Diffusion of hydrocarbon mixtures in MFI zeolite: Influence of intersection blocking

Branched and cyclic hydrocarbons such as iso-butane, 2-methylpentane, 3-methylpentane, 2,2-dimethyl-butane and benzene are preferentially adsorbed at the intersections of the channels of MFI zeolite; they serve as bottlenecks for molecular traffic in mixtures with linear C1–C6 alkanes. Molecular dynamics simulations show that as the loadings of tardier iC4, 2MP, 3MP, 22DMB, and Bz is progressively increased to four molecules per unit cell the diffusivity of the more mobile linear alkane reduces nearly to zero. The reduction in the n-alkane diffusivity is quantitatively similar irrespective of the branched/cyclic hydrocarbon.     

CFD simulation of the high shear mixing process using kinetic theory of granular flow and frictional stress models

In order to enhance process understanding and to develop predictive process models in high shear granulation, there is an ongoing search for simulation tools and experimental methods to model and measure the velocity and shear fields in the mixer. In this study, the Eulerian-Eulerian approach to model multiphase flows has been used to simulate the mixer flow. Experimental velocity profiles for the solid phase at the wall in the mixer have been obtained using a high speed camera following the experimental procedure as described by Darelius et al. [2007a. Measurement of the velocity field and frictional properties of wet masses in a high shear mixer. Chemical Engineering Science, 62, 2366-2374]. The governing equations for modelling the dense mixer flow have been closed by using closure relations from the kinetic theory of granular flow (KTGF) combined with frictional stress models. The free slip and partial slip boundary conditions for the solid phase velocity at the vessel wall have been utilized. The partial slip model originally developed for dilute flows by Tu and Fletcher [1995. Numerical computation of turbulent gas-solid particle flow in a 90^° bend. A.I.Ch.E. Journal, 41, 2187-2197] has been employed. It was found that the bed height could be well predicted by implementing the partial slip model, whereas the free slip model could not capture the experimentally found bed height satisfactorily. In the simulation, the swirling motion of the rotating torus formed was over-predicted and the tangential wall velocity was under-predicted, probably due to the fact that the frictional stress model needs to be further developed, e.g. to tackle cohesive particles in dense flow. The advantage of using the Eulerian-Eulerian approach compared to discrete element methods is that there is no computational limitation on the number of particles being modelled, and thus manufacturing scale granulators can be modelled as well.     

Self-assembling multimeric integrin alpha5beta1 ligands for cell attachment and spreading

Substrates utilising clustered arginine-glycine-aspartic acid (RGD) ligand displays support greater cell adhesion over random displays. However, cell adhesion to integrin alpha5beta1 requires the synergy site on the 9th type III fibronectin domain (FIII) in addition to RGD on the 10th FIII domain. Here, we have designed and expressed soluble protein chimeras consisting of an N-terminal 9th-10th FIII domain pair, IgG-derived hinge and leucine zipper-derived helix; the latter mutated to yield di-, tri- and tetrameric coiled coils and thus self-assembling, multimeric integrin alpha5beta1 ligands. A unique C-terminal cysteine was appended to the helix to facilitate 'anchoring' of the chimeras with a defined orientation on a surface. Size-exclusion chromatography and circular dichroism demonstrated that the chimeras self-assembled as multimers in solution with defined secondary structures predicted from theoretical calculations. Biotinylation via a thioether bond was used to selectively bind the chimeras to streptavidin-coated surfaces, each of which was then shown to bind integrin alpha5beta1 by surface plasmon resonance. Spreading of fibroblasts to surfaces derivatised with the chimeras was found to proceed in the order: tetramer > trimer > dimer > monomer. Thus, we describe novel polyvalent integrin alpha5beta1 ligands for facile derivatisation of substrates to improve cell adhesion in vitro.     

Exposure to diesel exhaust induces changes in EEG in human volunteers

Background  

Ambient particulate matter and nanoparticles have been shown to translocate to the brain, and potentially influence the central nervous system. No data are available whether this may lead to functional changes in the brain.     

Inverse gas chromatography for the determination of the dispersive surface free energy and acid–base interactions of a sheet molding compound. I. Matrix material and glass

Sheet molding compound is a material composed of a polyester thermosetting matrix with a thermoplastic, an inorganic filler, a metal oxide, reinforcement fibers, and material performance enhancers embedded in the crosslinked matrix. To achieve the optimum mechanical properties required for the composite material, the surface free energy of the polyester composite needs to be understood. In this study, the composite matrix and glass reinforcement fibers are compared with respect to their surface free energy and acid–base characteristics on the basis of inverse gas chromatography measurements. The inverse gas chromatography results for the matrix and glass are compared to previous results found for sized and unsized cellulosic fibers. The inverse gas chromatography data are used to assess chemical modifications performed on the biobased fibers to predict improvements in the fiber/matrix interaction, and this provides inferences on the overall composite cohesion. Our results show first that any fiber reinforcement system for the polyester composite material has to be acidic to promote good adhesion as the matrix system is very basic and second that the individual dispersive surface energies of the components of the matrix interact in a weighted average to determine the overall surface energy of the composite. Also, a commercial glass reinforcement sized for polyester has been found to have a lower interaction parameter than literature values for cellulosic fibers. This finding suggests that cellulosic fibers might have an advantage in competing with a conventional glass‐fiber reinforcement system in fiber/matrix bonding for sheet molding compound composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New aspects for heterogeneous cobalt-catalyzed hydroamination of ethanol

Gas-phase hydroamination of ethanol and ammonia over supported cobalt on silica catalysts was investigated at 103 kPa. Besides the desired products, mono-, di- and triethylamine, acetonitrile, diethylimine, and hydrocarbons (methane, ethene, ethane, propane, and propene) were identified as byproducts. The formation of hydrocarbons was found to depend on the cobalt loading of the catalyst and on the pretreatment of the catalyst. Guaranteeing a sufficient reduction of the cobalt catalyst allows a reduction in the selectivity of hydrocarbons from 25 to 10 mol% at a constant conversion of 90%. In addition, rapid deactivation of the catalyst was observed in the absence of hydrogen. The deactivation was ascribed to the interaction of ammonia with the catalyst and is largely reversible. Carbonaceous species are present on the spent catalyst, as shown by temperature-programmed reduction. These species are thought to be responsible for a slow deactivation in the presence of hydrogen.     

Towards monitoring electrostatics in gas–solid fluidized beds

The electrostatic charge distribution in a lab‐scale 2‐D fluidized bed of 900 µm glass beads was determined using arrays of induction probes, and the influence of relative humidity and superficial gas velocity was examined. The bubble presence, relative humidity, and superficial gas velocity were found to influence charge separation. Bipolar charging was observed; the net charge build‐up was found to be negligible. Moreover, the system was monitored by applying the attractor comparison method to the electrostatic charge signals from an induction probe. It was concluded that this approach can indeed be used to monitor changes in the electrostatic behaviour.     

Effects of Aramchol on in vitro bile cholesterol crystallization and bile acid detergency

The hydrophilic bile acid ursodeoxycholic acid may dissolve cholesterol gallstones and is beneficial in cholestatic liver diseases. The C20 fatty acid‐bile acid conjugate arachidyl amido cholanoic acid (Aramchol) could be a more effective option. We therefore studied its effects on cholesterol crystallization and on bile salt‐induced cytotoxicity. Effects of Aramchol at therapeutically relevant concentrations on crystallization in supersaturated model biles (by microscopy and chemical measurement), on the ternary cholesterol‐taurocholate‐phosphatidylcholine phase diagram, and on micelle ? vesicle transitions (by serial dilution or by incubation of cholesterol‐phosphatidylcholine vesicles with taurocholate) were evaluated. Effects on bile salt‐induced cytotoxicity were determined in erythrocytes and CaCo2 cells. Incorporation of Aramchol in model biles did not change micellar cholesterol solubilization, induced a small rightward shift of crystal‐containing zones of the ternary phase diagram, exerted no appreciable effects on vesicle ? micelle transitions and had only minor effects on cholesterol crystallization. Bile salt‐induced cytotoxicity was increased by Aramchol in all models. Since Aramchol does not affect cholesterol crystallization, its previously reported beneficial effects in animal gallstone models should relate to other mechanisms. Since Aramchol increases bile salt detergency, it is not likely to be beneficial in cholestatic liver disease.     

Electrodeposition of PbO2 and Bi–PbO2 on Ebonex

Electrodeposition of PbO2 and Bi–PbO2 on Ebonex was carried out under various conditions, and the surfaces and coating/substrate interfaces examined by SEM, XPS and SIMS. Excellent adhesion to Ebonex was obtained with both crystalline and amorphous surfaces. Low plating temperatures resulted in dark grey, bright PbO2 and black, mirror-like Bi–PbO2 surfaces. Extrapolation of electrode lifetime test data indicated corrosion rates of 716 m yr–1 for PbO2 and 158 m yr–1 for Bi–PbO2.