Anion binding by bambus[6]uril probed in the gas phase and in solution

Electrospray ionization mass spectrometry (ESI-MS) is used to probe the binding of small anions to the macrocycle of bambus[6]uril. For the halide ions, the experimental patterns suggest F(-) < Cl(-) < Br(-) < I(-), which is consistent with the order of anion binding found in the condensed phase. Parallel equilibrium studies in the condensed phase establish the association constants of halide anions and bambus[6]uril in mixed solvents. A detailed analysis of the mass spectrometric data is used to shed light on the correlations between the binding constants in the condensed phase and the ion abundances observed using ESI-MS. From the analysis it becomes apparent that ESI-MS can indeed represent the situation in solution to some extent, but the sampling in the gas-phase experiment is not 1:1 compared to that in solution.     

Catalytic enantioselective conjugate allylation of unsaturated methylidene ketones

The use of unsaturated methylidene ketones in catalytic conjugate allylations allows a significant expansion in substrate scope and, with appropriate chiral ligands, occurs in a highly enantioselective fashion.     

Existence, uniqueness and behavior of solutions for a class of nonlinear parabolic problems

We prove existence, uniqueness, regularity results and estimates describing the behavior (both for large and small times) of a solution u of some nonlinear parabolic equations of Leray-Lions type including the p-Laplacian. In particular we show how the summability of the initial datum u₀ and the value of p influence the behavior of the solution u, producing ultracontractive or supercontractive estimates or extinction in finite time or different kinds of decay estimates.     

Conformational transitions of glycine induced by vibrational excitation of the O-H stretch

Vibrational energy flow and conformational transitions following excitation of the OH stretching mode of the most stable conformer of glycine are studied by classical trajectories. "On the fly" simulations with the PM3 semiempirical electronic structure method for the potential surface are used. Initial conditions are selected to correspond to the ν=1 excitation of the OH stretch. The main findings are: (1) An an equilibrium-like ratio is established between the populations of the 3 lowest-lying conformers after about 10 picoseconds. (2) There is a high probability throughout the 150 ps of the simulations for finding the molecule in geometries far from the equilibrium structures of the lowest-energy conformers. (3) Energy from the initial excited OH (ν=1) stretch flows preferentially to 5 other vibrational modes, including the bending motion of the H atom. (4) RRK theory yields conformational transition rates that deviate substantially from the classical trajectory results. Possible implication of these results for vibrational energy flow and conformational transitions in small biological molecules are discussed.     

MAFF — The Munich accelerator for fission fragments

At the new high flux reactor FRM-II in Munich the accelerator MAFF (Munich accelerator for fission fragments) is under design. In the high neutron flux of 10¹⁴ n/cm² s up to 10¹⁴ neutron-rich fission fragments per second are produced in the 1 g U-235 target. Ions with an energy of 30 keV are extracted from the ion source. In the mass separator two isotopes can be selected. One of the beams is used for low energy experiments, the other one is injected into an ECRIS (or EBIS) for charge breeding to a q/A≥0.16. A gas filled RFQ cooler is used for emittance improvement. The subsequent LINAC delivers beams with an energy ranging from 3.7 MeV/u to 5.9 MeV/u. New IH structures are being developed at the Munich tandem laboratory. A small storage ring is planned in a further stage to recycle the fission fragments. A thin target foil can be placed into this ring, e.g., for synthesis of super-heavy elements. The through-going beam tube has been installed in the heavy water tank of the reactor. Tests of the target ion source in a special oven to test long term stability and safety tests were in progress.     

Carbin-carben-umwandlung durch protonierung

Dicarbonyl(η⁵-cyclopentadienyl)(diethylaminocarbyne)tungsten reacts with hydrogen chloride to form an aminocarbene complex.     

Thermal Cyclization of 2-Acyl-1-azido-3-phenalenones to Phenaleno[1,2-c]isoxazol-7-ones

1-Azido-3-phenalenones 5 with acyl substituents in position 2, obtained by acylation and azidation of 1-hydroxy-3-phenalenones 1 , cyclized by thermolysis to give phenaleno[1,2-c]isoxazol-7-ones 9 . The thermolysis conditions were studied by differential scanning calorimetry.