Giant anisotropy of Zeeman splitting of quantum confined acceptors in Si/Ge

Shallow acceptor levels in Si/Ge/Si quantum well heterostructures are characterized by resonant-tunneling spectroscopy in the presence of high magnetic fields. In a perpendicular magnetic field we observe a linear Zeeman splitting of the acceptor levels. In an in-plane field, on the other hand, the Zeeman splitting is strongly suppressed. This anisotropic Zeeman splitting is shown to be a consequence of the huge light-hole--heavy-hole splitting caused by a large biaxial strain and a strong quantum confinement in the Ge quantum well.     

Multitude of core-localized shear Alfvén waves in a high-temperature fusion plasma

Evidence is presented for a multitude of discrete frequency Alfvén waves in the core of magnetically confined high-temperature fusion plasmas. Multiple diagnostic instruments confirm wave excitation over a wide spatial range from the device size at the longest wavelengths down to the thermal ion Larmor radius. At the shortest scales, the poloidal wavelengths are comparable to the scale length of electrostatic drift wave turbulence. Theoretical analysis confirms a dominant interaction of the modes with particles in the thermal ion distribution traveling well below the Alfvén velocity.     

Stochastic elastohydrodynamics of a microcantilever oscillating near a wall

We consider the thermally driven motion of a microcantilever in a fluid environment near a wall, a configuration characteristic of the atomic force microscope. A theoretical model is presented which accounts for hydrodynamic interactions between the cantilever and wall over a wide range of frequencies and which exploits the fluctuation-dissipation theorem to capture the Brownian dynamics of the coupled fluid-cantilever system. Model predictions are tested against experimental thermal spectra for a cantilever in air and water. The model shows how, in a liquid environment, the effects of non-delta-correlated Brownian forcing appear in the power spectrum, particularly at low frequencies. The model also predicts accurately changes in the spectrum in liquid arising through hydrodynamic wall effects, which we show are strongly mediated by the angle at which the cantilever is tilted relative to the wall.     

Diastereoselective synthesis of (+/-)-(3-aminocyclopentane)alkylphosphinic acids, conformationally restricted analogues of GABA

A divergent synthesis of both diastereoisomers of (+/-)-(3-aminocyclopentane)alkylphosphinic acid is described. Both diastereoisomers are obtained in 5 steps from the key (+/-)-(3-hydroxycyclopent-1-ene)alkylphosphinate esters which are prepared via a palladium catalysed C-P bond forming reaction.     

Electrochemical properties of core-shell TiC-TiO2 nanoparticle films immobilized at ITO electrode surfaces

Titanium carbide (TiC) nanoparticles are readily deposited onto tin-doped indium oxide (ITO) electrodes in the form of thin porous films. The nanoparticle deposits are electrically highly conducting and electrochemically active. In aqueous media (at pH 7) and at applied potentials positive of 0.3 V vs. SCE partial anodic surface oxidation and formation (at least in part) of novel core-shell TiC-TiO2 nanoparticles is observed. Significant thermal oxidation of TiC nanoparticles by heating in air occurs at a temperature of 250 degrees C and leads first to core-shell TiC-TiO2 nanoparticles, next at ca. 350 degrees C to TiO2 (anatase), and finally at temperatures higher than 750 degrees C to TiO2 (rutile). Electrochemically and thermally partially oxidized TiC nanoparticles still remain very active and for some redox systems electrocatalytically active. Scanning and transmission electron microscopy (SEM and TEM), temperature dependent XRD, quartz crystal microbalance, and voltammetric measurements are reported. The electrocatalytic properties of the core-shell TiC-TiO2 nanoparticulate films are surveyed for the oxidation of hydroquinone, ascorbic acid, and dopamine in aqueous buffer media. In TiC-TiO2 core-shell nanoparticle films TiO2 surface reactivity can be combined with TiC conductivity.     

Advances in methods and algorithms in a modern quantum chemistry program package

Advances in theory and algorithms for electronic structure calculations must be incorporated into program packages to enable them to become routinely used by the broader chemical community. This work reviews advances made over the past five years or so that constitute the major improvements contained in a new release of the Q-Chem quantum chemistry package, together with illustrative timings and applications. Specific developments discussed include fast methods for density functional theory calculations, linear scaling evaluation of energies, NMR chemical shifts and electric properties, fast auxiliary basis function methods for correlated energies and gradients, equation-of-motion coupled cluster methods for ground and excited states, geminal wavefunctions, embedding methods and techniques for exploring potential energy surfaces.     

Electroosmotic flow patterning using microfluidic delay loops

A theoretical and experimental investigation of alternating electroosmotic flow patterns by means of specially designed delay loops is presented. Using elementary methods of compact network modeling and detailed FEM simulations the flow behavior and, in particular, the rearrangement of sample plugs is modeled. The proposed designs rely on flow splitting in combination with electroosmotic delay loops leading to a runtime difference or phase shift between two sub-streams. Due to this phase shift, a new fluid interface is generated at the merging point. The approach is experimentally validated by injection of a Rhodamine 6G solution into an aqueous sodium tetraborate buffer.     

Extended weak bonding interactions in DNA: pi-stacking (base-base), base-backbone, and backbone-backbone interactions

We report on several weak interactions in nucleic acids, which, collectively, can make a nonnegligible contribution to the structure and stability of these molecules. Fragments of DNA were obtained from previously determined accurate experimental geometries and their electron density distributions calculated using density functional theory (DFT). The electron densities were analyzed topologically according to the quantum theory of atoms in molecules (AIM). A web of closed-shell bonding interactions is shown to connect neighboring base pairs in base-pair duplexes and in dinuleotide steps. This bonding underlies the well-known pi-stacking interaction between adjacent nucleic acid bases and is characterized topologically for the first time. Two less widely appreciated modes of weak closed-shell interactions in nucleic acids are also described: (i) interactions between atoms in the bases and atoms belonging to the backbone (base-backbone) and (ii) interactions among atoms within the backbone itself (backbone-backbone). These interactions include hydrogen bonding, dihydrogen bonding, hydrogen-hydrogen bonding, and several other weak closed-shell X-Y interactions (X, Y = O, N, C). While each individual interaction is very weak and typically accompanied by perhaps 0.5-3 kcal/mol, the sum total of these interactions is postulated to play a role in stabilizing the structure of nucleic acids. The Watson-and-Crick hydrogen bonding is also characterized in detail at the experimental geometries as a prelude to the discussion of the modes of interactions listed in the title.     

Total syntheses of (+/-)-cis-trikentrin A and (+/-)-cis-trikentrin B via electrocyclic ring closures of 2,3-divinylpyrrolines

[Structure: see text] A convergent and versatile strategy for the diastereoselective syntheses of (+/-)-cis-trikentrin A and B in 10 and 12 steps, respectively, from commercially available N-BOC-2-pyrrolidinone is described. The key step in each of the total syntheses is the construction of the central benzene ring via a facile 6pi-electrocyclic ring closure of an appropriately substituted 2,3-divinylpyrroline, in turn, readily available by a Stille coupling reaction.