The McCormack model for gas mixtures: The temperature-jump problem

An analytical version of the discrete-ordinates method (the ADO method) is used to establish a concise and particularly accurate solution to the temperature-jump problem for a binary gas mixture described by the McCormack kinetic model. The solution yields, in addition to the temperature-jump coefficient for the general (specular–diffuse) case of Maxwell boundary conditions for each of the two species, the density and temperature profiles for both types of particles. Numerical results are reported for two binary mixtures (Ne-Ar and He-Xe) with various molar concentrations. The algorithm is considered especially easy to use, and the developed (FORTRAN) code requires typically less than a second on a 2.2 GHz Pentium 4 machine to compute all quantities of interest.Received: November 18, 2003; revised April 14, 2004     

Strong evaporation into a half space. II. The three-dimensional BGK model

Evaporation of a liquid into a vacuum occupying a half space is investigated on the basis of the BGK equation for a three-dimensional gas linearized about a drifting Maxwellian distribution. The theory of singular integral equations is used and numerical results are given.

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Zusammenfassung Die Verdampfung einer Flüssigkeit im Vakuum, die den Halbraum füllt, wird untersucht mit Benützung der BGK-Gleichung für ein dreidimensionales Gas, linearisiert in bezug auf eine mitbewegte Maxwell-Verteilung. Es wird die Theorie der singulären Integralgleichungen benützt, und es werden numerische Resultate gegeben.

     

Analytical solutions to two matrix Riemann-Hilbert problems

Two matrix Riemann-Hilbert problems derived from boundary-value problems in the kinetic theory of gases are solved analytically.

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Riassunto Vengono risolti analiticamente due problemi relativi alla matrice di Riemann-Hilbert, che si incontrano in problemi con condizioni al contorno nella teoria cinetica dei gas.

     

Cholesterol shows preference for the interior of polyunsaturated lipid membranes

Recent neutron scattering experiments showed a striking manifestation of the aversion between polyunsaturated fatty acid (PUFA)-containing lipids and cholesterol. Selectively deuterated cholesterol/ 1,2-diarachidonylphosphatidylcholine (DAPC) samples revealed that the hydroxyl of the sterol resides at the center of the bilayer. Here we use a recently parametrized coarse grain simulation model to shed light on these puzzling experimental observations. Using a simulation setup in close correspondence to the experimental conditions, we reproduce the experimental neutron scattering profiles to a large extent. The simulations allow us to analyze the behavior of cholesterol in detail; we show that the interaction of cholesterol with the PUFA chains of DAPC leads to a fast flip-flop rate for the sterol and an increased preference of the sterol for the unusual location embedded between the monolayer leaflets.     

Proton‐Coupled Electron Transfer Reactions Catalysed by 3 d Metal Complexes

Proton‐coupled electron transfer (PCET) reactions are essential for a wide range of natural energy‐conversion reactions and recently, the impact of PCET pathways has been exploited in artificial systems, too. The Minireview highlights PCET reactions catalysed by first‐row transition‐metal complexes, with a focus on the water oxidation, the oxygen reduction, the hydrogen evolution, and the CO₂ reduction reaction. Special attention will be paid to systems in which the impact of such pathways is deduced by comparison to systems with “electron‐only”‐transfer pathways.     

Electrocatalytic Dihydrogen Production with a Robust Mesoionic Pyridylcarbene Cobalt Catalyst

A Co^III complex with a mesoionic pyridylcarbene ligand is presented. This complex is an efficient electrocatalyst for H₂ production at very low overpotential and high turnovers when using a (glassy carbon) GC electrode. The corresponding triazole complexes display no catalytic activity whatsoever under identical conditions. The remarkable robustness of the Co? C(carbene) bond towards acids is likely responsible for the high efficiency of this catalyst. The present results thus open new avenues for carbene‐based ligands for generating functional models for hydrogenases.     

Probing the influence of steric bulk on anion binding by triarylboranes: comparative studies of FcB(o-Tol)2, FcB(o-Xyl)2 and FcBMes2

Steric crowding brought about on pyramidalization at boron has been predicted computationally to be of central importance to the strength and selectivity of anion binding by triarylboranes. The role of steric factors in systems containing a ferrocenyl reporter unit has been systematically probed in the current study by comparison of the F(-)/CN(-) binding properties of FcB(o-Tol)(2) (1, o-Tol = C(6)H(4)Me-2), FcB(o-Xyl)(2) (2, o-Xyl = C(6)H(3)Me(2)-2,6) and FcBMes(2) (3, Mes = C(6)H(2)Me(3)-2,4,6)), both in solution and in the solid state. Somewhat surprisingly, the inclusion of an extra ortho-methyl aryl substituent (e.g. for 2/3vs.1) is found to have a relatively small effect on the binding affinities of these boranes (e.g. log(10)K(CN) = 5.94(0.02), 4.73(0.01), 5.56(0.02), for 1, 2 and 3 respectively). Consistent with this observation, the degree of pyramidalization at boron determined for the cyanide adducts [1·CN](-), [2·CN](-) and [3·CN](-) in the solid state is also found to be essentially invariant (∠C(aryl)-B-C(aryl) = 338, 337, 337°, respectively), as are the B-CN and mean B-C(aryl) distances. In the solid state at least, it is apparent that the adverse steric effects potentially brought about by increasing ortho substitution are mitigated by a greater degree of synchronous rotation of the aryl substituents about the B-C(aryl) bonds. Thus a mean inter-plane angle of 71° is observed for [1·CN](-) while the corresponding values for [2·CN](-) and [3·CN](-) are 78° and 79°.     

Mechanical erosion by flowing lava

Hot lava is a viscous fluid that, driven by gravity, moves along the Earth's surface. Intuitively, one attributes constructional properties to lava–it accumulates in volcanic landforms, compound lava fields and, in the end, entire mountains. On the other hand, there are also examples of the erosive power of lava: on Earth and especially on other planets in the Solar System, there exist channels incised by flowing lava. The origins of these erosive features have long been debated among volcanologists and planetologists. The dominant paradigm is thermal erosion, although it leaves many questions open. After the 2001 eruption on Mount Etna we found a lava channel whose features cannot be explained in the frame of thermal erosion. On the basis of our observations, we have developed a model for mechanical erosion that explains the main field observations, and opens alternative ways to describe erosion by flowing lava.     

Structural determinants of the supramolecular organization of G protein-coupled receptors in bilayers

The G protein-coupled receptor (GPCR) rhodopsin self-assembles into supramolecular structures in native bilayers, but the structural determinants of receptor oligomerization are not known. We carried out multiple self-assembly coarse-grained molecular dynamics (CGMD) simulations of model membranes containing up to 64 molecules of the visual receptor rhodopsin over time scales reaching 100 μs. The simulations show strong preferential interaction modes between receptors. Two primary modes of receptor-receptor interactions are consistent with umbrella sampling/potential of mean force (PMF) calculations as a function of the distance between a pair of receptors. The preferential interfaces, involving helices (H) 1/8, 4/5 and 5, present no energy barrier to forming a very stable receptor dimer. Most notably, the PMFs show that the preferred rhodopsin dimer exists in a tail-to-tail conformation, with the interface comprising transmembrane H1/H2 and amphipathic H8 at the extracellular and cytoplasmic surfaces, respectively. This dimer orientation is in line with earlier electron microscopy, X-ray, and cross-linking experiments of rhodopsin and other GPCRs. Less stable interfaces, involving H4 and H6, have a free energy barrier for desolvation (delipidation) of the interfaces and appear to be designed to stabilize "lubricated" (i.e., lipid-coated) dimers. The overall CGMD strategy used here is general and can be applied to study the homo- and heterodimerization of GPCRs and other transmembrane proteins. Systematic extension of the work will deepen our understanding of the forces involved in the membrane organization of integral membrane proteins.     

Mechanical model of a mistuned 2DOF-structure coupled by viscous damping

In this paper the vibration amplitude reduction of a mechanical system is investigated when applying a damper between different DOF of that structure. Thereby, an elementary mechanical model consisting of two mass-spring elements with slightly differing eigenfrequencies and which are connected via a viscous dashpot damper is regarded. To investigate the systems behavior, an analysis of the transfer function and its poles and zeros in the L APLACE domain is performed when varying the damping constant. This reveals that the achievable amplitude reduction depends on the mistuning of the system and that even ideal viscous damping leads to a coupling which results in a shift of eigenfrequencies. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)