The remarkable effect of the 7-substituent in the diastereoselective oxidative rearrangement of indoles: asymmetric synthesis of 3,3-disubstituted oxindoles

The nature of the 7-substituent has a remarkable effect on the diastereoselectivity of the oxidative rearrangement of indole-2-carboxamides derived from (S)-2-methoxymethylpyrrolidine into chiral 3,3-disubstituted oxindoles.     

Finite amplitude one-dimensional wave propagation in a thermoelastic half-space

The problem of finite wave propagation in a nonlinearly thermoelastic half-space is considered. The surface of the half-space is subjected to a time-dependent thermal and normal mechanical loading. The solution is obtained by a numerical procedure, which is shown to furnish accurate results, and linear dynamic thermoelastic problems are obtained as special cases. The accuracy of the results is checked by comparison with some known analytical solutions which can be obtained in some special cases of both the linear and the nonlinear problems. In those cases where the solution contains shocks, it is shown that the numerical results satisfy the necessary jumps conditions which need to hold across such discontinuities.     

Sur le cone des 1-cycles effectifs en dimension 3

Sans résumé     

Nature-inspired dimerization as a strategy to modulate neuropeptide pharmacology exemplified with vasopressin and oxytocin

Vasopressin (VP) and oxytocin (OT) are cyclic neuropeptides that regulate fundamental physiological functions via four G protein-coupled receptors, V_1aR, V_1bR, V₂R, and OTR. Ligand development remains challenging for these receptors due to complex structure–activity relationships. Here, we investigated dimerization as a strategy for developing ligands with novel pharmacology. We regioselectively synthesised and systematically studied parallel, antiparallel and N- to C-terminal cyclized homo- and heterodimer constructs of VP, OT and dVDAVP (1-deamino-4-valine-8-d-arginine-VP). All disulfide-linked dimers, except for the head-to-tail cyclized constructs, retained nanomolar potency despite the structural implications of dimerization. Our results support a single chain interaction for receptor activation. Dimer orientation had little impact on activity, except for the dVDAVP homodimers, where an antagonist to agonist switch was observed at the V_1aR. This study provides novel insights into the structural requirements of VP/OT receptor activation and spotlights dimerization as a strategy to modulate pharmacology, a concept also frequently observed in nature.

Structural and pharmacological study of parallel, antiparallel and N- to C-terminal cyclized homo- and heterodimers of vasopressin and oxytocin. This study spotlights dimerization as a strategy to modulate the pharmacology of neuropeptides.     

On the effective thermal conductivity of multiphase composites

While several micromechanical models have been developed today in the literature for two-phase media, the extent of their applicability to multiphase materials need yet to be investigated. The present paper studies the effective thermal conductivity of multicomponent composites, and concentrates on two methods: (a) the Mori-Tanaka model, (b) The generalized self-consistent scheme. The Mori-Tanaka method of back-stress previously developed in the context of elasticity of composites is applied here to the conduction problem. The generalized self-consistent scheme, based on a particle-matrix embedding in the effective medium, is studied in this paper in the context of multicomponent media and two variations of this method distinctly different in their imbedding procedure are proposed.Numerical results are given for three-phase composites illustrating and comparing the proposed methods.

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Resumé Plusieurs modéles de micromécanique existent aujoud'hui dans la litérature des matériaux á deux phases. L'applicabilité de ces modéles aux matériaux á multi-phases nécessite d'autre part d'être examinée. Ce travail étudie la conductivité thermale des matériaux á multi-phases et se concentre sur deux méthodes: a) le modéle de Mori-Tanaka b) la méthode auto-consistante généralisée. La méthode de Mori-Tanaka, développée auparavant dans le cadre des propriétés mécaniques des composites est appliquée ici au probléme de conduction. La méthode autoconsistante généralisée est étudiée dans le cadre des matériaux á multi-phases et deux alternatives de cette méthode distinctement différentes dans leur formalisme sont proposées. Pour des matériaux á trois phases on donne des resultats numériques qui illustrent et comparent les méthodes proposées.

     

6π/10π-Electrocyclization of ketene-iminium salts for the synthesis of substituted naphthylamines

An intramolecular 6π/10π-electrocyclization from ketene-iminium salts was developed for the preparation of naphthylamines. Various substituents on the nitrogen, on the aromatic ring, and on the olefin were studied. Tricyclic skeletons were obtained in few steps and good overall yields. The electrocyclization of ketene-iminium salts has been computationally explored by means of DFT calculations and their activation barriers were compared to the parent triene as well as the corresponding dienyl allenes and dienyl ketenes. Electrocyclizations for ketene-iminium salts were shown to be highly exergonic and have much smaller barriers to activation.     

Mercury speciation analysis in human hair by species-specific isotope-dilution using GC–ICP–MS

We optimized a mercury (Hg) speciation extraction method for human hair in combination with species-specific isotope-dilution analysis by gas chromatography–inductively coupled plasma–mass spectrometry (GC–ICP–MS). The method was validated on human hair reference material RM (IAEA-086), which is recommended for analysis of monomethylmercury (MMHg) and inorganic mercury (IHg). Three reagents, hydrochloric acid (HCl), nitric acid (HNO₃), and tetramethylammonium hydroxide (TMAH), and three extraction procedures, at ambient temperature for 12 h, microwave-assisted at 75 °C for 6 min, and oven heated at 80 °C for 2 h were tested. Extraction efficiency, recovery, and potential species transformations were evaluated for each method. The most efficient procedures, with recovery of ~90 % for each species with limited demethylation (<5 %) and methylation (0 %), were HNO₃ digestion, irrespective of temperature, and microwave-assisted TMAH extraction. Acidic extraction with HCl induces significant demethylation, with production of artifacts. To correct for potential demethylation artifacts we recommend spiking with isotopically enriched standards before the extraction step.     

Ene-reaction between a dienolic compound and 2-methyl-2-nitrosopropane: an EPR-MS study

The combination of electron paramagnetic resonance (EPR) and mass spectrometry (MS) was used as an efficient tool to elucidate the mechanism of an ene-reaction between a dienol compound and 2-methyl-2-nitrosopropane.