum. It follows from a preliminary analysis of the obtained results that this maximum corresponds to the viscosity of a PVC solution in which average apparent mass is many times larger than true average molecular mass of the studied sample. It mans that into the solution enter single chains and some formations, called microdomains in the literature, that are composed of tens of macromolecules. The microdomains disintegrate later to single macromolecules.     

Fabrication of Fischer–Tropsch Catalysts by Deposition of Iron Nanocrystals on Carbon Nanotubes

The fabrication of supported catalysts consisting of colloidal iron oxide nanocrystals with tunable size, geometry, and loading—homogeneously dispersed on carbon nanotube (CNT) supports—is described herein. The catalyst synthesis is performed in a two‐step approach. First, colloidal iron and iron oxide nanocrystals with a narrow size distribution are produced. Second, the nanocrystals are attached to CNT grains serving as support structure. Important features, like iron loading and nanocrystal density on the CNT support, are controlled by changing the nanocrystal concentration and ligand concentration, respectively. The Fischer–Tropsch performance reveals these new materials to be active, selective toward lower olefins (60% C of hydrocarbons produced in the absence of promoters), and remarkably stable against particle growth.