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     

Distribution results for lattices in SL(2,ℚ p )

In this paper we study the ergodic properties of the linear action of lattices Γ of SL(2,ℚ_p) on ℚ_p × ℚ_p and distribution results for orbits of Γ. Following Serre, one can define a “geodesic flow” for an associated tree (actually associated to GL(2,ℚ_p)). The approach we use is based on an extension of this approach to “frame flows” which are a natural compact group extension of the geodesic flow.     

The strong relaxation limit of the multidimensional isothermal Euler equations

We construct global smooth solutions to the multidimensional isothermal Euler equations with a strong relaxation. When the relaxation time tends to zero, we show that the density converges towards the solution to the heat equation.

     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

Fonctions constructibles et intégration motivique II

We extend the formalism of an earlier Note to a global setting for which a theorem on fiber integrals and a Fubini theorem are obtained. We compare our formalism to the previous constructions given by Denef and Loeser. To cite this article: R. Cluckers, F. Loeser, C. R. Acad. Sci. Paris, Ser. I 339 (2004).     

Markovian Solutions of Inviscid Burgers Equation

For solutions of (inviscid, forceless, one dimensional) Burgers equation with random initial condition, it is heuristically shown that a stationary Feller–Markov property (with respect to the space variable) at some time is conserved at later times, and an evolution equation is derived for the infinitesimal generator. Previously known explicit solutions such as Frachebourg–Martin's (white noise initial velocity) and Carraro–Duchon's Lévy process intrinsic-statistical solutions (including Brownian initial velocity) are recovered as special cases.     

Speed of adaptation in structured populations

Adaptation of populations takes place with the occurrence and subsequent fixation of mutations that confer some selective advantage to the individuals which acquire it. For this reason, the study of the process of fixation of advantageous mutations has a long history in the population genetics literature. Particularly, the previous investigations aimed to find out the main evolutionary forces affecting the strength of natural selection in the populations. In the current work, we investigate the dynamics of fixation of beneficial mutations in a subdivided population. The subpopulations (demes) can exchange migrants among their neighbors, in a migration network which is assumed to have either a random graph or a scale-free topology. We have observed that the migration rate drastically affects the dynamics of mutation fixation, despite of the fact that the probability of fixation is invariant on the migration rate, accordingly to Maruyama's conjecture. In addition, we have noticed a topological dependence of the adaptive evolution of the population when clonal interference becomes effective.     

Inherited LU-factorizations of matrices

Various types of LU-factorizations for nonsingular matrices, where L is a lower triangular matrix and U is an upper triangular matrix, are defined and characterized. These types of LU-factorizations are extended to the general m × n case. The more general conditions are considered in the light of the structures of [C.R. Johnson, D.D. Olesky, P. Van den Driessche, Inherited matrix entries: LU factorizations, SIAM J. Matrix Anal. Appl. 10 (1989) 99-104]. Applications to graphs and adjacency matrices are investigated. Conditions for the product of a lower and an upper triangular matrix to be the zero matrix are also obtained.     

Multipole-Bound Molecular Negative Ions

 Within the framework of a simple electrostatic model, as compared to recent experimental results, we here discuss the stability of very weakly bound molecular negative ions. In contrast with the case of conventional valence anions, the excess electron is then located in a very diffuse orbital and is mainly bound by electrostatic dipolar, quadrupolar, and polarization forces, at large distances from the neutral molecular core. By fitting a single repulsion parameter of the model to the available experimental data, it is possible to make quantitative predictions of the excess-electron binding energies in these species. Critical values of the dipole moment, quadrupole moment or polarizability required for the observation of stable multipole-bound negative ions are predicted and compared to available experimental data and ab initio calculations. Received October 24, 2001; accepted for publication November 16, 2001