Reverse versus Normal Prenyl Transferases in Paraherquamide Biosynthesis Exhibit Distinct Facial Selectivities

Both a face-selective and a non-face-selective mode of formation of quaternary centers of isoprene-derived structural moieties of the natural alkaloid paraherquamide A ( 1 ) have been discovered by feeding experiments on Penicillium fellutanum with [U-¹³C₆]-glucose and [¹³C₂]-acetate. The labeling patterns suggest that the methyl groups (C22, C23) are introduced in a non-face-selective manner by a reverse prenyl transferase. The C₅ unit comprising the dioxepin moiety retains stereochemical integrity indicative of a single, face-selective addition of the phenolic group to the dimethylallyl group.     

The effects of pulsed introduction of buffer gas on ion storage and detection efficiencies in a quadrupole ion trap

The quadrupole ion trap is commonly operated with a constant background pressure of an inert, low molecular weight buffer gas. This inclusion of a buffer gas has been shown to increase the sensitivity and mass resolution of the instrument. Research to gain an understanding of these effects, both experimental and through simulations, has typically assumed that it is optimal to maintain a constant buffer gas pressure throughout the entire experiment This article describes the effects of the pulsed introduction of buffer gas at strategic points within the analytical scan and evaluates those events during which the presence of buffer gas is critical. By incorporating a pulsed valve within the ion trap manifold, both the presence and pressure of the buffer gas can be controlled and varied during the individual steps of the scan. The presence of helium buffer gas just before the ion ejection and detection event showed a greater increase in intensity of the ion signal than at any other time in the analytical scan. In addition, this increase in intensity upon pulsed introduction of buffer gas prior to detection is constant over a wide range of pulsed valve open times (i.e., pressures), whereas the signal enhancement upon pulsed introduction of the buffer gas before ionization is observed only over a narrow range of pulsed valve open times.     

Rheological and DSC studies of mixtures of gellan gum and konjac glucomannan

The interaction between gellan gum (GELL) and konjac glucomannan (KGM) with and without sodium chloride, potassium chloride, calcium chloride and magnesium chloride has been monitored using mechanical spectroscopy and differential scanning calorimetry (DSC). The rheological results indicated that the synergism occurred at sufficient low temperatures where individual helices of GELL molecules were sufficiently aggregated. With progressive addition of monovalent cations, storage shear modulus G' and loss shear modulus G” for mixtures gradually increased, and not only the helix-coil transition temperature of GELL molecules in mixtures but also the sol-gel transition temperature for mixtures shifted to higher temperatures with increasing concentration of salts. Moreover, in the presence of sufficient monovalent cations, mixtures formed an elastic gel with large thermal hysteresis. In the presence of divalent cations, the synergistic interaction was promoted up to a certain concentration, however, with more progressive addition of divalent cations, the main structure formed by aggregates of GELL helices would be smaller, so that mixtures could not form a gel in the presence of excessive divalent cations. DSC results indicated that the intermolecular binding complexes between GELL and KGM molecules would not occur, but KGM markedly influenced the disorder-order transition of GELL molecules. We have suggested that KGM was attached to the surface of large aggregates of GELL helices, and since cations promote GELL self-aggregation by a screening effect, the synergistic interaction between GELL and KGM was promoted with increasing concentration of salts. However, excessive divalent cations formed various aggregates of GELL helices with different thermal stabilities, so that the phase-separation in GELL/KGM mixtures was promoted in the presence of excessive divalent cations.     

Application of molecular mechanics to refine and understand the crystal structure of polythiophene and its oligomers

A molecular mechanics computational procedure, previously used for the refinement and the analysis of several crystalline polymers, was applied to investigate the crystal structures of the tetramer (T4) and hexamer (T6) of thiophene, as well as the crystal structure of polythiophene (PT). Simultaneous minimization of intra- and intermolecular energies of the T4 and T6 structures, obtained by Rietveld analysis of powder X-ray diffraction profiles, leads to molecular conformations showing smaller deviations from the ring co-planarity than the original models. For both oligomers the calculations confirm that the molecular centre of inversion is not a crystallographic centre of symmetry, as also revealed by X-ray diffraction of the T6 single crystal. This surprising effect appears to arise from intermolecular interactions between the terminal residues, hence is not relevant with respect to the PT polymer structure. The small energy cost for constraining the molecules at the crystallographic centre of symmetry is in agreement with experimental findings that reveal the existence of polymorphs for both T4 and T6. The calculations on the T6 single crystal were used to upgrade the MM2-like force field, which was then used to determine the minimum-energy model of the monoclinic crystal structure of polythiophene.     

Influences of stoichiometry on steadily propagating triple flames in counterflows

Most studies of triple flames in counterflowing streams of fuel and oxidizer have been focused on the symmetric problem in which the stoichiometric mixture fraction is 1/2. There then exist lean and rich premixed flames of roughly equal strengths, with a diffusion flame trailing behind from the stoichiometric point at which they meet. In the majority of realistic situations, however, the stoichiometric mixture fraction departs appreciably from unity, typically being quite small. With the objective of clarifying the influences of stoichiometry, attention is focused on one of the simplest possible models, addressed here mainly by numerical integration. When the stoichiometric mixture fraction departs appreciably from 1/2, one of the premixed wings is found to be dominant to such an extent that the diffusion flame and the other premixed flame are very weak by comparison. These curved, partially premixed flames are expected to be relevant in realistic configurations. In addition, a simple kinematic balance is shown to predict the shape of the front and the propagation velocity reasonably well in the limit of low stretch and low curvature.     

Nanostructured thin films obtained by ultra-short pulse laser deposition of vanadium carbide

In this paper we will report the results obtained by femtosecond Pulsed Laser Deposition on vanadium carbide. These results, compared with those obtained for another group 5 carbide, tantalum carbide, evidence large analogies between the two systems. Optical emission spectroscopy shows in both cases the presence of particles in the secondary plume and in both cases the films are formed by nanoparticles and present a stoichiometry corresponding to the hemicarbide.     

Exponential ionic drift: fast switching and low volatility of thin-film memristors

We investigate the exponential dependence of switching speeds in thin-film memristors for high electric fields and elevated temperatures. An existing nonlinear ionic drift model and our simulation results explain the very large ratios for the state lifetime to switching speed experimentally observed in devices for which resistance switching is due to ion migration. Given the activation barriers of the drifting species, it is possible to predict the volatility and switching time for various material systems.     

Synthesis of VO2 (B) nanorods for Li battery application

Vanadium dioxide nanorods were synthesized through a hydrothermal reaction from V₂O₅ xerogel, poly(vinyl pyrrolidone) (PVP) and lithium perchlorate (LiClO₄). The prepared samples were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical discharge–charge cycling in lithium battery. SEM images reveal the nanorods to have dimensions on the order of 1–3 μm in length and 10–50 nm in diameter. The measured initial discharge capacity of the lithium battery with a cathode made of VO₂ (B) nanorods was 152 mA h/g.     

Magneto-optical and micromagnetic simulation study of the current-driven domain wall motion in ferromagnetic (Ga,Mn)As

We have studied current-driven domain wall motion in modified Ga_0.95Mn_0.05As Hall bar structures with perpendicular anisotropy by using spatially resolved polar magneto-optical Kerr effect microscopy and micromagnetic simulation. Regardless of the initial magnetic configuration, the domain wall propagates in the opposite direction to the current with critical current of 1-2×10⁵ A/cm². Considering the spin-transfer torque term as well as various effective magnetic field terms, the micromagnetic simulation results are consistent with the experimental results. Our simulated and experimental results suggest that the spin-torque rather than Oersted field is the reason for current-driven domain wall motion in this material.     

MORPHOLOGY EVOLUTION IN PTFE AS A FUNCTION OF MELT TIME AND TEMPERATURE Ⅰ. HIGH MOLECULAR WEIGHT SINGLE- AND MULTI-MOLECULE FOLDED CHAIN SINGLE CRYSTALS AND BAND STRUCTURES

The effect of sintering dispersed dispersion and nano-emulsion particles of high molecular weight polytetrafluoroethylene (PTFE) on a substrate as a function of "melt" time and temperature is described. Folded chain single crystals parallel to the substrate and as ribbons on-edge (with double striations), as well as bands, are produced for longer sintering times; particle merger and diffusion of individual molecules, crystallizing as folded chain, single (or few) molecule,single crystals when "trapped" on the substrate by cooling occur for shorter sintering times. It is suggested the observed structures develop with sintering time, in a mesomorphic melt. The structure of the nascent particles is also discussed.