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.     

Preparation of optically active poly β-propiolactones

Racemic -methyl--n-propyl--propiolactone is readily polymerized with zinc and cadmium chiral glycolates leading to optically active polyesters. The stereoelectivities observed are lower than for oxiranes and thiiranes with the same initiator system. A value of rotatory power for pure enantiomer _o, is deduced from NMR measurements in the presence of chiral solvent. The structure of polymers is discussed on the basis of NMR results.     

Feeding rats with liposomes or fish oil differently affects their lipid metabolism

Two n‐3 polyunsaturated fatty acid (PUFA)‐rich diets differing in their chemical and physical forms were given to rats during 2 wk. Liposomes [phospholipids (PL) organized in bilayer structures] made from a natural marine lipid extract or a mixture of fats containing fish oil [similar fatty acids esterified in triacylglycerols (TAG)] were used. The influence of n‐3 PUFA dietary sources on plasma parameters, i.e. TAG, cholesterol and PL concentrations, was investigated. A similar hypotriglyceridemic effect of n‐3 PUFA from liposomes or fish oil was observed. In contrast, feeding rats with liposomes led to different PL and cholesterol patterns. In the plasma of rats fed liposomes, total cholesterol amounts were positively correlated with PL levels. Liposome and fish oil feedings caused a marked increase in the amounts of n‐3 PUFA, which occurred mainly at the expense of n‐6 PUFA. However, the enrichment in n‐3 PUFA in the different plasma lipid classes differed substantially when ingested in the form of fish oil or liposomes. These results were interpreted in terms of different lipid bioavailability and metabolic fate during the digestive steps and in the liver, with the dietary source.     

Viscoelastic effects on the scratch resistance of polymers: relationship between mechanical properties and scratch properties at various temperatures

Scratch durability of polymer surfaces and coatings is becoming critical for the increasing use of these materials in new applications, replacing other materials with harder surfaces.

Scratch resistance of polymers has been the subject of numerous studies, which have led to specific definitions for plastic deformation characterization and fracture resistance during scratch testing. Viscoelastic and viscoplastic behavior during a scratch process have been related to dynamic mechanical properties that can be measured via dynamic nano-indentation testing. Yet, the understanding of the origin of the fracture process of a polymer during scratch remains approximate. Parameters like tip shape and size, scratch velocity and loading rate, applied strain and strain rates, have been considered critical parameters for the fracture process, but no correlation has been clearly established.

The goal of this work is to define and analyze scratch parameters that relate to mechanical properties. The evolution of scratch resistance parameters as a function of temperature and strain rate, compared to the evolution of dynamic mechanical properties obtained from indentation and uniaxial tensile tests over a range of temperature for poly(methyl methacrylate) (PMMA) helped in identifying a correlation between the tensile stress–strain behavior and scratch fracture toughness.

This correlation brings a new understanding of the origin of the fracture mechanisms during a scratch process. In particular, it is demonstrated that the characteristic strain applied by the indenter is a most relevant parameter to describe the fracture resistance during a scratch process, independently of the indenter geometry.     

Mechanical analysis of hollow fiber membrane integrity in water reuse applications

In order to gain insight into membrane fiber failure (i.e., loss of integrity), properties of five hollow fiber membranes and four hollow fiber modules were evaluated. Specifically, membrane material, membrane symmetry, fiber modulus of elasticity, fiber diameter and thickness, module potting technique, module flow pattern (inside-out or outside-in), and coliform breakthrough were investigated. The approach combined evaluation of the above properties with mathematical modeling of structure-fluid interactions to comprehensively evaluate the properties most important for maintaining hollow fiber membrane integrity. Tensile strength testing revealed that the strongest fiber was an asymmetric polyacrylonitrile membrane fiber. The weakest fiber was a symmetric polyethylene membrane fiber. Pilot plant testing on the four membrane modules revealed that membrane symmetry may be a more important factor than potting technique for hollow fiber integrity. Results from the SEM and tensile testing were used as input to a finite element analysis model used to evaluate time-dependent structure-fluid interactions. It was found that additional stresses at the juncture of the potting material and the hollow fiber membranes exist. These stresses likely lead to the formation of fractures.