Influence of drying and wetting on the wave propagation in partially saturated soils

The propagation of sound waves in Del Monte sand filled by an air-water mixture is studied by a linear model. Even if it does not include an operator to describe the hysteresis of the capillary pressure curve, hysteresis is accounted for: the wave analysis is performed for the two limit cases of main drying and main wetting. In the van Genuchten law both drying and wetting data are applied. Four waves appear: one transversal wave and three longitudinal waves. For the waves driven mainly by the skeleton it could be expected that the influence of consideration of the hysteresis in the capillary pressure curve is negligible. In contrast, the numerical results for the waves driven by the pore fluids exhibit a smaller influence than expected. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

VLES Modeling of Flow Over Walls with Variably-shaped Roughness by Reference to Complementary DNS

Turbulent flow over variably-shaped rough walls, characterized by either a regular or a random arrangement of axisymmetric roughness elements in an open channel flow configuration, is investigated computationally within a VLES (Very Large Eddy Simulation) framework by utilizing a volumetric forcing-based roughness model. The prime objective of the present work is to assess the roughness model’s capability to predict mean velocities and turbulent intensities in conjunction with this recently formulated hybrid LES/RANS (Reynolds-Averaged Navier-Stokes) model. The friction velocity-based Reynolds number is in the range Re_τ =?460 ? 500. A non-dimensional drag function accounting for the shape of the roughness elements is introduced and evaluated based on the results of complementary direct numerical simulations (DNS). The dynamics of the residual motion of the presently adopted VLES methodology is described by an appropriately modified elliptic-relaxation-based ζ ? f (\(\zeta =\overline {v^{2}}/k\)) RANS model.     

Synthesis of 2,3-benzoxepins by sequential cyclopropanation/ring-enlargement reactions of benzopyrylium triflates with diazoesters

Functionalized 2,3-benzoxepins were prepared by cyclopropanation of benzopyrylium triflates with diazoesters and subsequent TFA-mediated ring enlargement.     

Engineering Rieske Non‐Heme Iron Oxygenases for the Asymmetric Dihydroxylation of Alkenes

The asymmetric dihydroxylation of olefins is of special interest due to the facile transformation of the chiral diol products into valuable derivatives. Rieske non‐heme iron oxygenases (ROs) represent promising biocatalysts for this reaction as they can be engineered to efficiently catalyze the selective mono‐ and dihydroxylation of various olefins. The introduction of a single point mutation improved selectivities (≥95 %) and conversions (>99 %) towards selected alkenes. By modifying the size of one active site amino acid side chain, we were able to modulate the regio‐ and stereoselectivity of these enzymes. For distinct substrates, mutants displayed altered regioselectivities or even favored opposite enantiomers compared to the wild‐type ROs, offering a sustainable approach for the oxyfunctionalization of a wide variety of structurally different olefins.     

The influence of SO2 and NO2 impurities on CO2 gas hydrate formation and stability

The sequestration of industrially emitted CO(2) in gas hydrate reservoirs has been recently discussed as an option to reduce atmospheric greenhouse gas. This CO(2) contains, despite much effort to clean it, traces of impurities such as SO(2) and NO(2) . Here, we present results of a pilot study on CO(2) hydrates contaminated with 1% SO(2) or 1% NO(2) and show the impact on hydrate formation and stability. Microscopic observations show similar hydrate formation rates, but an increase in hydrate stability in the presence of SO(2). Laser Raman spectroscopy indicates a strong enrichment of SO(2) in the liquid and hydrate phase and its incorporation in both large and small cages of the hydrate lattice. NO(2) is not verifiable by laser Raman spectroscopy, only the presence of nitrate ions could be confirmed. Differential scanning calorimetry analyses show that hydrate stability and dissociation enthalpy of mixed CO(2)-SO(2) hydrates increase, but that only negligible changes arise in the presence of NO(2) impurities. X-ray diffraction data reveal the formation of sI hydrate in all experiments. The conversion rates of ice+gas to hydrate increase in the presence of SO(2), but decrease in the presence of NO(2). After hydrate dissociation, SO(2) and NO(2) dissolved in water and form strong acids.     

Extension of the benzyl alcohol route to metal sulfides: "nonhydrolytic" thio sol-gel synthesis of ZnS and SnS2

Crystalline ZnS and SnS(2) particles were synthesized by a modified benzyl alcohol route using benzyl mercaptan as solvent.     

Thermodynamics of an interfacial fluid membrane

We discuss a closed system of field equations for a semipermeable membrane which has particle and heat exchange with its surroundings. In this case we consider a surface with an arbitrary shape for specific quantities and mechanical properties. A representation of the constitutive equations follows from the principle of material objectivity in space as well as on surfaces. The constitutive equations can be restricted by an entropy principle. We present both the Gibbs equation and the entropy flux. Furthermore, we obtain the surface stress and the chemical potential in terms of the specific free energy of the membrane. Both the heat flux and the particle flux normal to the membrane depend on the mean curvature and the friction between the particle across the membrane. The interaction tangential to the interface is dependent up on gradients of the surface stress as well as the chemical potential of the interface.     

Unsaturated porous media flow with thermomechanical interaction

We propose a model for unsaturated poro‐plastic flow derived from the thermodynamic principles. For the isothermal case, the problem consists of a degenerate coupled system of two PDEs with two independent hysteresis operators describing hysteresis phenomena in both the solid and the pore fluids. Under natural hypotheses, we prove the existence of a global strong solution for this system. Copyright © 2015 John Wiley & Sons, Ltd.