Three-dimensional imaging of sulfides in silicate rocks at submicron resolution with multiphoton microscopy

We report the first application of multiphoton microscopy (MPM) to generate three-dimensional (3D) images of natural minerals (micron-sized sulfides) in thick (～120 μm) rock sections. First, reflection mode (RM) using confocal laser scanning microscopy (CLSM), combined with differential interference contrast (DIC), was tested on polished sections. Second, two-photon fluorescence (TPF) and second harmonic signal (SHG) images were generated using a femtosecond-laser on the same rock section without impregnation by a fluorescent dye. CSLM results show that the silicate matrix is revealed with DIC and RM, while sulfides can be imaged in 3D at low resolution by RM. Sulfides yield strong autofluorescence from 392 to 715 nm with TPF, while SHG is only produced by the embedding medium. Simultaneous recording of TPF and SHG images enables efficient discrimination between different components of silicate rocks. Image stacks obtained with MPM enable complete reconstruction of the 3D structure of a rock slice and of sulfide morphology at submicron resolution, which has not been previously reported for 3D imaging of minerals. Our work suggests that MPM is a highly efficient tool for 3D studies of microstructures and morphologies of minerals in silicate rocks, which may find other applications in geosciences.     

Integral Representation Results for Energies Defined on Stochastic Lattices and Application to Nonlinear Elasticity

This article is devoted to the study of the asymptotic behavior of a class of energies defined on stochastic lattices. Under polynomial growth assumptions, we prove that the energy functionals F_e{F_\varepsilon} stored in the deformation of an e{{\varepsilon}}-scaling of a stochastic lattice Γ-converge to a continuous energy functional when e{{\varepsilon}} goes to zero. In particular, the limiting energy functional is of integral type, and deterministic if the lattice is ergodic. We also generalize, to systems and nonlinear settings, well-known results on stochastic homogenization of discrete elliptic equations. As an application of the main result, we prove the convergence of a discrete model for rubber towards the nonlinear theory of continuum mechanics. We finally address some mechanical properties of the limiting models, such as frame-invariance, isotropy and natural states.     

Methyl proton contacts obtained using heteronuclear through-bond transfers in solid-state NMR spectroscopy

A two-dimensional proton-mediated carbon-carbon correlation experiment that relies on through-bond heteronuclear magnetization transfers is demonstrated in the context of solid-state NMR of proteins. This new experiment, dubbed J-CHHC by analogy to the previously developed dipolar CHHC techniques, is shown to provide selective and sensitive correlations in the methyl region of 2D spectra of crystalline organic compounds. The method is then demonstrated on a microcrystalline sample of the dimeric protein Crh (2 x 10.4 kDa). A total of 34 new proton-proton contacts involving side-chain methyl groups were observed in the J-CHHC spectrum, which had not been observed with the conventional experiment. The contacts were then used as additional distance restraints for the 3D structure determination of this microcrystalline protein. Upon addition of these new distance restraints, which are in large part located in the hydrophobic core of the protein, the root-mean-square deviation with respect to the X-ray structure of the backbone atom coordinates of the 10 best conformers of the new ensemble of structures is reduced from 1.8 to 1.1 A.     

Biosynthesis of conjugatable saccharidic moieties of GM2 and GM3 gangliosides by engineered E. coli

Oligosaccharidic moieties of GM(2) and GM(3) gangliosides bearing an allyl or a propargyl aglycon, are efficiently biosynthesized on the gram scale by growing metabolically engineered Escherichia coli cells in the presence of the corresponding lactoside acceptors and sialic acid.     

Quinone transfer radical polymerization (QTRP) of styrene: Catalysis by different metal complexes

Styrene has been polymerized by a Quinone Transfer Radical Polymerization (QTRP) based on the redox reaction of an ortho‐quinone and a metal catalyst. Several metal acetylacetonates have been tested in this work. The radical polymerization of styrene is largely controlled when phenanthrenequinone (PhQ) is used with catalytic amounts of Co(acac)₂, Ni(acac)₂, Mn(acac)_{2 or 3}, and Al(acac)₃. As a rule, in the presence of all these metallic complexes, the polystyrene molar mass increases with the monomer conversion, and polydispersity (M_w/M_n) is in the 1.3–1.6 range (at least until 40% monomer conversion). Styrene polymerization has also been resumed by polystyrene chains prepared by QTRP. In the specific case of manganese acetylacetonates, an amine or phosphine ligand has to be added for the control to be effective. Finally, two mechanistic hypotheses have been proposed, depending on whether the oxidation state of the metal can be easily changed or not. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2723‐2733, 2005     

Classical Yang-Mills-Dirac equations: Qualitative analysis of some solutions with a noncompact symmetry group

We consider classical Yang-Mills and Yang-Mills-Dirac equations on Minkowski space, with gauge group SU(2), and look for solutions invariant (up to a gauge transformation) under SO(3)×SO₀(1, 1) and SO₀(2, 1)×SO(2), respectively. In each case, we analyze the qualitative features of the solutions, in particular the asymptotic behavior as the solution approaches its singularities. The method is based on standard theorems from the theory of nonlinear ordinary differential equations.     

Preliminary Communications Thermotropic liquid crystal behaviour of 5,5'-[(4-hexadecyloxyphenyl)ethynyl]-2,2'-bipyridine

5,5'-[(4-Hexadecyloxyphenyl)ethynyl]-2,2'-bipyridine was synthesized by a palladium(O) cross-coupling reaction. Its thermotropic liquid crystalline behaviour was analysed using differential scanning calorimetry, polarizing microscopy, and X-ray diffraction. Three enantiotropic tilted smectic phases were identified upon heating: S_F, S_I, and S_C.