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     

Thermodynamic non-additivity in disordered systems with extended phase space

Non-additivity effects in coupled dynamic-stochastic systems are investigated. It is shown that there is a mapping of the replica approach to disordered systems with finite replica indexn on Tsallis non-extensive statistics, if the average thermodynamic entropy of the dynamic subsystem differs from the information entropy for the probability distribution in the stochastic subsystem. The entropic indexq is determined by the entropy difference ΔS. In the case of incomplete information, the entropic indexq=1−n is shown to be related to the degree of lost information.     

Boundary blow-up for differential equations with indefinite weight

We obtain results of existence and multiplicity of solutions for the second-order equation x″+q(t)g(x)=0, with x(t) defined for all t∈]0,1[ and such that x(t)→+∞ as t→0⁺ and t→1⁻. We assume g having superlinear growth at infinity and q(t) possibly changing sign on [0,1].     

Mössbauer study on LiFePO4 cathode material for lithium ion batteries

Crystalline LiFePO₄ has been synthesized using solid-state, spray pyrolysis, and wet chemical methods. The crystal parameters were obtained from Rietveld’s refinement methods of the X-ray diffraction patterns. A detailed investigation of the Fe valency carried out using Mössbauer spectroscopy at room temperature indicates that Fe is predominantly present in its bivalent state.