Spectroscopic observation of bipolaronic point defects in Ba(1-x)KxBiO3

An infrared-absorption band centered at 0.85 eV, which is below the big optical absorption at the charge-density-wave (CDW) gap energy of 1.85 eV, has been observed for semiconducting single crystalline Ba(1-x)KxBiO3. With substituting K for Ba, the spectral weight of the new band increases with x, while that of the CDW-gap excitation decreases. Since the impurity state with the K substitution is known to be nonmagnetic at low temperatures, Bi3+ the state with 6s2 electrons surrounded by the six Bi5+ ions forms a small bipolaron by losing a pair of electrons in the Rice-Sneddon model. The new band is assigned to a transition from the lower-Peierls band to a state of the bipolaronic point defect.     

Dynamics of a quantum phase transition

We present two approaches to the dynamics of a quench-induced phase transition in the quantum Ising model. One follows the standard treatment of thermodynamic second order phase transitions but applies it to the quantum phase transitions. The other approach is quantum, and uses Landau-Zener formula for transition probabilities in avoided level crossings. We show that predictions of the two approaches of how the density of defects scales with the quench rate are compatible, and discuss the ensuing insights into the dynamics of quantum phase transitions.     

Optimal accumulation of Jacobian matrices by elimination methods on the dual computational graph

The accumulation of the Jacobian matrix F of a vector function can be regarded as a transformation of its linearized computational graph into a subgraph of the directed complete bipartite graph K_n,m. This transformation can be performed by applying different elimination techniques that may lead to varying costs for computing F. This paper introduces face elimination as the basic technique for accumulating Jacobian matrices by using a minimal number of arithmetic operations. Its superiority over both edge and vertex elimination methods is shown. The intention is to establish the conceptual basis for the ongoing development of algorithms for optimizing the computation of Jacobian matrices.     

Dynamical model for chemically driven running droplets

We propose coupled evolution equations for the thickness of a liquid film and the density of an adsorbate layer on a partially wetting solid substrate. Therein, running droplets are studied assuming a chemical reaction underneath the droplets that induces a wettability gradient on the substrate and provides the driving force for droplet motion. Two different regimes for moving droplets--reaction-limited and saturated regime--are described. They correspond to increasing and decreasing velocities with increasing reaction rates and droplet sizes, respectively. The existence of the two regimes offers a natural explanation of prior experimental observations.     

Highly resolved fluid flows: "liquid plasmas" at the kinetic level

Fluid flow around an obstacle was observed at the kinetic (individual particle) level using "complex (dusty) plasmas" in their liquid state. These "liquid plasmas" have bulk properties similar to water (e.g., viscosity), and a comparison in terms of similarity parameters suggests that they can provide a unique tool to model classical fluids. This allows us to study "nanofluidics" at the most elementary-the particle-level, including the transition from fluid behavior to purely kinetic transport. In this (first) experimental investigation we describe the kinetic flow topology, discuss our observations in terms of fluid theories, and follow this up with numerical simulations.     

Atomic structure of a (2 x 1) reconstructed NiSi2/Si(001) interface

Nickel disilicide/silicon (001) interfaces were investigated by aberration corrected scanning transmission electron microscopy (STEM). The atomic structure was derived directly from the high spatial resolution high angle annular dark field STEM images without recourse to image simulation. It comprises fivefold coordinated silicon and sevenfold coordinated nickel sites at the interface and shows a 2 x 1 reconstruction. The proposed structure has not been experimentally observed before but has been recently predicted theoretically by others to be energetically favored.     

Quantification of mephenytoin and its metabolites 4'-hydroxymephenytoin and nirvanol in human urine using a simple sample processing method

A reliable and easy to use liquid chromatography/tandem mass spectrometry (LC/MS/MS) method without the use of sample extraction was developed for the simultaneous quantification of urinary concentrations of mephenytoin, a standard phenotyping substrate for the cytochrome P450 enzyme CYP2C19, and its phase I metabolites 4'-hydroxymephenytoin and nirvanol. Fifty microL of urine were diluted with a buffered beta-glucuronidase solution and incubated at 37 degrees C for 6 h followed by addition of methanol, containing the internal standard 4'-methoxymephenytoin. The chromatographic separation was achieved using a 100 x 3 mm, 5 micro Thermo Electron Aquasil C18 column with a gradient flow, increasing the organic fraction (acetonitrile/methanol 50:50) of the mobile phase from 10 to 90%. Quantification by triple-stage mass spectrometry (TSQ Quantum, Thermo Electron) was accomplished by negative electrospray ionization in the selected reaction monitoring mode. Linearity was observed for all substances in the concentration range 15-10 000 ng/mL. The lower limit of quantification (LLOQ) was 20 ng/mL for 4'-hydroxymephenytoin and 30 ng/mL for nirvanol and mephenytoin, respectively. Intra- and inter-day inaccuracy did not exceed 9.5% for all substances from LLOQ to 10 000 ng/mL. Intra- and inter-day precision were in the range of 0.8-10.5%. The method was validated according to international ICH and FDA guidelines and successfully applied for phenotyping of Caucasian male volunteers who received an oral dose of 50 mg mephenytoin.     

Synthesis of 4,5-benzotropones by cyclization of 1,3-bis-silyl enol ethers with 1,2-dialdehydes

The cyclization of 1,3-bis-silyl enol ethers or (2,4-dioxobutylidene)triphenylphosphoranes with phthalic dialdehyde allowed a convenient synthesis of a variety of 4,5-benzotropones. The hydrogenation of benzotropones afforded functionalized benzocycloheptanones which were transformed into tricyclic butenolides.     

Practical synthesis of new and highly efficient ligands for the Suzuki reaction of aryl chlorides

A practical synthesis of a novel class of phosphine ligands, phosphino substituted N-aryl pyrroles (PAP ligands), has been developed. These ligands are applied in the palladium-catalyzed coupling of a variety of aryl and heteroaryl chlorides with phenylboronic acid showing exceedingly high turnover numbers at mild reaction temperatures and even at room temperature.