Cartesian currents,weak diffeomorphisms and existence theorems in nonlinear elasticity

Summary In this paper we introduce some new classes of functions, among these a class of weak diffeomorphisms. In these classes we prove by direct methods the existence of minimizers for several kinds of variational integrals. In particular, we prove the existence of one-to-one orientation-preserving maps that minimize suitable energies associated with hyperelastic materials. The minimizers are also proved to satisfy equilibrium equations. Finally radial deformations are discussed in connection with cavitation.     

Analysis of citrates and benzoates used in poly(vinyl chloride) by supercritical fluid extraction and gas chromatography

Supercritical fluid extraction (SFE) has been demonstrated to be a useful tool in the determination of additives in polymeric materials. This paper describes the determination of some citrates and benzoates in poly(vinyl chloride) blended with 33–34% of plasticizer using off-line SFE followed by gas chromatography. Experimental factors affecting SFE have been studied by gravimetric analysis, followed by analysis of the extracts using a gas chromatograph equipped with a flame ionization detector. The extraction process is governed by the solubility of the plasticizers in the supercritical fluid or by their diffusion through the polymer matrix, which depend on the pressure and temperature used. Maximum extraction (>99%) is obtained at pressures and temperatures higher than 40 MPa and 80 °C, respectively. Due to purge losses, the collection efficiency of plasticizers into a liquid solvent ranges from 85 to 90%. The applicability of the SFE method is demonstrated using real samples and comparing the results with those obtained by conventional Soxhlet extraction.     

The Effect of Preparation Method and Calcination Temperature on the Crystallite Size and Surface Area of Perovskite-Type SrFeO x

We have investigated the synthesis of perovskite-type SrFeO_x (2.5 x 3.0) using three preparative methods: sol-gel, mechanochemical processing and solid state reactions at high temperature of the corresponding oxides. The sample obtained after calcination of the gel from sol-gel method, contained the least amount of strontium carbonate impurity. The amount of strontium carbonate impurity decreased with the increase in calcination temperature. Perovskites obtained have been characterized by X-ray diffraction (XRD) and nitrogen adsorption isotherms. Samples obtained from three methods have been compared with respect to calcination temperature, crystallite size and specific surface area.Issued as NRCC No. 46479.     

Characterization and complementation of a Pichia stipitis mutant unable to grow on d-xylose or l-arabinose

Pichia stipitis CBS 6054 will grow on d-xylose, d-arabinose, and l-arabinose. d-Xylose and l-arabinose are abundant in seed hulls of maize, and their utilization is important in processing grain residues. To elucidate the degradation pathway for l-arabinose, we obtained a mutant, FPL-MY30, that was unable to grow on d-xylose and l-arabinose but that could grow on d-arabinitol. Activity assays of oxidoreductase and pentulokinase enzymes involved in d-xylose, d-arabinose, and l-arabinose pathways indicated that FPL-MY30 is deficient in d-xylitol dehydrogenase (D-XDH), d- and l-arabinitol dehydrogenases, and d-ribitol dehydrogenase. Transforming FPL-MY30 with a gene for xylitol dehydrogenase (PsXYL2), which was cloned from CBS 6054 (Gen Bank AF127801), restored the D-XDH activity and the capacity for FPL-MY30 to grow on l-arabinose. This suggested that FPL-MY30 is critically deficient in XYL2 and that the d-xylose and l-arabinose metabolic pathways have xylitolas a common intermediate. The capacity for FPL-MY30 to grow on d-arabinitol could proceed through d-ribulose.     

Synthesis and structural characterisation of [(Ph3P)AuCo(CO)3(PPh3)]

Summary [(Ph₃P)AuCo(CO)₃(PPh₃)] has been synthesised from [(Ph₃P)AuCo(CO)₄], PPh₃v and Me₃NO in acetonitrile. Its molecular structure, determined by single-crystal x-ray crystallography, consists of an almost linear P-Au-Co-P arrangement in which the Co atom is in a slightly distorted trigonalbipyramidal geometry, with the Au and P atoms occupying the apical sites. The Au-Co bond length of 2.450(1) ? is shorter than that reported for [(Ph₃P)AuCo(CO)₄]. The carbonyl ligands are bent towards the Au atom and the mean Au-Co-C angle is 81(1)°.     

Formation of the unusual alkynyl carboxamide complex, C2H5N(H)C(O)CC[Co2(CO)6]CCo3(CO)9

The reaction of the cluster complex HCC[Co₂(CO)₆]CCo₃(CO)₉ with (or without) BrCCo₃(CO)₉ under Cadiot-Chodkiewicz coupling conditions gave the unusual alkynyl carboxamide complex C₂H₅N(H)C(O)CC[Co₂(CO)₆]CCo₃(CO)₉ rather than a coupled product containing two tricobalt cluster units. Steric demands imposed by the Co₃ cluster allow attack at the least hindered alkyne carbon and stabilise the formed ynamine, so allowing subsequent CO insertion. The product has been characterised by X-ray crystallography.     

Kinetically inert transition metal complexes that reversibly bind to DNA

Transition metal complexes that reversibly bind to DNA have been studied for almost 30 years. In the last few years a variety of new systems have been developed, employing a range of metal ions and ligand architectures. In many cases, high affinity binding and specific selectivities have been observed. These complexes display properties that make them attractive as probes of DNA structure and function, suggesting that they may find a r?le as prototypical tools for a spectrum of applications, from basic molecular biology to medicine. This review presents an overview of some of the structures and properties of such complexes.     

Binary mixtures based on polycaprolactone and cellulose derivatives

Pyrolytic process has a promising potential for the environmentally friendly upgrading of lignocellulosic and plastic waste. Thermogravimetry and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) were used to get information about the reactive decomposition of PCL in binary mixtures with microcrystalline cellulose (MC) or sisal fibres (SF). Preliminary thermogravimetric investigation showed that biomass is thermally degraded at lower temperatures than PCL and this process has a predominant influence on the thermal behaviour of the mixtures. Discrepancies between the experimental and predicted TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. It was found that reactivity of PCL was slightly increased in PCL-SF binary mixtures. Evolution of acidic products from cellulose and hemicelluloses decomposition may promote PCL degradation in binary mixtures with SF. It seems that the co-pyrolysis process could have potential for the environmentally friendly transformation of biocomposites.     

Synthesis and conformational analysis of novel N(OCH3)-linked disaccharide analogues

N(OMe)-linked disaccharide analogues, isosteric to the corresponding natural disaccharides, have been synthesized by chemoselective assembly of unprotected natural monosaccharides with methyl 6-deoxy-6-methoxyamino-alpha-D-glucopyranoside in an aqueous environment. The coupling reactions were found to be chemo- and stereoselective affording beta-(1-->6) disaccharide mimics when using Glc and GlcNAc; in the case of Gal, the beta-anomer was prevalent (beta:alpha=7:1). An iterative method for the synthesis of linear N(OMe) oligosaccharide analogues was demonstrated, based on the use of an unprotected monosaccharide building block in which an oxime functionality at C-6 is converted during the synthesis into the corresponding methoxyamino group. The conformational analysis of these compounds was carried out by using NMR spectroscopy, ab initio, molecular mechanics, and molecular dynamics methods. Optimized geometries and energies of fourteen conformers for each compound have been calculated at the B3LYP/6-31G* level. Predicted conformational equilibria were compared with the results based on NMR experiments and good agreement was found. It appears that N(OMe)-linked disaccharide analogues exhibit a slightly different conformational behavior to their parent natural disaccharides.