Synthesis of Benzazepine Analogues of Noscapine

The synthesis of benzazepine analogues of the opium alkaloid noscapine ( 1 ) is described. The benzazepines 2 and 3 were prepared starting from nornarceine ethyl ester ( 4 ; readily available from 1 ) in several steps. X-Ray analysis of compound 2 revealed that it is not a diastereosisomer mixture but a racemate of the threo-form and thus has the same configuration as 1 .     

Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Possible evidence for a narrow isovectorB=2 resonance below pion production threshold

Some evidence is presented for a narrow peak at 1969±2 MeV (FWHM=9±2 MeV) in the missing mass spectrum of the³He(p, d) reaction, with 3 standard deviations. The nature of this state, the mass of which is below the NN threshold, is discussed in connection with structures found in other experiments.     

Luminescent Labels—More than Just an Alternative to Radioisotopes?

Chemical, chromatographic, or spectrometric methods are generally unsuitable for the detection of molecules in the nano and subnanogram region because of their low sensitivity. The radioimmunoassay (RIA) developed by Yalow and Berson in 1959 combined the high sensitivity of radioactively labeled substances with the high specificity of immunological reactions for the first time. In this way it was possible to detect quantitatively the tiniest traces of substances in the presence of an excess of other, in some cases, similar foreign substances without prior enrichment. Immunoassays have certainly developed to become the most valuable analytical tool of in vitro diagnostics and are today routinely employed for the detection of endogenous and exogenous substances (e.g. hormones, tumor-associated proteins, bacteria, viruses, toxins, drugs, etc). The many disadvantages of radioactivity such as the required handling licenses, disposal costs, precautions necessary to prevent risks to health, short shelf-life, and limited sensitivity soon led to the search for other nonradioactive labeling methods. Encouraged by the development of light measuring techniques and the commercial availability of highly sensitive apparatus, radioactive isotopes as labels are today being replaced increasingly by enzymes, fluorophores, or luminophores. Some of the new luminescent labels have, however, not only facilitated replacement of radioisotopes, but also a breakthrough into what has until now been unattainable levels of sensitivity. The following article reviews the methods of luminescent labeling and their applications mainly in the area of immunoassays.     

A procedure for clean deposition of100Pd on surfaces

For a program of surface and interface experiments with the PAC isotope¹⁰⁰Pd, a procedure has been developed to chemically separate¹⁰⁰Pd from irradiated rhodium and deposit it on surfaces by evaporation under UHV conditions. First results have been obtained for¹⁰⁰Pd on an Ni(111) surface.     

Aerodynamics of ski jumping: experiments and CFD simulations

The aerodynamic behaviour of a model ski jumper is investigated experimentally at full-scale Reynolds numbers and computationally applying a standard RANS code. In particular we focus on the influence of different postures on aerodynamic forces in a wide range of angles of attack. The experimental results proved to be in good agreement with full-scale measurements with athletes in much larger wind tunnels, and form a reliable basis for further predictions of the effects of position changes on the performance. The comparison of CFD results with the experiments shows poor agreement, but enables a clear outline of simulation potentials and limits when accurate predictions of effects from small variations are required.     

Rigidity in holomorphic and quasiregular dynamics

We consider rigidity phenomena for holomorphic functions and then more generally for uniformly quasiregular maps.