High- and low-confinement modes in simple magnetized toroidal plasmas

Three-field simulations of interchange turbulence are presented for a simple magnetized toroidal plasma with a vertical magnetic field. The simulations show the presence of two turbulent regimes characterized by low (L) and high (H) confinement properties. We evaluate analytically the properties of the L regime, obtaining expressions for the plasma gradients and for the density and heat fluxes that agree well with the simulations. By increasing the plasma source strength or reducing the vertical magnetic field, a transition to a H regime occurs, in which a strong velocity shear limits the perpendicular transport with respect to the L scaling and the plasma profiles steepen. The analytic estimate of the transition condition is in accord with the simulations.     

Determination of positron beam parameters by various diagnostic techniques

Various diagnostic techniques have been applied at the neutron-induced positron source Munich NEPOMUC in order to determine the positron beam parameters such as intensity, beam shape and energy distribution. The positron beam intensity is determined by the detection of the annihilation radiation of positrons, which annihilate in a movable target. The use of a micro-channel plate (MCP) detector with a CCD-camera allows a direct measurement of the positron beam shape and the lateral resolved intensity distribution. At NEPOMUC a movable MCP-assembly inside the evacuated beam line enables a quick examination of the beam shape during operation. A retarding grid was mounted inside the homogeneous magnetic guiding field in order to determine the distribution of the longitudinal positron momentum, and hence estimate the energy distribution of the positrons.     

Als Oxydationsmittel

Ohne Zusammenfassung     

Tandem cyclopropanation with dibromomethane under Grignard conditions

Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnesium and CH2Br2 under Barbier conditions at higher temperatures. The reaction rates depend on the substitution pattern of the (homo)allylic alcoholates and on the counterion with lithium giving best results. Good to excellent syn-selectivities are obtained from alpha-substituted substrates, which are in accord with a staggered Houk model. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.     

Phase equilibria of the ternary system vinyl acetate/(R,S)-1-phenylethanol/carbon dioxide at high pressure conditions

Phase equilibrium measurements, correlations and predictions are presented for the binary systems (R,S)-1-phenylethanol/CO₂ and vinyl acetate/CO₂ and for the ternary system vinyl acetate/(R,S)-1-phenylethanol/CO₂. Experiments for the ternary system were performed in the temperature range of 323–343 K and in the pressure range of 7–12 MPa, using a high pressure phase equilibrium apparatus with a high pressure visual variable volume cell. Phase compositions were determined by taking samples of each phase and analysing them by gas chromatography. Equilibrium data were correlated with the Peng–Robinson equation of state combined with the Mathias–Klotz–Prausnitz mixing rule. A good correlation of both phases behaviour was obtained with an average absolute deviation (AAD) of 6.80%. Predictions for the binary sub-systems and for the ternary system were performed using the Peng–Robinson and the Soave–Redlich–Kwong equation of state, with the predictive mixing rule MHV1.     

Bioorthogonal Probes for the Study of MDM2‐p53 Inhibitors in Cells and Development of High‐Content Screening Assays for Drug Discovery

To study the behavior of MDM2‐p53 inhibitors in a disease‐relevant cellular model, we have developed and validated a set of bioorthogonal probes that can be fluorescently labeled in cells and used in high‐content screening assays. By using automated image analysis with single‐cell resolution, we could visualize the intracellular target binding of compounds by co‐localization and quantify target upregulation upon MDM2‐p53 inhibition in an osteosarcoma model. Additionally, we developed a high‐throughput assay to quantify target occupancy of non‐tagged MDM2‐p53 inhibitors by competition and to identify novel chemical matter. This approach could be expanded to other targets for lead discovery applications.     

Solid-state 31P NMR spectroscopy of precipitated guanine nucleotide-binding protein Ras in complexes with its effector molecules Raf kinase and RalGDS

Liquid-state 31P NMR spectroscopy is a well-established method for the study of guanine nucleotide-binding proteins (GNB proteins) such as the proto-oncogene Ras. Solid-state 31P NMR spectroscopy could meanwhile also be used to study microcrystalline samples of Ras as well as its partial loss-of-function mutants Ras(T35S) and Ras(T35A). However, solid-state NMR studies of the latter mutants in complex with effector molecules such as RalGDS or Raf kinase were so far prevented, since it has been impossible to crystallize these complexes yet. The aim of the present contribution is to make such complexes accessible to solid-state 31P NMR spectroscopy by the application of precipitation methods. The complex formed by Ras(T35S) and Raf kinase is preserved during precipitation. In contrast, the weakly bound complex of Ras(T35S) with RalGDS is dissociated or at least perturbed by the precipitation procedure. Solid-state 31P NMR experiments on precipitates of these complexes deliver spectra of high resolution and signal-to-noise ratio which allows the application of two-dimensional techniques. Precipitates prepared using polyethylene glycol 6000 (PEG) as precipitant were found to exhibit spectra of maximum resolution and signal-to-noise ratio. Interestingly, the 31P signal due to the alpha-phosphate of GppNHp bound to Ras(T35S) in crystalline samples or aged precipitates has a significantly different isotropic chemical shift than in the liquid state or in freshly prepared precipitates. This directly indicates that the crystal structure differs from the equilibrium solution structure at least in the neighborhood of the alpha-phosphate group.     

Gas flow MRI using circulating laser-polarized 129Xe.

We describe an experimental approach that combines multidimensional NMR experiments with a steadily renewed source of laser-polarized 129Xe. Using a continuous flow system to circulate the gas mixture, gas phase NMR signals of laser-polarized 129Xe can be observed with an enhancement of three to four orders of magnitude compared to the equilibrium 129Xe NMR signal. Due to the fact that the gas flow recovers the nonequilibrium 129Xe nuclear spin polarization in 0.2 to 4 s, signal accumulation on the time scale of seconds is feasible, allowing previously inaccessible phase cycling and signal manipulation. Several possible applications of MRI of laser-polarized 129Xe under continuous flow conditions are presented here. The spin density images of capillary tubes demonstrate the feasibility of imaging under continuous flow. Dynamic displacement profiles, measured by a pulsed gradient spin echo experiment, show entry flow properties of the gas passing through a constriction under laminar flow conditions. Further, dynamic displacement profiles of 129Xe, flowing through polyurethane foams with different densities and pore sizes, are presented.