Novel Aluminum-Containing Ring Systems: An Octanuclear Structural Analogue of a Calix[4]pyrrole

Depending on the hydrazine reagent , Me₃Al reacts to afford novel aluminum-containing macrocyclic ring structures. The reaction of Me₃Al with Me₂NNH₂ provides the octanuclear calix[4]pyrrole-like 1 , while under analogous conditions the reaction with MePhNNH₂ gives a tetranuclear complex. Both complexes are formed by incorporation of acetonitrile.     

The Vancomycin Group of Antibiotics and the Fight against Resistant Bacteria

A last line of defence against “superbugs” are the vancomycin group antibiotics. This review describes the determination of their mode of action, and a mechanism of resistance to them. Remarkably, this mechanism of resistance can be overcome without directly modifying the binding site of the antibiotics for the cell-wall precursors of pathogenic bacteria.     

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.     

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.