Serine sublimes with spontaneous chiral amplification

Sublimation of near-racemic samples of serine yields a sublimate which is highly enriched in the major enantiomer; this simple one-step process occurs under relatively mild conditions, and represents a possible mechanism for the chiral amplification step in homochirogenesis.     

Supported ionic liquid phase rhodium nanoparticle hydrogenation catalysts

Rh(0) nanoparticles (ca. 4 nm) dispersed in an ionic liquid (1-n-butyl-3-methylimidazolium tetrafluoroborate) were immobilized within a silica network, prepared by the sol-gel method. The effect of the sol-gel catalyst (acid or base) on the encapsulated ionic liquid and Rh(0) content, on the silica morphology and texture, and on the catalyst alkene hydrogenation activity was investigated. The Rh(0) content in the resulting xerogels (ca. 0.1 wt% Rh/SiO(2)) was shown to be independent of the sol-gel process. However, acidic conditions afforded higher contents of encapsulated ionic liquid and xerogels with larger pore diameters, which in turn might be responsible for the higher catalyst activity in hydrogenation of the alkenes.     

Biotransformations of imbricatolic acid by Aspergillus niger and Rhizopus nigricans cultures

Microbial transformation of imbricatolic acid (1) by Aspergillus niger afforded 1alpha-hydroxyimbricatolic acid (2), while transformation with Rhizopus nigricans yielded 15-hydroxy-8,17-epoxylabdan-19-oic acid (3). When the diterpene 1 was added to a Cunninghamella echinulata culture, the main products were the microbial metabolites mycophenolic acid (4) and its 3-hydroxy derivative 5. All the structures were elucidated by spectroscopic methods. The cytotoxicity of these compounds towards human lung fibroblasts and AGS cells was assessed. While 4 and 5 showed low cytotoxicity, with IC50 values > 1000 microM against AGS cells and fibroblasts, 1alpha-hydroxyimbricatolic acid (2) presented moderate toxicity towards these targets, with IC50 values of 307 and 631 microM, respectively. The structure of 2 is presented for the first time.     

A finite element thermally coupled flow formulation for phase‐change problems

A finite element, thermally coupled incompressible flow formulation considering phase‐change effects is presented. This formulation accounts for natural convection, temperature‐dependent material properties and isothermal and non‐isothermal phase‐change models. In this context, the full Navier–Stokes equations are solved using a generalized streamline operator (GSO) technique. The highly non‐linear phase‐change effects are treated with a temperature‐based algorithm, which provides stability and convergence of the numerical solution. The Boussinesq approximation is used in order to consider the temperature‐dependent density variation. Furthermore, the numerical solution of the coupled problem is approached with a staggered incremental‐iterative solution scheme, such that the convergence criteria are written in terms of the residual vectors. Finally, this formulation is used for the solutions of solidification and melting problems validating some numerical results with other existing solutions obtained with different methodologies. Copyright © 2000 John Wiley & Sons, Ltd.     

Results coming from homogeneous and supported metallocene catalysts in the homo- and copolymerization of olefins

Ethylene, propylene and α-olefins were homo- and copolymerized in the presence of a series of homogeneous catalytic systems consisting of methylaluminoxane (MAO) and group IV metallocenes such as Et(Ind)₂ZrCl₂ (I), Me₂Si(Ind)₂ZrCl₂ (II), Et(2-Me-Ind)₂ZrCl₂ (III), Ph₂C(Flu)(Cp)ZrCl₂ (IV). It was found that the catalytic activity, the incorporation of comonomer in the case of copolymers, and the microstructure of the polymers depend on the catalyst's structure. For heterogeneous catalysts, several supports based on metal oxide compounds have been investigated, with special emphasis in those obtained by the sol-gel preparation technique. The homo- and copolymerization of the monomers in the homogeneous systems studied where also investigated using the same catalyst system, but in a heterogeneous medium. Comparative results from the homogeneous and heterogeneous systems are presented and discussed.