The diastereofacial selectivity of the addition of various 1-metalated 1-heptynes to substituted cyclopentanecarbaldehydes. – The use of 1-titanated 1-heptyne for the construction of the alkyl side chain of Prostaglandins

A highly diastereoselective addition of 1-heptyne to substituted cyclopentanecarbaldehydes is one of the indispensable prerequisites to the construction of the (S)-3-hydroxy-1(E)-octenyl side chain of prostaglandins by palladium(II)-catalyzed [3,3]-sigmatropic rearrangement of allylic acetates. It was found that 1-titanated 1-heptynes afford the Cram product at best with a diastereofacial selectivity of 92.5%. The corresponding lithium and magnesium compounds are less diastereoselective.     

The busbar system for Wendelstein 7-X prepared for assembly and operational loads

Forschungszentrum Jülich has taken over the design, manufacturing and assembly of the superconducting busbar system for the stellarator Wendelstein 7-X. This includes the busbars itself, the support structure consisting of supports and clamps, and the joints for electrical and hydraulic connection of the busbars and coil terminals. Apart from providing the required electrical connection scheme, the busbar system has to be designed for relevant electrical and mechanical loads. Numerous interfaces and geometric boundary conditions define the confined space to accommodate the busbars and their support elements. This article describes how the individual challenges to engineering have been met in the course of the project. This includes design concepts and the method for iterative design of supports with respect to the individual load distribution caused by the supports itself.     

Enzymes in organic synthesis. 2. Synthesis of enantiomerically pure prostaglandin intermediates by Enzymatic Hydrolysis of (1SR, 5RS, 6RS, 7RS)-7-acetoxy-6-acetoxymethyl-2-oxabicyclo[3.3.0]octan-3-one

Subtilisin DY as well as alkaline protease from Bacillus licheniformis 41 p catalyze the hydrolysis of (1SR, 5RS, 6RS, 7RS)-7-acetoxy-6-acetoxymethyl-2-oxabicyclo[3.3.0]octan-3-one ( rac-1 ) with practically useful enantio- and regioselectivity. Under the hitherto found optimal conditions (1S, 5R, 6R, 7R)-7-hydroxy-6-hydroxymethyl-2-oxabicyclo[3.3.0]octan-3-one ( 4 ), an important intermediate in prostaglandin syntheses, could be prepared in a yield of 16% with an enantiomeric excess of 99%. The enantiomer ( ent-4 ) was obtained with the same enantiomeric excess in 20% yield. The chemical yields are related to the racemic starting material rac-1 .     

Time Dependent Effects in Surface Tension Measurements of an Industrial Fe‐alloy

The surface tension of an industrial FeC‐alloy containing Si, Mn and S in the few atomic per cent range was measured by the oscillating drop method in ground based electromagnetic levitation and under reduced gravity conditions on board a parabolic flight. The results from the parabolic flight exhibited a large variation between different heating cycles and a discrepancy with the ground based experiments with regard to the value of the surface tension at the liquidus temperature and the temperature coefficient. The variation of the surface tension temperature coefficient is interpreted as resulting from the loss of volatile surface active components such as S and Si in subsequent heating cycles. The results demonstrate the importance of the time scale of the measurement and ambient atmosphere for surface tension measurements of industrial alloys containing volatile surface active components. For comparison with the experimental values the surface tension and segregation were modelled using different models. As a result of the analysis, the surface tension as a function of temperature best representing the starting industrial alloy is obtained as σ(T) = 1.52–1.53 10^‐4 (T–1752K) Nm^‐1.     

Thermal Effects and Small Signal Modulation of 1.3-μm InAs/GaAs Self-Assembled Quantum-Dot Lasers

We investigate the influence of thermal effects on the high-speed performance of 1.3-μm InAs/GaAs quantum-dot lasers in a wide temperature range (5–50°C). Ridge waveguide devices with 1.1 mm cavity length exhibit small signal modulation bandwidths of 7.51 GHz at 5°C and 3.98 GHz at 50°C. Temperature-dependent K-factor, differential gain, and gain compression factor are studied. While the intrinsic damping-limited modulation bandwidth is as high as 23 GHz, the actual modulation bandwidth is limited by carrier thermalization under continuous wave operation. Saturation of the resonance frequency was found to be the result of thermal reduction in the differential gain, which may originate from carrier thermalization.     

Computer-algebra calculations and measurements on AB spin systems for double-spin-echo sequences

The time evolution of the density operator of an AB spin system during a double-spin-echo pulse sequence is evaluated analytically by a computer-algebra system. The computer-algebra system allows one to generate the extensive formulas describing the density operator and yields an expression for the integral of the spectral signals. The simulation of spectra for arbitrary sequence timings can be easily performed by this new tool without risking errors that might occur in conventional calculations. The computer-algebra method can be extended straightforward to other pulse angles and types of sequences. The double-spin-echo pulse sequence is used in the point-resolved spectroscopy (PRESS) method which is often applied for volume selective examinationsin vivo. For verification of the results generated by the computer-algebra system,¹H spectra from a half-liter spherical sample with an aqueous solution that was 0.1 M in sodium citrate and 0.1 M in sodium acetate were recorded after 90°-180°-180° double-spin-echo pulse sequences on a 1.5-T whole-body unit. The measured behavior of the citrate AB spin system corresponds very well with the theoretical predictions. Thus, the theory provides the basis for the optimization of sequence timings for double-spin-echo measurements with high signal gain from AB systems as, for example, citrate. In addition, the theoretically predicted signal modulations could be fitted to the experimental data, providing the transverse relaxation time of the AB-coupled protons.     

Numerically optimized hard pulse sequences for fast frequency selective excitation and inversion

Numerically optimized hard pulse sequences were developed providing a frequency selective response of the transverse and longitudinal magnetization for several applicationsin vivo. The sequences are based on pulse trains with binomial ratios of the pulse angles and constant time intervals between the pulses. These pulse trains were systematically optimized to obtain broad Larmor frequency ranges in which the magnetization is not markedly influenced by the pulse sequence. In addition, the sequences had to provide maximum transverse magnetization or complete inversion of the magnetization beside the suppression range. Such behaviour is needed for chemical shift selective imaging, pulsed magnetization transfer, and frequency selective spectroscopyin vivo. The phase of the magnetization response is shown and adequate rephasing conditions are discussed as well as the actual phase duration. Short optimized hard pulse sequences for water and fat-selective imaging provide lowT ₂-sensitivity of the resulting magnetization. The new optimized hard pulse sequences are suitable, if optimum suppression of signals at one single point in the Larmor frequency spectrum is less important than good suppression in a larger frequency range.     

Videoendoscopic diagnosis of esophageal motility disorders

PURPOSE: Looking for a valid, reliable, and feasible method to collect data on the performances of practicing family physicians, the authors compare the measurement characteristics of a multiple-station examination (MSE) using standardized patients with those of a video assessment of regular consultations in daily practice (practice video assessment, PVA). METHOD: In a cross-sectional study, consultations of 90 family physicians were videotaped both in an MSE and in their daily practices. Peer-observers used a validated instrument (MAAS-Global) to assess the physicians' communication with patients and their medical performances. The physicians were randomly divided into two groups, comparable for demographic characteristics, and half underwent the assessments in reverse order to test for time-order effects. Content validity, criterion validity, reliability, and feasibility of the two methods were compared. RESULTS: Content validity of the PVA was superior to that of the MSE, since the domain of general family practice care was better covered. Observed participants judged the videotaped practice consultations to be "natural," whereas hardly any family physician, after reviewing the videotaped consultations of the MSE, recognized his or her usual working style. Specific criteria made it possible to standardize real practice. Concerning criterion validity, only the medical-performance components of the two methods correlated. No correlation was found for the communication components. Real-practice performance proved to be less influenced by observation than was performance during the MSE. The reliabilities of the two methods, expected to be better in the controlled MSE, were comparable. The administration of the PVA was more flexible, less costly, and better accepted by the family physicians than was that of the MSE. CONCLUSION: Assessment for quality improvement of family physicians' practices by video observation in daily practice is superior to video assessment in a simulated setting using standardized patients.     

Kainate-induced apoptosis in cultured murine cerebellar granule cells elevates expression of the cell cycle gene cyclin D1

Recent evidence suggests that neuronal apoptosis is the consequence of an inappropriate reentry into the cell cycle. Expression of the cell cycle gene cyclin D1, a G1-phase cell cycle regulator, was examined in primary cultures of murine cerebellar granule cells (CGCs) during kainate (KA)-mediated apoptosis. Using cultures of CGCs, we found that a 24-h exposure to KA (1-3,000 microM) induced a concentration-dependent cell death with neurons exhibiting characteristic apoptotic morphology and extensive labeling using the terminal transferase-mediated nick end-DNA labeling (TUNEL) method. KA induced a time- and concentration-dependent increase in expression of cyclin D1 as determined by immunocytochemistry and western blot analysis. KA-induced apoptosis and cyclin D1 expression exhibited a similar concentration dependence and were significantly attenuated by the non-NMDA receptor antagonist 6-cyano-7-nitroquinoxaline-2,3-dione (50 microM), indicating a KA receptor-mediated effect. Here we present evidence for the first time that KA-induced apoptosis in cultured CGCs involves the induction of cyclin D1, suggesting its involvement in excitotoxic receptor-mediated apoptosis.