The role of the hydration configuration in electronic processes involving ions in aqueous solution

The nature of small ions in electrolytic (e.g., aqueous) solutions is discussed in terms of the configuration of the adjoining polarized medium, and the role of this configuration in electronic transitions involving one or a pair of ions is treated in a general way. Light absorption by a single ion is shown to depend critically on this configuration; a theory developed previously by the authors is reviewed, and future possibilities of exploring the nature of the configuration by investigation of such spectra are explained. Electronic transitions, such as an “electron transfer” process, during binary collisions of ions are treated, and a general method is developed, based uponDebye's “diffusion” theory for ion collision rates and a nonadiabatic type of potential curve. Rates of chemical processes are found to depend decisively on the interaction of two ions at separations where the simple coulomb law is not valid.     

Double deprotonation of acetylenic oxiranes: synthesis of allenic ketones through Dilithio Ynenolates

[reaction: see text] The double deprotonation of acetylenic oxiranes gives allenic ketones through the 1,2-H or 1,2-Ar shift on the transient oxiranyl dianion intermediates. The resulting dilithium ynenolates give allenic ketones upon hydrolysis or can be quenched with various electrophiles.     

Kinematic regimes of convection at high Prandtl number in a shallow cavityRégimes cinématiques de la convection à haut nombre de Prandtl dans une cavité allongée.

We consider free convection in a horizontal shallow cavity with different end temperatures, filled with a high Prandtl number fluid. From scaling analysis, we find two kinematic regimes resulting from the competition of heat transfer by conduction and by convection. Numerical simulations realized for a large range of Rayleigh number and aspect ratio confirm the phenomenological analysis and provide the threshold between the two regimes. The conductive and convective regimes occur at $\mathit{Ra}{A}^2$ smaller and larger than 443 respectively, where Ra is the Rayleigh number and A is the aspect ratio. In the convective regime, the characteristic velocity is independent of depth of the cavity. To cite this article: J.-M. Flesselles, F. Pigeonneau, C. R. Mecanique 332 (2004).     

Synthesis of l-cyclopentenyl nucleosides using ring-closing metathesis and palladium-mediated allylic alkylation methodologies

The enantiomeric synthesis of l-cyclopentenyl nucleosides is described. The key intermediate (+)-cyclopentenyl alcohol (8) was prepared from methyl-α-d-galactopyranoside 1 using a ring closing metathesis reaction. Transformation of the allylic alcohol 8 into the allylic acetate (9) or carbonate (10), allows their coupling with purine and pyrimidine bases under Pd(0)-catalyzed Tsuji-Trost allylic alkylation's to yield 12a-c. The Pd catalyzed reaction was found to require the use of AlEt₃.     

Singular electromagnetic fields: inductive approach

In a non-convex polyhedral domain, we describe the local trace (i.e. defined on a face) of the normal derivative of an $L^2$ function, with $L^2$ Laplacian. We then provide generalized integration by parts formulae for the Laplace, divergence and curl operators. Finally, these results allow us to split electromagnetic fields into regular and singular parts, which can be characterized. To cite this article: F. Assous et al., C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

Protochlorophyllide reduction: mechanisms and evolutions

Protochlorophyllide (Pchlide) reductases are key enzymes in the process of chlorophyll biosynthesis. In this review, current knowledge on the molecular organization, substrate specificity and assembly of the light-dependent reduced nicotinamide adenine dinucleotide phosphate:Pchlide oxidoreductases are discussed. Characteristics of light-independent enzymes are also described briefly, and the possible reasons for the selection of light-dependent enzymes during the course of evolution are discussed.     

Stereoselective Barbier-type allylation reaction of trifluoromethyl aldimines

Trifluoromethyl aldimines could react, under Barbier conditions in the presence of activated zinc, in DMF at room temperature or in THF at reflux, with various allyl bromides to provide the corresponding homoallylamines. Secondary homoallyl trifluoromethylamines were stereoselectively obtained from the optically active aldimine 12 with an excellent diastereoisomeric excess (98%).     

Hydrogen adsorption in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-CO2) (M = Al3+, Cr3+), MIL-53

Hydrogen adsorption has been studied in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-CO2) (M = Al3+, Cr3+); these solids show a hydrogen storage capacity of 3.8 and 3.1 wt.% respectively when loaded at 77 K under 1.6 MPa.     

Asymptotique des approximants de Hermite–Padé quadratiques de la fonction exponentielle et problèmes de Riemann–Hilbert

We describe the asymptotic behavior of the polynomials $\text{p,}\text{q,}\text{r}$ of degree n in type I Hermite–Padé approximation to the exponential function, i.e., $\text{p(z)}\text{e}{}^{\mathrm{?z}}\text{+q(z)+r(z)}\text{e}{}^{\mathrm{z}}\text{=}\text{O}\text{(z}{}^{\mathrm{3n+2}}\text{)}$ as z→0. A steepest descent method for Riemann–Hilbert problems, due to Deift and Zhou, is used to obtain strong uniform asymptotics for the scaled polynomials $\text{p(3nz),}\text{q(3nz),}\text{r(3nz)}$ in every domain of the complex plane. An important role is played by a three-sheeted Riemann surface and certain measures and functions defined on it. To cite this article: A. Kuijlaars et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003).