Stability of ruthenium catalysts supported on TiO2 or ZrO2 in catalytic wet air oxidation

The stability of ruthenium catalysts supported on TiO₂ and ZrO₂ were studied in the wet air oxidation of aqueous solution of succinic and p-hydroxybenzoic acids taken as model effluent and on real effluents from the paper-pulp industry. Catalyst recycling experiments were conducted in batch reactor and long-term stability tests were conducted in trickle-bed reactor. In all experiments, ruthenium and support materials were perfectly stable to leaching, sintering and fouling. Ruthenium catalysts experienced a weak deactivation as they were exposed to air, e.g., in recycling experiments however the loss of activity occurred only after the first exposure and was completely reversible upon catalyst reduction. The deactivation was attributed to an over-oxidation of the catalyst surface particularly noticeable in the case of very small Ru-clusters (1 nm).     

A generalist herbivore in a specialist mode Metabolic,sequestrative, and defensive consequences

Adults of a generalist herbivore, the lubber grasshopper,Romalea guttata, can be converted to functional specialists by feeding them exclusively on catnip,Nepeta cataria. No obvious adverse effects on adult development resulted from this enforced monophagy. Notwithstanding the fact thatR. guttata has had no coevolutionary relationship with this Eurasian mint, it readily sequesters compounds that are identical to or derived from the terpenoid lactones that are characteristic ofN. cataria. R. guttata appears to both biomagnify minor allelochemicals and to sequester metabolites of theNepeta terpenes in its paired defensive glands. The levels of autogenously produced phenolics are not affected by feeding onN. cataria and the defensive secretions of catnip-fed grasshoppers are more repellent to ants than those of wild-fed acridids. Metabolites of theN. cataria monoterpenes are sequestered in the defensive glands when catnip is added to the natural diet ofR. guttata. The ability of a generalist,R. guttata, to facilely bioaccumulate a potpourri of foreign allelochemicals when feeding in a specialist mode is analyzed in terms of its biochemical, physiological, and functional significance. Sequestration is examined as a response to the enteric effronteries represented by the phytochemicals that can be characteristic of the overload in a monophagous diet.     

Esterification and Transesterification of Renewable Chemicals

An overview is given of newly developed Lewis or Brønsted acid and base catalysts for esterification, transesterification and ester interchange reactions. The most relevant applications of these catalysts and reactions in the domain of renewable resources, in particular, oils and fats, are discussed.     

Adaptive speckle imaging interferometry (ASII): New technology for advanced drying analysis of coatings

In this work a new optical technology, ASII, is presented, for the study of film formation from all kinds of dispersed systems, such as latexes, emulsions or solvent-borne suspensions. Various film-forming products have been investigated, including water-borne coatings, on various types of substrates. A wide range of information can be extracted such as objective drying times (dust-free, dry-hard times, etc) or mechanism taking place, thereby offering new possibilities to analyse film formation from complex colloidal systems.     

Aerobic selective oxidation of (hetero)aromatic primary alcohols to aldehydes or carboxylic acids over carbon supported platinum

The synthesis of substituted benzaldehydes, benzoic acids, heterocyclic aromatic aldehydes and acids has been studied via the oxidation of the aromatic alcohols with air under mild pressure (<20 bar) at 100 °C, in the presence of a 1.95 wt.% Pt/C catalyst. The solvent was found to play the most important role in determining the selectivity of the oxidation products. Changing the solvent enabled tuning the reaction either to the aldehyde (pure dioxane), or the carboxylic acid (dioxane/aqueous solution without or with addition of sodium hydroxide). This oxidation method allowed to effectively oxidize many substituted benzylalcohols with various electron-releasing or -attracting groups (NO₂, Me, OMe, Cl, Br, OH, phenyl, …) and heterocyclic alcohols including nitrogen and sulphur atoms (2-thiophenemethanol, 2- and 4-pyridine methanol compounds).     

Sodium Coordination Environments in Silica Films

The local structure centered on sodium after diffusion in silica (Na-SiO₂ samples) has been determined by means of extended X-ray absorption fine structure (EXAFS) studies. The Na-SiO₂ samples are of particular interest because (i) their sodium content can be varied over a wide range of concentration and (ii) their local structure is representative of that of soda–silica glass. EXAFS analyses reveal the existence of a well-defined local structure involving oxygen, sodium, and silicon neighbors. The Na-O, Na-Na, and Na-Si bonds lengths, which amount to 0.23, 0.30, and 0.38 nm, respectively, do not depend on sodium concentration. This environment closely resembles that found in soda–silica glass. Moreover, it is compatible with the "target site" and "the site memory effect" suggested by recent theories of the ionic conductivity in oxide glasses.     

Cell structure and dynamic properties of injection molded polypropylene foams

The cell structure and properties of branched and linear polypropylene (PP) foams containing organically modified nanoclay and maleic anhydride grafted polypropylene (PPMA) have been thoroughly investigated. X-ray diffraction (XRD) and melt rheometry were used to identify the structure and linear viscoelastic properties of the nanocomposites, as well as the effectiveness of two different compatibilizers. These nanocomposites were used in injection molding to investigate their foamability and the influence of experimental conditions such as chemical foaming agent concentration, shot size, back pressure, injection speed, as well as melt temperature and different injection methods on the resulting cell structure of the foams. Quite different results were obtained with the linear and the branched PP. While the foamability of the branched PP was intrinsically good, that of the linear one could largely be improved by modifying its rheological properties and favoring nucleation through the addition of nanoclay. The effect of cell structure on the dynamic mechanical properties of the foams was also investigated using dynamic mechanical analysis (DMA). POLYM. ENG. SCI., 47:1070–1081, 2007. © 2007 Society of Plastics Engineers     

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.     

Mixing in the transition flow regime with helical ribbon agitators

The effects of the non-Newtonian properties on the effective deformation rate, mixing and circulation times and flow behaviour have been investigated in the transition flow regime of mixing systems. Based on the equivalent Couette flow, three models are proposed and are shown to predict similar and drastic increases of the effective deformation rate with the impeller rotational speed in the transition regime. The predictions are shown to fit very well data obtained for various non-Newtonian fluids mixed with helical ribbon agitators, and with literature data for anchor, blade turbine and flat disc agitators. The elasticity along with shear-thinning properties appear to have slight effects on the dimensionless mixing and circulation times in the transition regime, whereas their effects in the laminar regime are quite drastic, as reported by others.     

Deactivation of metal catalysts in liquid phase organic reactions

The paper gives a general survey of the factors contributing to the deactivation of metal catalysts employed in liquid phase reactions for the synthesis of fine or intermediate chemicals. The main causes of catalyst deactivation are particle sintering, metal and support leaching, deposition of inactive metal layers or polymeric species, and poisoning by strongly adsorbed species. Weakly adsorbed species, poisons at low surface coverage and solvents, may act as selectivity promoters or modifiers. Three examples of long term stability studies carried out in trickle-bed reactor (glucose to sorbitol hydrogenation on Ru/C catalysts, hydroxypropanal to 1,3-propanediol hydrogenation on Ru/TiO₂ catalysts, and wet air oxidation of paper pulp effluents on Ru/TiO₂) are discussed.