Surface Modification of Smectite Clay Induced by Non-thermal Gliding Arc Plasma at Atmospheric Pressure

Smectite clay from Sabga (west-Cameroon) was treated in aqueous suspension by gliding arc plasma to modify its surface properties. The evolution of the modifications was followed with the exposure time and post-discharge duration using Fourier transformed infra red spectroscopy and scanning electron microscopy. X-ray diffraction and nitrogen physisorption analyses were also performed to evaluate if both crystalline and textural properties of the material are affected by the treatment. The results obtained show that the plasma treatment causes the breakdown of structural bounds at the clay surface and induces the formation of new hydroxyl groups (Si–OH and Al–OH) on the clay edges. Crystallinity, sheet structure and textural properties are not significantly affected by the plasma treatment. However, it should be noted that an intensive treatment of the clay lowers the pH of the suspension, which subsequently induces an acid attack of the clay. In such case, the specific surface area of the clay increases. This study demonstrates that gliding arc plasma treatments can be used to activate clay minerals for environmental application.     

Acetylene Derivatives of Cationic Diazaoxatriangulenes and Diaza [4]Helicenes - Access to Red Emitters and Planar Chiral Stereochemical Traits

Cationic triangulenes, and related helicenes, constitute a rich class of dyes and fluorophores, usually absorbing and emitting light at low energy, in the orange to red domains. Recently, to broaden the scope of applications, regioselective late-stage functionalizations on these core moieties have been developed. For instance, with the introduction of electron-donating groups (EDGs), important bathochromic shifts are observed pushing absorptions towards or in the near-infrared (NIR) spectral domain while emissive properties disappear essentially completely. Herein, to upset this drawback, acetylene derivatives of cationic diazaoxa triangulenes (DAOTA) and [4]helicenes are prepared (16 examples). Contrary to other EDG-functionalized derivatives, C≡C− functionalized products remain broadly fluorescent, with red-shifted absorptions (Δλ_abs up to 25 nm) and emissions (Δλ_em up to 73 nm, Φ_PL up to 51 %). Quite interestingly, a general dynamic stereoisomerism phenomenon is evidenced for the compounds derived from achiral DAOTA cores. At low temperature in ¹H NMR spectroscopy (218 K), N−CH₂ protons become diastereotopic with chemical shifts differences (Δδ) as high as +1.64 ppm. The signal coalescence occurs around 273 K with a barrier of ∼12 kcal mol⁻¹. This phenomenon is due to planar chiral conformations (S_p and R_p configurations), induced by the geometry of the alkyl (n-propyl) side-chains next to the acetylenic substituents. Ion pairing studies with Δ-TRISPHAT anion not only confirm the occurrence of the chiral conformations but evidence a moderate but definite asymmetric induction from the chiral anion onto the cations. Finally, DFT calculations offer a valuable insight on the geometries, the corresponding stereodynamics and also on the very large difference in NMR for some of the diastereotopic protons.     

Microstructure and physico-chemical transformation of some common woods from Cameroon during drying

Journal of Thermal Analysis and Calorimetry - The influence of drying on the microstructure, physical and chemical properties of some tropical wood species has been investigated using...     

Fuzzy Markov Chains and Decision-Making

Decision-making in an environment of uncertainty and imprecision for real-world problems is a complex task. In this paper it is introduced general finite state fuzzy Markov chains that have a finite convergence to a stationary (may be periodic) solution. The Cesaro average and the -potential for fuzzy Markov chains are defined, then it is shown that the relationship between them corresponds to the Blackwell formula in the classical theory of Markov decision processes. Furthermore, it is pointed out that recurrency does not necessarily imply ergodicity. However, if a fuzzy Markov chain is ergodic, then the rows of its ergodic projection equal the greatest eigen fuzzy set of the transition matrix. Then, the fuzzy Markov chain is shown to be a robust system with respect to small perturbations of the transition matrix, which is not the case for the classical probabilistic Markov chains. Fuzzy Markov decision processes are finally introduced and discussed.     

Facile synthetic access to and biological evaluation of the macrocyclic core of apoptolidin

Oxidative cleavage of the C-20/C-21 bond in apoptolidin (1) provides two fragments of similar complexity, facilitating a divide-and-diversify strategy for the determination of the structural basis for apoptolidin's biological activity, the remarkably selective induction of apoptosis in sensitive cell lines. The ability of compounds derived from this cleavage to inhibit mitochondrial F(0)F(1)-ATPase is reported. [structure: see text]     

Probabilistic representation and approximation for coupled systems of variational inequalities

Our study is dedicated to the probabilistic representation and numerical approximation of solutions of coupled systems of variational inequalities. We interpret the unique viscosity solution of a coupled system of variational inequalities as the solution of a one-dimensional constrained BSDE with jumps. This new representation allows for the introduction of a natural probabilistic numerical scheme for the resolution of these systems.     

Sur les représentations linéaires des groupes clos

Sans résumé     

Surface morphology of Ge‐modified 3C‐SiC/Si films

The influence of Ge deposition prior to carbon interaction with 3° off‐axis Si(111) substrates on the structural and morphological properties of the formed silicon carbide (SiC) layer is studied. In situ reflection high‐energy electron diffraction (RHEED) and X‐ray diffraction (XRD) revealed the formation of the cubic silicon carbide (3C‐SiC) modification. In situ spectroscopic ellipsometry measurements revealed a decreasing 3C‐SiC thickness with increasing Ge predeposition. Atomic force microscopy (AFM) studies revealed that the surface overlayer morphology is mainly formed by periodic step arrangements whose relevant geometric parameters, i.e. lateral separation, height and terrace width, depend on the Ge content. Besides the changes of the step morphology, the surface roughness and the grain size and the strain of the formed 3C‐SiC decreases with increasing germanium precoverage. Copyright © 2008 John Wiley & Sons, Ltd.