Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Ground state systematics and collective dipole excitations of spheroidally deformed sodium clusters in a diffuse jellium model

We solve the Kohn-Sham equations self-consistently in the local density approximation for spheroidal sodium clusters in the particle range 8 ≤ Z ≤ 40. We use a smooth fermi-like jellium density to simulate the influence of the ions in the surface region and obtain similar results as Ekardt and Penzar, but slightly different regions of prolate-to-oblate transitions. We present the systematics of potential energy curves with respect to transitions between oblate, prolate and spherical shapes. Shape transitions occur at particle numbers 12/14 (prolate/oblate), 18/20/22 (oblate/spherical/prolate) and 30/32 (prolate/oblate), which are in good agreement with experimental results. The quadrupole and hexadecupole overlap of the electron density with the jellium is investigated, showing a strong hexadecupole dependence for selected clusters. Collective dipole resonances are described in a simple sum rule approach, which reveals a double splitting according to the different resonance frequencies along the principal axes of the spheroid. The systematics of the resonance peaks for the larger clusters with Z ≥ 20 is in good agreement with experimental results.     

Prebiotic synthesis of sequential peptides on the Hadean beach by a molecular engine working with nitrogen oxides as energy sources

Addressing the still open question of the prebiotic origin of sequential macromolecules (peptides, nucleic acids) on the primitive Earth, we describe a molecular engine (the primary pump), which works at ambient temperature and continuously generates, elongates and complexifies sequential peptides. This new scenario is based on a cyclic reaction sequence, whose keystep is the activation of amino acids into their N‐carboxyanhydrides (NCA) through nitrosation by NOx. This process could have taken place on tidal beaches; it requires a buffered ocean, emerged land and a nitrosating atmosphere. With the help of geochemical studies and computer simulations of atmosphere photochemistry, we show that the primitive Earth during the Hadean may have satisfied all these requirements. © 2001 Society of Chemical Industry.     

Immunoregulatory functions of paf-acether. VI. Dual effect on human B cell proliferation

The role of paf-acether (paf), a phospholipid cytokine, in the modulation of human B cell function was investigated. Paf, from 1×10⁻⁵ M to 10⁻⁶ M, decreased B cell proliferation induced by both phorbol myristate acetate (PMA) and anti-IgM antibodies (anti-IgM Ab). By contrast, 1×10⁻⁷ M to 1×10⁻⁹ M paf enhanced PMA triggered, but not anti-IgM triggered B cell proliferation. B cell proliferation was modulated between 24 and 72 hr of culture indicating that the effect of paf did not merely reflect a shift in proliferation kinetics. Interestingly, paf also enhanced the spontaneous proliferation of a Burkitt lymphoma-derived B cell line, Raji, which suggests that paf can directly act on B cells. The modulatory effect of paf on peripheral blood B cells was independent of PMA concentration, yet the effect on Raji cells was dependent upon cell density. The data suggest that paf is a potent modulator of B cell function, and may be involved in the control of humoral immune response. Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl Ether Lipids, Tokyo, Japan, May 1989.     

Prediction of environmental stress cracking of polycarbonate from solubility considerations

Simple thermodynamic relationships as well as semiempirical solubility parameter plotting techniques were examined as methods for predicting critical crazing strains of polycarbonate exposed to linear and branched alkanes. In general, measured critical strains correlated with predicted solubilities based on the Flory–Huggins equation. Solubility parameters could also be used to predict critical strains if molecular size differences between specific alkanes were taken into account. These techniques were then extended to polar and hydrogen bonding liquids using two-dimensional solubility parameter plotting representations. A comprehensive listing of critical strains for polycarbonate exposed to over 80 liquids and liquid mixtures is included.     

An analysis of thermal warpage in injection molded flat parts due to unbalanced cooling

To illustrate the potential effect of unbalanced cooling on warpage of flat parts, a simplified two-part analysis is presented. First a computational model for amorphous polymers cooling in an injection molding cavity is presented. The simulation is a finite difference solution of the one-dimensional, transient heat conduction equation with constant material properties. Plastic and mold temperature profiles are calculated through the cooling cycle and the transients from cycle to cycle are included. Temperatures are predicted for both sides of the mold allowing asymmetrical cooling to be analyzed. The model is verified analytically and is in agreement with published data. Secondly, a simplified method of predicting the thermal warpage of a fiat part from calculated temperature profiles is discussed and illustrated. The relative effects on calculated part warpage of asymmetric mold geometry and cooling fluid temperature are predicted with this analysis method. The sensitivity of warpage to these design factors is illustrated for an example part.     

Tar sand extractions with microemulsions: I-the dissolution of light hydrocarbons by microemulsions using 2-butoxyethanol and diethylmethylamine as cosurfactants

For oil sand extractions with microemulsions it is important to disperse large quantities of light hydrocarbons in an aqueous medium. Fundamental studies on the properties of 2-butoxyethanol (BE) and diethylmethylamine (Et₂McN) in water suggest that these two liquids could be more effective cosurfactants than the usual alcohols used for this purpose. The phase diagrams of microemulsions using BE and Et₂MeN as cosurfactants, combined with typical ionic and non-ionic surfactants and typical aliphatic and aromatic hydrocarbons, were therefore investigated and compared with microemulsions based on n-butanol. Although the phase diagrams depend significantly on the nature of the surfactant and of the oil, the monophasic region generally increases with the cosurfactant in the order n-butanol < Et₂McN < BE. With the active mixture BE-cetyltrimethylammonium bromide, temperature has little effect on the phase diagram and NaCl generally destabilizes the microemulsion.     

A wireless embedded tongue tactile biofeedback system for balance control

We describe the architecture of an original biofeedback system for balance improvement for fall prevention and present results of a feasibility study. The underlying principle of this biofeedback consists of providing supplementary information related to foot sole pressure distribution through a wireless embedded tongue-placed tactile output device.Twelve young healthy adults voluntarily participated in this experiment. They were asked to stand as immobile as possible with their eyes closed in two conditions of no-biofeedback and biofeedback. Centre of foot pressure (CoP) displacements were recorded using a force platform. Results showed reduced CoP displacements in the biofeedback relative to the no-biofeedback condition.On the whole, the present findings evidence the effectiveness of this system in improving postural control on young healthy adults. Further investigations are needed to strengthen the potential clinical value of this device.