Plume dynamics in quasi-2D turbulent convection

We have studied turbulent convection in a vertical thin (Hele-Shaw) cell at very high Rayleigh numbers (up to 7x10(4) times the value for convective onset) through experiment, simulation, and analysis. Experimentally, convection is driven by an imposed concentration gradient in an isothermal cell. Model equations treat the fields in two dimensions, with the reduced dimension exerting its influence through a linear wall friction. Linear stability analysis of these equations demonstrates that as the thickness of the cell tends to zero, the critical Rayleigh number and wave number for convective onset do not depend on the velocity conditions at the top and bottom boundaries (i.e., no-slip or stress-free). At finite cell thickness delta, however, solutions with different boundary conditions behave differently. We simulate the model equations numerically for both types of boundary conditions. Time sequences of the full concentration fields from experiment and simulation display a large number of solutal plumes that are born in thin concentration boundary layers, merge to form vertical channels, and sometimes split at their tips via a Rayleigh-Taylor instability. Power spectra of the concentration field reveal scaling regions with slopes that depend on the Rayleigh number. We examine the scaling of nondimensional heat flux (the Nusselt number, Nu) and rms vertical velocity (the Peclet number, Pe) with the Rayleigh number (Ra(*)) for the simulations. Both no-slip and stress-free solutions exhibit the scaling NuRa(*) approximately Pe(2) that we develop from simple arguments involving dynamics in the interior, away from cell boundaries. In addition, for stress-free solutions a second relation, Nu approximately nPe, is dictated by stagnation-point flows occurring at the horizontal boundaries; n is the number of plumes per unit length. No-slip solutions exhibit no such organization of the boundary flow and the results appear to agree with Priestley's prediction of Nu approximately Ra(1/3). (c) 1997 American Institute of Physics.     

The epitaxial growth of cholesterol crystals from bile solutions on calcite substrates

Epitaxial relationships between the surfaces of inorganic and bioorganic crystals can be an important factor in crystal nucleation and growth processes in a variety of biological environments. Crystalline cholesterol monohydrate (ChM), a constituent of both gallstone and atherosclerotic plaques, is often found in association with assorted mineral phases. Using in situ atomic force microscopy (AFM) and well-characterized model bile solutions, the nucleation and epitaxial growth of ChM on calcite (104) surfaces in real-time is demonstrated. The growth rates of individual cholesterol islands formed on calcite substrates were determined at physiological temperatures. Evidence of Ostwald's ripening was also observed under these experimental conditions. The energetics of various (104) calcite/(001) ChM interfaces were calculated to determine the most stable interfacial structure. These simulations suggest that the interface is fully hydrated and that cholesterol hydroxyl groups are preferentially positioned above carbonate ions in the calcite surface. This combination of experimental and theoretical work provides a clearer picture of how preexisting mineral seeds might provide a viable growth template that can reduce the energetic barrier to cholesterol nucleation under some physiological conditions.     

Zink und Cadmium

Ohne ZusammenfassungChemikerfachausschuß der Gesellschaft Deutscher Metallhütten- und Bergleute     

Design of functional ferritin-like proteins with hydrophobic cavities

Ferritin four-helix bundle subunits self-assemble to create a stable multimer with a large central hydrophilic cavity where metal ions bind. To explore the versatility of this reaction vessel, computational design was used to generate cavities with increasingly apolar surface areas inside a dodecameric ferritin-like protein, Dps. Cavity mutants, in which as many as 120 surface accessible hydrophilic residues were replaced with hydrophobic amino acids, were shown to still assemble properly using size-exclusion chromatography and dynamic light scattering measurements. Wild-type Dps exhibited highly cooperative subunit folding and assembly, which was monitored by changes in Trp fluorescence and UV circular dichroism. The hydrophobic cavity mutants showed distinctly less cooperative unfolding behavior, with one mutant forming a partially assembled intermediate upon guanidine denaturation. Although the stability of Dps to such denaturation decreased with increasing apolar surface area, all proteins exhibited high melting temperatures, T(m) = 74-90 degrees C. Despite the large number of mutations, near-native ability to mineralize iron was maintained. This work illustrates the versatility of the ferritin scaffold for engineering large protein cavities with novel properties.     

Stereocontrol of palladium(II)-catalysed aza-Claisen rearrangements using a combination of 1,3-allylic strain and a solvent mediated directing effect

The use of a non-coordinating solvent for the aza-Claisen rearrangement of delta,epsilon-disubstituted acetimidates switches on a substrate directing effect that gives excellent stereoselectivity.