Water condensation in hydrophobic silicalite-1 zeolite: a molecular simulation study

We report grand canonical Monte Carlo simulations of the gas and liquid phase adsorption of water in silicalite-1 zeolite. Simple but effective models and simulation methods, found useful for studying gas adsorption in nanoporous materials, have been extended to describe the intrusion/extrusion cycle of water in this hydrophobic solid. The picture of water confined to hydrophobic spaces of nanoscopic dimensions that emerges from this study is one of a strongly depleted and highly inhomogeneous fluid.     

Molecular modeling studies focused on 5-HT7 versus 5-HT1A selectivity. Discovery of novel phenylpyrrole derivatives with high affinity for 5-HT7 receptors

The present study discusses the well-known 5-HT7/5-HT1A selectivity issue through a new series of phenylpyrrole derivatives. The first hits emerged from a virtual screening performed on a chemolibrary. Further study led to an optimization of a preliminary 5-HT7 pharmacophore model. The importance of each pharmacophoric feature is confirmed, but these characteristics have to be coupled to geometric constraints in order to achieve a 5-HT7 selectivity. Indeed, 5-HT1A affinity probably arises from extended conformations, whereas a bent one appears to be best suited for 5-HT7 selectivity.     

Syntheses and reactivity of 'sulfur rich' Re(iii) and Tc(iii) complexes containing trithioperoxybenzoate, dithiobenzoate and dithiocarbamate ligands

Reduction-substitution reactions of [M(O)Cl(4)](-)(M=Re, (99)Tc) precursors with an excess of substituted dithiobenzoate ligands (R-PhCS(2))(-) in dichloromethane/methanol mixtures afford a series of six-coordinated neutral mixed-ligand complexes of the type M(III)(R-PhCS(3))(2)(R-PhCS(2))(M=Re; Rel--9; M=99)Tc; Tel--9). The coordination sphere is entirely filled by sulfur donor atoms, and the complexes adopt a distorted trigonal prismatic arrangement, as assessed by the X-ray crystal structure analysis of Re(4-Me-PhCS(3))(2)(4-Me-PhCS(2)), Re 2. These compounds show sharp proton and carbon NMR profiles, in agreement with the diamagnetism typical of low spin d(4) trigonal prismatic configurations. The red-ox processes involve reduction of the metal from Re(v) to Re(iii) and oxidation of dithiobenzoate to trithioperoxybenzoate. M2--9 complexes contain a substitution-inert [M(R-PhCS(3))(2)](+) moiety including the metal and two trithioperoxybenzoate fragments, while the third dithiobenzoate ligand is labile. The latter is efficiently replaced by reaction with better nucleophiles such as diethyldithiocarbamate giving a further class of mixed ligand complexes of the type M(III)(R-PhCS(3))(2)(Et(2)NCS(2))(M=Re; Re 10--18; M=(99)Tc; Tc--18), which retain the trigonal prismatic arrangement, as determined by the X-ray analyses of the representative compounds Re(PhCS(3))(2)(Et(2)NCS(2)), Re 10 and (99)Tc(PhCS(3))(2)(Et(2)NCS(2)), Tc 10.     

Existence of Self-Similar Solutions to Smoluchowski’s Coagulation Equation

The existence of self-similar solutions to Smoluchowskis coagulation equation has been conjectured for several years by physicists, and numerical simulations have confirmed the validity of this conjecture. Still, there was no existence result up to now, except for the constant and additive kernels for which explicit formulae are available. In this paper, the existence of self-similar solutions decaying rapidly at infinity is established for a wide class of homogeneous coagulation kernels.     

A domino ring-closing metathesis as a key-step in the synthesis of chiral lactones from d-mannitol

Chiral lactones were synthesized in six steps from d-mannitol. The key-step was a domino ring-closing metathesis reaction leading to the symmetric cleavage of a d-mannitol triene derivative and to the formation of two molecules of the desired lactone.     

Nonequilibrium desorption of atoms and molecules from surfaces

A model, based on concepts from the theory of atom-surface accommodation coefficients, for nonequilibrium desorption of atoms and molecules from surfaces is proposed. We contend that the nonequilibrium effects should be expected to be general properties of not only polyatomic molecule-surface systems, but of all desorbing systems. The model predicts large deviations from the equilibrium dependences, on desorption angle, of (a) the desorbing atomic flux, (b) the average energy of desorbing atoms and (c) the desorbing atomic speed ratio. The deviations are larger when the accommodation coefficient is smaller.     

Theoreme de Donsker et formes de Dirichlet

We use the language of errors to handle local Dirichlet forms with squared field operator (cf. [N. Bouleau, Error Calculus for Finance and Physics, the Language of Dirichlet Forms, De Gruyter, 2003]). Let us consider, under the hypotheses of Donsker theorem, a random walk converging weakly to a Brownian motion. If, in addition, the random walk is supposed to be erroneous, the convergence occurs in the sense of Dirichlet forms and induces the Ornstein-Uhlenbeck structure on the Wiener space. This quite natural result uses an extension of Donsker theorem to functions with quadratic growth. As an application we prove an invariance principle for the gradient of the maximum of the Brownian path computed by Nualart and Vives.     

Macroscopic thermodynamics of porous media

A macroscopic thermodynamical theory of unsaturated porous media is studied. The porous media under consideration contain air, liquid water and its vapour encountering phase changes. To the classical state quantities, viz. temperature and densities, we add the volume fractions. These fractions are submitted to constraints, for instance their values lie between 0 and 1. The constraints are taken into account by the free energies which become non-smooth functions. The constitutive laws are obtained by classical thermodynamics and a careful treatment of the non-smooth functions. The constitutive laws account for experimental properties of unsaturated porous media: hysteresis of the sorption and desorption, capillary suction ...     

Sur la variation quadratique de certaines mesures vectorielles

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