Remarques sur l'application Hom (G,H)→[B G,B H]

Sans résumé     

Real Lightlike Hypersurfaces of Paraquaternionic Kähler Manifolds

The main purpose of this paper is to give basic properties of real lightlike hypersurfaces of paraquaternionic manifold and to prove the nonexistence of real lightlike hypersurfaces in paraquaternionic space forms under some conditions. Dedicated to the memory of Professor Aldo Cossu     

Synthesis of micelle templated silico-aluminas with different alumina contents

The computer aided analysis of the EPR spectra of radical surfactant probes inserted in cetyltrimethylammonium bromide micelles provided information on the kinetics of formation of micelle templated silico-aluminas (MTSA) at 343 K, obtained by means of silica and alumina alkaline solutions at different Si/Al ratios (from infinity to 4). Mainly two spectral components were analyzed and relatively quantified in the EPR spectra: (1) the micellar component, due to probes inserted in the surfactant aggregates, whose mobility decreases over the synthesis time, thus reporting on the progressive modification of the micelle structure and the solid condensation; (2) the interacting component, mainly arising from the electrostatic interactions between the surfactant heads and the charged surface sites. This last component increases its relative intensity over the synthesis time, informing about condensation and structuration of the silico-alumina at the micelle surface. X-ray diffraction (XRD), nitrogen sorption isotherms at 77 K, thermogravimetric analysis, TEM and chemical analysis were performed to characterize both as-synthesized and calcined MTSA materials. Nitrogen sorption isotherms allowed us to evaluate the pore diameter, the specific surface area and the pore volume. At Si/Al<15 a decrease in pore volume and specific surface area was interpreted as due to the contemporaneous presence of a hexagonal MTSA and an amorphous material, which was ascertained by means of XRD as the only present at Si/Al=4. The amorphous structure at Si/Al<15 used Na+ as contraions, whereas the surfactants are no more needed to neutralize the negatively charged groups at the solid surface. The hypothesis of a "break" at Si/Al=15 was supported by EPR: the interactions between the surfactant probe heads and the negatively charged surface groups are drastically reduced at Si/Al<15. On the contrary, at Si/Al>15, increasing amounts of alumina slow the kinetics of the synthesis but enhance electrostatic interactions between the surfactant heads and the negatively charged surface groups. Dilution of the synthesis mixture decreased the extent of the interactions, due to partial protonation of the silanol groups, and slowed the synthesis process.     

Stereoselective synthesis of novel beta,gamma-epoxyhydroxylamines and 4-hydroxyalkyl-1,2-oxazetidines

A simple and efficient stereoselective synthesis of polysubstituted beta,gamma-epoxyhydroxylamines and 4-hydroxyalkyl-1,2-oxazetidines, based on the addition of alpha-lithiated aryloxiranes to nitrones and subsequent cyclization of the corresponding intermediates in a 4-exo-tet mode, is described.     

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ6‐sulfanenitrile Intermediate

Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry, and provide attractive bioisosteres for sulfonamides. However, there remain few operationally simple methods for their preparation. Here, the synthesis of NH‐sulfonimidamides is achieved directly from sulfenamides, themselves readily formed in one step from amines and disulfides. A highly chemoselective and one‐pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source, and in the presence of 1 equivalent of acetic acid. A wide range of functional groups are tolerated under the developed reaction conditions, which also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel S≡N sulfanenitrile species as intermediates. Several alkoxy‐amino‐λ⁶‐sulfanenitriles are prepared with different alcohols, and shown to be alkylating agents to a range of nucleophiles.     

Regio- and stereoselective lithiation of 2,3-diphenylaziridines: a multinuclear NMR investigation

The alpha-lithiation-trapping sequence of trans-N-alkyl-2,3-diphenylaziridines (s-BuLi or s-BuLi/TMEDA), taking place with a stereochemistry which dramatically depends on the solvent coordinating ability (inversion of configuration in THF and retention in toluene), has been carefully investigated. 1H,13C, and 7Li multinuclear NMR investigations at low temperature suggest that two differently configured lithiated aziridines (monomeric cis-1-Li in THF and dimeric trans-1-Li in toluene) are involved.     

Adsorption of simple fluid on silica surface and nanopore: effect of surface chemistry and pore shape

This paper reports a molecular simulation study on the adsorption of simple fluids (argon at 77 K) on hydroxylated silica surfaces and nanopores. The effect of surface chemistry is addressed by considering substrates with either partially or fully hydroxylated surfaces. We also investigate the effect of pore shape on adsorption and capillary condensation by comparing the results for cylindrical and hexagonal nanopores having equivalent sections (i.e., equal section areas). Due to the increase in the polarity of the surface with the density of OH groups, the adsorbed amounts for fully hydroxylated surfaces are found to be larger than those for partially hydroxylated surfaces. Both the adsorption isotherms for the cylindrical and hexagonal pores conform to the typical behavior observed in the experiments for adsorption/condensation in cylindrical nanopores MCM-41. Capillary condensation occurs through an irreversible discontinuous transition between the partially filled and the completely filled configurations, while evaporation occurs through the displacement at equilibrium of a hemispherical meniscus along the pore axis. Our data are also used to discuss the effect of surface chemistry and pore shape on the BET method. The BET surface for fully hydroxylated surfaces is much larger (by 10-20%) than the true geometrical surface. In contrast, the BET surface significantly underestimates the true surface when partially hydroxylated surfaces are considered. These results suggest that the surface chemistry and the choice of the system adsorbate/adsorbent is crucial in determining the surface area of solids using the BET method.     

Regio- and stereoselective lithiation and electrophilic substitution reactions of N-Alkyl-2,3-diphenylaziridines: solvent effect

[structure: see text]. The lithiation reaction of cis- and trans-N-alkyl-2,3-diphenylaziridines has been investigated. While cis-diphenylaziridines do not undergo any lithiation upon treatment with organolithiums, the lithiation reaction of the trans counterparts is completely alpha-regioselective and the stereochemical course of the lithiation-trapping sequence is solvent dependent: inversion of configuration in coordinating solvents (THF or toluene/crown ether) and retention in hexane, ether, or toluene. The preparation of stereodefined functionalized N-alkyl-2,3-diphenylaziridines is described.     

A multireference perturbation theory study on the vertical electronic spectrum of thiophene

The vertical electronic spectrum of the thiophene molecule is investigated by means of second and third order multireference perturbation theory (NEVPT). Single-state and quasi-degenerate NEVPT calculations of more than 25 singlet excited states have been performed. The study is addressed to the theoretical characterization of the four lowest-energy valence states, as well as the 3s, 3p and 3d Rydberg states. In addition, the excitation energies of two and valence states are also reported. For almost all the excited states, coupled cluster calculations (CCSD and CCSDR(3)) have been also carried out, using the same geometry and basis set used for the NEVPT ones, in order to make the comparison between the results of the two methods meaningful. A remarkable accordance between the NEVPT and CC excitation energies is found. The present results, over all, confirm the experimental assignments but, above all, represent an important contribution to the assignments of some low-energy states, valence and Rydberg, for which a firm interpretation is not available in the literature.