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     

Broken hyperbolic structures and affine foliations on surfaces

In this paper, we introduce two new kinds of structures on a non-compact surface: broken hyperbolic structures and broken measured foliations. The space of broken hyperbolic structures contains the Teichmüller space of the surface as a subspace. The space of broken measured foliations is naturally identified with the space of affine foliations of the surface. We describe a topology on the union of the space of broken hyperbolic structures and of the space of broken measured foliations which generalizes Thurston's compactification of Teichmüller space.     

Asymptotic approximation of functions and their derivatives by Müller’s Gamma operators

We obtain the complete asymptotic expansion of the image functions of Müller’s Gamma operators and of their derivatives. All expansion coefficients are explicitly calculated. Moreover, we study linear combinations of Gamma operators having a better degree of approximation than the operators themselves. Using divided differences we define general classes of linear combinations of which special cases were recently introduced and investigated by other authors.     

The mathematics of playing golf, or: a new class of difficult non-linear mixed integer programs

We consider a class of non-linear mixed integer programs with n integer variables and k continuous variables. Solving instances from this class to optimality is an NP-hard problem. We show that for the cases with k=1 and k=2, every optimal solution is integral. In contrast to this, for every k≥3 there exist instances where every optimal solution takes non-integral values. Received: August 2001 / Accepted: January 2002?Published online March 27, 2002     

Depth profiling of latex blends of fluorinated and fluorine‐free acrylates with laser‐induced secondary mass spectrometry

We explored phase separation and self‐assembly of perfluoroalkyl segments at the surface of polymer films obtained from latices of semifluorinated acrylate copolymers and the corresponding latex blends of nonfluorinated and semifluorinated polyacrylates. With laser‐induced secondary mass spectrometry the fluorine distribution was measured after annealing above the minimum film‐forming temperature of the polymers up to a depth of several micrometers. Depth profiles of a semifluorinated acrylate homopolymer and latex blends thereof with fluorine‐free alkylacrylates with 25, 50, and 75 mol % semifluorinated acrylate as well as a copolymer comprised of alkyl acrylate and semifluorinated acrylate (50/50 mol %) were investigated. In the case of latex blends containing both semifluorinated polyacrylates and fluorine‐free or low‐fluorine polymers, self‐assembly accounted for enrichment of the perfluoroalkyl segments at the surface. Coatings exhibiting low surface energy and having a substantially reduced total fluorine content were obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 360–367, 2003     

A complete asymptotic expansion of power means

The complete asymptotic expansion of power means in terms of Bell polynomials is obtained. Some results recently obtained by M. Bjelica are generalized.