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     

Multiple-scattering-theory analysis of XANES spectra of SO2 adsorbed on Cu(100)

The sulphur K-edge x-ray absorption spectra of SO₂ multilayer and of SO₂ submonolayer adsorbed on Cu(100) are analysed. It is found that the dominant spectral features are of a molecular origin. The results support earlier findings that the SO₂ molecule stands perpendicular to the surface. Use of non-selfconsistent potentials does not lead to a good quantitative agreement between theory and experiment.     

Parity violation at neutron p-wave resonances of238U and232Th and related questions

Parity violation effects have been studied at 40 neutron p-wave resonances of the even-even nuclei²³⁸U and²³²Th. Of these 11 show parity violation effects larger than 2 standard deviations, making parity violation a rather common phenomenon. Parity mixing up to 10% has been found. The root-mean squared matrix elements for parity violation derived from these resonances are M=0.58 (+0.50/-0.25) meV for²³⁸U, respectively 1.39 (+0.35/-0.38) meV for²³²Th.     

Preparation of silane-grafted pellets: silica bound reagents in a very convenient form

High surface area silica pellets are excellent supports for the preparation of silica supported reagents and solid-phase basal linkers through reaction with (RO)₃Si(CH₂)₃FG (FG=NH₂, NHMe, Cl, NHC(O)NH₂, OC(O)CMe(CH₂), NCO, NEt₂). High loadings (0.66-2.15 mmol g⁻¹) of grafted silane materials are realised at synthetically useful loadings per pellet (ca. 0.06 mmol). Preliminary trials show that trial linker chemistry and ligand synthesis can be carried out on these materials and that these reactions can be monitored by solid state ¹³C NMR studies on individual pellets.     

The Cosmological Constant in the Framework of Gravito-Magnetodynamic Waves in Weak Gravitational Fields

Using the linearization of Einstein's equations for weak gravitational fields, a specific model of gravito-magnetofluid is elaborated. The study of wave formation and propagation in such a medium is necessarily connected to the existence of the cosmological constant.     

Metallo‐supramolecular micelles: Studies by analytical ultracentrifugation and electron microscopy

In aqueous solutions, amphiphilic block copolymers in which a polystyrene (PS) segment is connected to a poly(ethylene oxide) (PEO) block via a bis(2,2′:6′,2″‐ terpyridine ruthenium) complex can form micelles. Such micelles of the protomer type PS₂₀‐[Ru]‐PEO₇₀, according to the preparation procedure representing frozen micelles, were studied by sedimentation velocity and sedimentation equilibrium analysis in an analytical ultracentrifuge and by transmission electron microscopy, with different techniques applied for the sample preparation. The particles obtained were surprisingly multifarious in size. In ultracentrifugation experiments performed at relatively low salt concentrations, the distributions of the sedimentation coefficient s_20,w showed a pronounced peak at 9.6 S and a broad, only partly separated second peak around 14 S. The molar mass of the particles at the peak was around 430,000 g/mol, corresponding to an aggregation number of approximately 85. The average hydrodynamic diameter of the particles in the peak fraction was approximately 13 nm. In electron micrographs of negatively stained samples, spheres of diameters between 10 and 25 nm were the most abundant particles, but larger ones with a wide size range were also visible. The latter particles apparently were composed of smaller ones. The data from both sedimentation analysis and electron microscopy showed that (1) the studied compound formed primary micelles of diameters around 20 nm and (2) the primary micelles had a tendency toward aggregation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3159–3168, 2003     

The course scheduling problem at Lufthansa Technical Training

Lufthansa Technical Training GmbH (LTT) performs training courses for Lufthansa Technik AG as well as for several other international airlines. Courses of about 670 different types are offered of which several hundred take place each year. The course scheduling problem faced by LTT is to construct a yearly schedule which maximizes the profit margin incurred while meeting a variety of complex precedence, temporal, and resource-related constraints. A “good” operational schedule should also meet a number of additional subordinate objectives. We formalize the problem and develop a heuristic scheme along with several priority rules, as well as a local search algorithm to determine well-suited weights for weighted composite rules. The operational planning situation of 1996 served as our major test instance; additional test instances were constructed by modifying this data. Several computational experiments were carried out to evaluate the performance of the algorithms. It turned out that the best so-found schedule is substantially better in terms of the profit margin incurred than the solution manually constructed by LTT.     

Parakristalline Gitterstörungen in Kettenrichtung von Cellulose I und II

Zusammenfassung Röntgenweitwinkelmessungen an Ramie sowie an einer Viskosefaser zeigen, daß in Kettenrichtung parakristalline Störungen vong=1,1% bzw.g=1,5% vorliegen. Die mittleren Kristallitgrößen in Kettenrichtung betragen¯D ₀₁₀=485 Å bzw.¯D ₀₁₀=112 Å, senkrecht dazu etwa¯D=52 Å bzw.¯D=41 Å. Aus Röntgenkleinwinkelmessungen ergeben sich kleinste Fibrillendurchmesser von 2R=52 Å bzw. 2R=45 Å. Die gefundenen Fibrillendurchmesser verhalten sich wie 1248.Für die Viskosefaser wird eine Langperiode vonP=168 Å gemessen, woraus mit¯D ₀₁₀=112 Å folgt, daß die ungeordneten Bereiche in Kettenrichtung eine Länge von etwa 56 Å haben.

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Summary Wide angle X-ray diffraction studies on ramie and on a viscose fibre show that paracrystalline distortions exist in chain direction havingg-values ofg=1.1% andg=1.5%, respectively. The mean crystallite sizes in chain direction are¯D ₀₁₀=485 Å and¯D ₀₁₀=112 Å, respectively. Perpendicular to the chain direction mean crystallite sizes of approximately¯D=52 Å and¯D=41 Å, respectively, are measured.Small angle X-ray diffraction studies give the diameters of the cellulose fibrils, the smallest of which are 2R=52 Å and 2R=45 Å, respectively. The diameters of the fibrils are in the ratio of 1248.A long period ofP=168 Å is measured for the viscose fibre implying a length of 56 Å for the disordered domains in chain direction.

     

Paketimpulse in der magnetischen Kernresonanz

Composite Pulses in Nuclear Magnetic Resonance For the compensation of spatial inhomogeneity of the radiofrequency field and a resonance offset in NMR experiments, composite pulses are used instead of the conventional single pulses. In the present work the effect of a resonance offset on composite pulses is treated quantitatively. It will be shown also experimentally that the various constructions for \documentclass{article}\pagestyle{empty}\begin{document}$ \frac{\pi }{2} $\end{document} composite pulses (contrary to π composite pulses) lead to only two different degrees of compensation depending on the choice of the phase of the pulses or the sign of the resonance offset.