Sufficient conditions for Willmore immersions in \mathbb{R }^3 to be minimal surfaces

We provide two sharp sufficient conditions for immersed Willmore surfaces in $\mathbb{R }^3$ to be already minimal surfaces, i.e. to have vanishing mean curvature on their entire domains. These results turn out to be particularly suitable for applications to Willmore graphs. We can therefore show that Willmore graphs on bounded $C^4$ -domains $\overline{\varOmega }$ with vanishing mean curvature on the boundary $\partial \varOmega $ must already be minimal graphs, which in particular yields some Bernstein-type result for Willmore graphs on $\mathbb{R }^2$ . Our methods also prove the non-existence of Willmore graphs on bounded $C^4$ -domains $\overline{\varOmega }$ with mean curvature $H$ satisfying $H \ge c_0>0 \,{\text{ on }}\, \partial \varOmega $ if $\varOmega $ contains some closed disc of radius $\frac{1}{c_0} \in (0,\infty )$ , and they yield that any closed Willmore surface in $\mathbb{R }^3$ which can be represented as a smooth graph over $\mathbb{S }^2$ has to be a round sphere. Finally, we demonstrate that our results are sharp by means of an examination of some certain part of the Clifford torus in $\mathbb{R }^3$ .     

Electronic and magnetic properties of double perovskites (, Ca)

We have studied the magnetic and electronic properties of double perovskites A₂FeReO₆ with A=Ba and Ca using ab initio methods based on density functional theory. It has been shown that when changing Ba by Ca the system undergoes a metal–insulator transition coincidentally to a structural phase transition, even if conduction band fillings are not significantly changed. Our results suggest that only considering a quite large correlation term on the Re site could explain an insulating character for Ca₂FeReO₆. Instead, we found that small correlations could induce a bad metallic behavior as suggested in more recent experiments.     

Preparation of self-supporting mesostructured silica thin film membranes as gateable interconnects for microfluidics

A methodology for the preparation of self-standing 100–200 nm thick mesoporous silica membrane interconnects is reported. Interconnects may become an important component in future microfluidic device technology since it allows extension of microfluidic architectures into the third dimension. The silica film was mechanically supported by a perforated silicon nitride microsieve and covered a hexagonal array of 500 nm-sized holes. The potential applicability of these films as gateable interconnects for controlled dosing of ions was demonstrated. The permeability of ionic species can be controlled by the ionic strength.     

Fission neutron multiplicity versus fragment mass and kinetic energy

High spin states of ¹²⁷ Ba have been investigated by means of the OSIRIS anti-compton γ -spectrometer. Five new bands, 48levels and 77transitions were found. Spin suggestions for four bandheads could be given. On ground of these suggestions routhians and alignments were compiled for the observed bands, giving a first insight into the high spin structure of this nucleus.     

The retro-aldol mechanism in the pyrolysis kinetics of primary,secondary, and tertiary β-hydroxy ketones in the gas phase

The pyrolysis kinetics of primary, secondary, and tertiary β-hydroxy ketones have been studied in static seasoned vessels over the pressure range of 21–152 torr and the temperature range of 190°–260°C. These eliminations are homogeneous, unimolecular, and follow a first-order rate law. The rate coefficients are expressed by the following equations: for 1-hydroxy-3-butanone, log k₁(s^?1) = (12.18 ± 0.39) ? (150.0 ± 3.9) kJ mol^?1 (2.303RT)^?1; for 4-hydroxy-2-pentanone, log k₁(s^?1) = (11.64 ± 0.28) ? (142.1 ± 2.7) kJ mol^?1 (2.303RT)^?1; and for 4-hydroxy-4-methyl-2-pentanone, log k₁(s^?1) = (11.36 ± 0.52) ? (133.4 ± 4.9) kJ mol^?1 (2.303RT)^?1. The acid nature of the hydroxyl hydrogen is not determinant in rate enhancement, but important in assistance during elimination. However, methyl substitution at the hydroxyl carbon causes a small but significant increase in rates and, thus, appears to be the limiting factor in a retroaldol type of mechanism in these decompositions. © John Wiley & Sons, Inc.     

Mechanism for room-temperature single-atom lateral manipulations on semiconductors using dynamic force microscopy

Vacancy-mediated lateral manipulations of intrinsic adatoms of the Si(111)-(7x7) surface at room temperature are reported. The topographic signal during the manipulation combined with force spectroscopy measurements reveals that these manipulations can be ascribed to the so-called pulling mode, and that the Si adatoms were manipulated in the attractive tip-surface interaction regime at the relatively low short-range force value associated to the manipulation set point. First-principles calculations reveal that the presence of the tip induces structural relaxations that weaken the adatom surface bonds and manifests in a considerable local reduction of the natural diffusion barriers to adjacent adsorption positions. Close to the short-range forces measured in the experiments, these barriers are lowered near the limit that enables a thermally activated hopping at room temperature.     

Relative Permeabilities for Strictly Hyperbolic Models of Three-Phase Flow in Porous Media

Traditional mathematical models of multiphase flow in porous media use a straightforward extension of Darcys equation. The key element of these models is the appropriate formulation of the relative permeability functions. It is well known that for one-dimensional flow of three immiscible incompressible fluids, when capillarity is neglected, most relative permeability models used today give rise to regions in the saturation space with elliptic behavior (the so-called elliptic regions). We believe that this behavior is not physical, but rather the result of an incomplete mathematical model. In this paper we identify necessary conditions that must be satisfied by the relative permeability functions, so that the system of equations describing three-phase flow is strictly hyperbolic everywhere in the saturation triangle. These conditions seem to be in good agreement with pore-scale physics and experimental data.     

Nickel‐Catalyzed Enantioselective C?C Bond Formation through C?O Cleavage in Aryl Esters

We report the first enantioselective C C bond formation through C O bond cleavage using aryl ester counterparts. This method is characterized by its wide substrate scope and results in the formation of quaternary stereogenic centers with high yields and asymmetric induction.     

Symmetry calculation for molecules and transition states

The symmetry of molecules and transition states of elementary reactions is an essential property with important implications for computational chemistry. The automated identification of symmetry by computers is a very useful tool for many applications, but often relies on the availability of three‐dimensional coordinates of the atoms in the molecule and hence becomes less useful when these coordinates are a priori unavailable. This article presents a new algorithm that identifies symmetry of molecules and transition states based on an augmented graph representation of the corresponding structures, in which both topology and the presence of stereocenters are accounted for. The automorphism group order of the graph associated with the molecule or transition state is used as a starting point. A novel concept of label‐stereoisomers, that is, stereoisomers that arise after labeling homomorph substituents in the original molecule so that they become distinguishable, is introduced and used to obtain the symmetry number. The algorithm is characterized by its generic nature and avoids the use of heuristic rules that would limit the applicability. The calculated symmetry numbers are in agreement with expected values for a large and diverse set of structures, ranging from asymmetric, small molecules such as fluorochlorobromomethane to highly symmetric structures found in drug discovery assays. The new algorithm opens up new possibilities for the fast screening of the degree of symmetry of large sets of molecules. © 2014 Wiley Periodicals, Inc.     

Analysis of sulfated peptides from the skin secretion of the Pachymedusa dacnicolor frog using IMAC-Ga enrichment and high-resolution mass spectrometry

Immobilized metal ion affinity chromatography (IMAC) has been widely used for the enrichment of phosphopeptides, whereas no report exists describing the use of IMAC columns for the enrichment of sulfopeptides. In this study, we used IMAC-Ga microcolumns for the enrichment of sulfopeptides from a complex mixture of peptides, extracted from skin secretions of the Pachymedusa dacnicolor frog. The enriched fraction obtained by IMAC-Ga was analyzed by liquid chromatograpy/electrospray ionization mass spectrometry (LC/ESI-MS) in an Orbitrap XL and by matrix-assisted laser desorption/ionization time-of-flight time-of-flight (MALDI-TOF/TOF) in an ABI 4800 instrument. From this fraction, different sulfated and non-sulfated peptides belonging to the caerulin and bradykinin families were structurally characterized. Other interesting negatively charged groups, such as phosphate adducts of dermaseptins and pyridoxal phosphate attached to a protease inhibitor, were also characterized. Unexpectedly, some dermaseptin antimicrobial peptides were also enriched by IMAC-Ga and a Sauvatine-like peptide was also fully sequenced. Furthermore, neutral loss of sulfated peptides and their fragmentation patterns in the gas phase were also compared using collision-induced dissociation (CID) and high-energy collision dissociation (HCD). Our present study provides evidence that IMAC-Ga enrichment is a fast, useful and promising method for high-throughput analysis of sulfated-peptides, since high-resolution mass spectrometers can be used for this purpose.