Detecting unalloyed tin in LiSn2(PO4)3-based anodes with Mössbauer spectroscopy

The first discharge of the Li⁺ ion anode material LiSn₂(PO₄)₃ was investigated with Mössbauer spectroscopy and electrochemical techniques. Mössbauer spectroscopy provided insight into the structure of the tin atoms of the fully discharged anode materials. Spectra consist of overlapping peaks, which are assigned to noncrystalline β-Sn and Li–Sn alloy domains. An analysis of the relative intensities of the Mössbauer spectra shows the relative abundance of β-Sn increases at the expense of the Li–Sn alloy as the discharge rate increases. Cell polarization occurs at higher discharge rates, leading to inefficient electrode utilization and poor cycling performance. Sluggish Li⁺ ion diffusion through the amorphous Li₃PO₄ network that is formed early in the discharge process might be responsible for the poor electrochemical performance and the accumulation of unalloyed tin.     

Synthesis of Functional Polymers by Post‐Polymerization Modification

Post‐polymerization modification is based on the direct polymerization or copolymerization of monomers bearing chemoselective handles that are inert towards the polymerization conditions but can be quantitatively converted in a subsequent step into a broad range of other functional groups. The success of this method is based on the excellent conversions achievable under mild conditions, the excellent functional‐group tolerance, and the orthogonality of the post‐polymerization modification reactions. This Review surveys different classes of reactive polymer precursors bearing chemoselective handles and discusses issues related to the preparation of these reactive polymers by direct polymerization of appropriately functionalized monomers as well as the post‐polymerization modification of these precursors into functional polymers.     

Grafting of Polyfluorene by Surface‐Initiated Suzuki Polycondensation

Graft work : The first surface‐initiated and site‐specific palladium‐catalyzed Suzuki polycondensation that allows selective grafting and patterning of semiconducting and emissive poly[9,9‐bis(2‐ethylhexyl)fluorene] ( 1 ) at room temperature is developed (see scheme). The pattering is demonstrated by AFM (see image).

     

Enantioselective Friedel–Crafts Reactions in Water Using a DNA‐Based Catalyst

Taking the plunge : The first example of a Lewis acid catalyzed asymmetric Friedel–Crafts alkylation with olefins in water is described. By using loadings of a DNA‐based copper catalyst as low as 0.15 mol %, good yields and excellent enantioselectivities were obtained in the reaction of α,β‐unsaturated 2‐acyl imidazoles with heteroaromatic π nucleophiles. dmbpy=4,4′‐dimethyl‐2,2′‐bipyridine.

     

Existence of non-trivial harmonic functions on Cartan–Hadamard manifolds of unbounded curvature

The Liouville property of a complete Riemannian manifold M (i.e., the question whether there exist non-trivial bounded harmonic functions on M) attracted a lot of attention. For Cartan–Hadamard manifolds the role of lower curvature bounds is still an open problem. We discuss examples of Cartan–Hadamard manifolds of unbounded curvature where the limiting angle of Brownian motion degenerates to a single point on the sphere at infinity, but where nevertheless the space of bounded harmonic functions is as rich as in the non-degenerate case. To see the full boundary the point at infinity has to be blown up in a non-trivial way. Such examples indicate that the situation concerning the famous conjecture of Greene and Wu about existence of non-trivial bounded harmonic functions on Cartan–Hadamard manifolds is much more complicated than one might have expected.      

On the complexity of hydromount-models in full vehicle simulation

The influence of the complexity of hydromount-models on the results in full vehicle simulation is studied. In particular, a Kelvin-Voigt model, a linear lever model and a non-linear model are assessed with respect to their predictive capabilities as compared to the necessary parameterization and computation efforts. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On triviality of the Kashiwara–Vergne problem for quadratic Lie algebras

We show that the Kashiwara–Vergne (KV) problem for quadratic Lie algebras (that is, Lie algebras admitting an invariant scalar product) reduces to the problem of representing the Campbell–Hausdorff series in the form $\ln (e^x{e}^y)=x+y+[x,a(x,y)]+[y,b(x,y)]$, where $a(x,y)$ and $b(x,y)$ are Lie series in x and y. This observation explains the existence of explicit rational solutions of the quadratic KV problem, whereas constructing an explicit rational solution of the full KV problem would probably require the knowledge of a rational Drinfeld associator. It also gives, in the case of quadratic Lie algebras, a direct proof of the Duflo theorem (implied by the KV problem). To cite this article: A. Alekseev, C. Torossian, C. R. Acad. Sci. Paris, Ser. I 347 (2009).     

Random and algebraic permutations’ statistics

An algebraic permutation $\hat{A}\in S(N=n^{m})$ is the permutation of the N points of the finite torus ? _n ^m , realized by a linear operator A∈SL(m,? _n ). The statistical properties of algebraic permutations are quite different from those of random permutations of N points. For instance, the period length T(A) grows superexponentially with N for some (random) permutations A of N elements, whereas $T(\hat{A})$ is bounded by a power of N for algebraic permutations  $\hat{A}$ . The paper also contains a strange mean asymptotics formula for the number of points of the finite projective line P¹(? _n ) in terms of the zeta function.     

Selective oxo functionalization of the uranyl ion with 3d metal cations

The linear uranyl dication [UO2]2+ can be bound in one of two coordination sites in the ditopic Pacman-shaped pyrrolic macrocyle H4L. Incorporation of Mn2+, Fe2+, or Co2+ cations in the second donor compartment affords the first uranyl complexes with a transition-metal-functionalized oxo group.     

The lipidated membrane anchor of full length N-Ras protein shows an extensive dynamics as revealed by solid-state NMR spectroscopy

Many proteins involved in signal transduction are equipped with covalently attached lipid chains providing a hydrophobic anchor targeting these molecules to membranes. Despite the considerable biological significance of this membrane binding mechanism for 5-10% of all cellular proteins, to date very little is known about structural and dynamical features of lipidated membrane binding domains. Here we report the first comprehensive study of the molecular dynamics of the C-terminus of membrane-associated full-length lipidated Ras protein determined by solid-state NMR. Fully functional lipid-modified N-Ras protein was obtained by chemical-biological synthesis ligating the expressed water soluble N-terminus with a chemically synthesized (2)H or (13)C labeled lipidated heptapeptide. Dynamical parameters for the lipid chain modification at Cys 181 were determined from static (2)H NMR order parameter and relaxation measurements. Order parameters describing the amplitude of motion in the protein backbone and the side chain were determined from site-specific measurements of (1)H-(13)C dipolar couplings for all seven amino acids in the membrane anchor of Ras. Finally, the correlation times of motion were determined from temperature dependent relaxation time measurements and analyzed using a modified Lipari Szabo approach. Overall, the C-terminus of Ras shows a versatile dynamics with segmental fluctuations and axially symmetric overall motions on the membrane surface. In particular, the lipid chain modifications are highly flexible in the membrane.