Hydrolysis of new phthalimide-derived esters catalyzed by immobilized lipase

The last step of the production of four phthalimide-derived acids, designed to act as antiasthma drugs, was performed by enzymatic hydrolysis of the respective methyl or ethyl esters. The esters 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic methyl ester (PHT-MET), 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic ethyl ester, 4-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester, and 2-(1,3-dioxo-1, 3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester were hydrolyzed by immobilized lipase. The enzymatic reaction could be used only to produce the desired 4-substituted compounds. The best result that was found to hydrolysis of PHT-MET, and, therefore, that ester was selected for optimization experiments in a three-phase system. Reactions were performed with solid biocatalyst (Lipozyme® RM IM), organic solvent phase (ethyl acetate), and aqueous phase (saturated Na₂CO₃ solution). To optimize the reaction conditions, an experimental design optimization procedure was used. The variables studied were the amount of enzyme, the temperature, and the volume of the aqueous solution. Time course experiments were then performed for different initial enzyme concentrations (0.5, 0.9, and 1.4 U_H/mL of solvent). The optimized reaction conditions found were 20 mg of Lipozyme (0.9 U_H/mL_solvent) and 5.0 mL of Na₂CO_3(sat) at 40°C for 6 h.     

catena-Poly­[[di­aqua(1,10-phen­anthroline-N,N′)­manganese(II)]-μ-(thiosulfato-O:S)] and bis(2,2′-bipyridyl-N,N′)(tetra­thionato-O,O′)manganese(II)

The structures of [Mn(S₂O₃)₂(C₁₂H₈N₂)(H₂O)₂] and [Mn(S₄O₆)(C₁₀H₈N₂)₂] are presented. The former consists of pairs of polymeric chains formed by manganese polyhedra bridged by bidentate thio­sulfate anions, which are in turn related to each other by a pseudo-twofold screw axis. The latter has crystallographic twofold symmetry and consists of monomers in which manganese displays its typical octahedral coordination provided by the bidentate bites of two bi­pyridine bases and a tetra­thionate anion, which is, to our knowledge, the first chelating tetra­thionate to be reported in the literature.     

The mobility in disordered molecular systems with energies given by a charge-induced dipoles interaction

We investigate the field dependence of the mobility in a model for a disordered molecular system containing spatial and energetic disorders. In this model we assign an isotropic polarizability to each site and take the site energies to be the site polarization energies, the interaction energy of a charge in the given site with the induced dipoles in the neighboring sites. This model was shown, in a previous publication, to contain short-ranged energetic correlations and we show in this work that this correlation produces a charge mobility proportional to the exponential of the square root of the applied field, the Poole-Frenkel dependence observed in various disordered organic materials, over a significant range of fields. We present an expression for the field dependence of the mobility in terms of the average intersite separation and of the isotropic polarizability of the electronic states, the two model parameters.     

Stress and Strain Analysis of Pipelines with Localized Metal Loss

This paper presents the analysis of stress and strain data acquired with the finite element method and with tests that used post-yielding strain gages bonded onto the external surface of pipes that suffered thickness metal loss and that had been loaded with internal pressure. These metal loss areas were produced by three different processes: actual internal corrosion, careful machining of external patches by spark-erosion, and milling of internal or external patches to simulate limited or extensive strip corrosion defects with depths up to 70% of the pipe’s thickness. Results show that: (1) the extensive longitudinal internal or external defect areas behave as extensive strips with a high degree of freedom to deform elastically and plastically in the circumferential and thickness directions, and (2) large restraints are offered to the longitudinal strains by the non-corroded thick walls parallel to the strip. Using the above experimental observation, a simple mathematical model was developed to predict the burst pressure of pipes with longitudinal extensive and reasonably constant depths of metal loss. This model employed thin-pipe-strength-of-material equations associated to a bulging correction factor, the material’s uniaxial ultimate strength and the von Mises criterion. The onset of plastic collapse predicted by the simple model was successfully compared with results determined from actual hydrostatic tests that were carried out with full scale pipe specimens and from finite element results generated by the use of a commercial program. The developed model was also helpful in showing that the yield and burst behaviors of new or corroded pipeline specimens under laboratory test conditions can be directly compared and extended to the yield and burst behaviors of buried pipeline in field operation.     

Near wall characterization of the flow over a two-dimensional steep smooth hill

Near-wall data for the strongly perturbed flow in a neutrally stable boundary layer encountering a steep, smooth, two-dimensional hill are presented. Observations were made on the centerplane of a water channel at thirteen stations relative to the hill by laser Doppler anemometry. The large reverse flow region that is formed on the lee of the hill was particularly scrutinized through seven measuring stations. Results are presented for the mean and turbulent properties of the flow. Wall shear stress was evaluated through fitting procedures that resorted to the near wall behavior of the velocity profile. Logarithmic fits as well as predictions through the Reynolds stress profiles are also presented.     

Analysis of Hopf and Takens–Bogdanov Bifurcations in a Modified van der Pol–Duffing Oscillator

We analyze a modified van der Pol–Duffing electronic circuit, modeled by a tridimensional autonomous system of differential equations with Z₂-symmetry. Linear codimension-one and two bifurcations of equilibria give rise to several dynamical behaviours, including periodic, homoclinic and heteroclinic orbits. The local analysis provides, in first approximation, the different bifurcation sets. These local results are used as a guide to apply the adequate numerical methods to obtain a global understanding of the bifurcation sets. The study of the normal form of the Hopf bifurcation shows the presence of cusps of saddle-node bifurcations of periodic orbits. The existence of a codimension-four Hopf bifurcation is also pointed out. In the case of the Takens–Bogdanov bifurcation, several degenerate situations of codimension-three are analyzed in both homoclinic and heteroclinic cases. The existence of a Hopf–Shil'nikov singularity is also shown.     

The Existence Problem for Steiner Networks in Strictly Convex Domains

We consider the existence problem for ‘Steiner networks’ (trivalent graphs with 2π/3 angles at each junction) in strictly convex domains, with ‘Neumann’ boundary conditions. For each of the three possible combinatorial possibilities, sufficient conditions on the domain are derived for existence. In addition, in each case explicit examples of nonexistence are given.     

Excess thermodynamics properties of propyl propanoate+hexane+cyclohexane at 298.15 K

Summary In this paper we present excess molar volumes and excess molar enthalpies of binary and ternary mixtures containing propyl propanoate, hexane and cyclohexane as components at 298.15 K. Excess molar volumes were calculated from the density of the pure liquids and mixtures. The density was measured using an Anton Paar DMA 60/602 vibrating-tube densimeter. Excess molar enthalpies were obtained using a Calvet microcalorimeter