Synthése d'héterocycles. XX. Reaction du malononitrile avec quelques cinnamonitriles

Reaction of cinnamonitriles with malononitrile, in methanolmethoxide, yield dihydropyridines, which by aromatisation give pyridines. Pyridine is directly obtained when p-nitrocinnamonitrile is used     

A new technique for calculating virtual photon spectra

A first-order matrix differential equation in energy is used to propagate radial matrix elements arising in DWBA of relativistic electron scattering from nuclei. Given an initial set of matrix elements at some value of the energy, this equation permits the evaluation of the radial matrix elements over the complete energy transfer range. A computer code has been written for this new procedure and the virtual photon spectra accompanying electron scattering from a point nucleus is calculated as a function of photon energy for various multipoles, nuclear charges, and incident electron energies.     

Catalyse et inhibition de deux reactions concurrentes en milieu micellaire cationique

The general acid catalysed hydrolysis and the intramolecular nucleophilic anionic cyclization of acyloximes operate concurrently in water at pH 7–9. Hydrolysis is inhibited by cationic micelles; changing the length of the acyl chain does not affect the micellar effect, possibly because the environment of the reacting species is not influenced by this variation in the structure of the micelle.     

Observations of plasma dynamics in a gas-embedded compressionalZ-pinch

A series of experiments carried out in a gas embedded compressional Z-pinch are presented. A dc micro discharge of 150 μA between two conical sharp edged electrodes is established to produce a hollow cylindrical discharge. A few nanoseconds before the application of the main voltage, a pulsed laser is focused through the anode onto the cathode. With this preionization scheme an initial coaxial current structure is established. H₂ and D₂ at a pressure of 1/3 atm were used as a working gas. The experiments have been carried out using a pulse power generator capable of delivering current of up to I~200 kA with a dI/dt>10¹² A/s. The use of H₂ and D₂ allows the study of discharges with the same electrical properties, but with different dynamics. At early times this preionization scheme produces a coaxial double column pinch, which as current rises, coalesces into a single column becoming a gas embedded compressional Z-pinch. Diagnostics used are current and voltage monitors, single frame holographic interferometry and shadowgraphy, visible streak camera, and single frame image converter camera. Electron density, line density, pinch radius, and plasma motion are obtained from the optical diagnostics. It was found that the maximum electron density achieved on axis is greater than twice the expected value according with the filling pressure used in the discharges, which contrasts with a traditional gas embedded pinch in which the density is lower than the expected value from filling pressure. The expansion rate of the plasma column is reduced to a third of the observed value for the single channel laser initiated gas embedded pinch. These measurements agree with the existence of a central current channel in this new configuration of gas embedded pinch. The experimental results clearly show that compression is achieved with the composite preionization scheme     

Sensory hybrid host materials for the selective chromo-fluorogenic detection of biogenic amines

Pyrylium-containing mesoporous materials have been used for the chromo-fluorogenic sensing of biogenic amines in an aqueous environment.     

Vacancy formation and CO adsorption on gold-doped ceria surfaces

We study the effect of gold doping on oxygen vacancy formation and CO adsorption on the (1 1 0) and (1 0 0) surfaces of ceria by using density functional theory, corrected for on-site Coulomb interactions (DFT + U). The Au dopant substitutes a Ce atom in the surface layer, leading to strong structural distortions. The formation of one oxygen vacancy near a dopant atom is energetically “downhill” while the formation of a second vacancy around the same dopant requires energy. When the surface is in equilibrium with gaseous oxygen at 1 atm and room temperature there is a 0.4 probability that no oxygen atom left the neighborhood of a dopant. This means that the sites where the dopant has not lost oxygen are very active in oxidation reactions. Above 400 K almost all dopants have an oxygen vacancy next to them and an oxidation reaction in such a system takes place by creating a second vacancy. The energy required to form a second vacancy is smaller on (1 1 0) than on (1 0 0). On the (1 1 0) surface, it is much easier to form a second vacancy on the doped surface than the first vacancy on the undoped surface. The energy required to form a second oxygen vacancy on (1 0 0) is comparable to that of forming the first vacancy on the undoped surface. Thus doping makes the (1 1 0) surface a better oxidant but it has a small effect on the oxidative power of the (1 0 0) surface. On the (1 1 0) surface CO adsorption results in formation of a carbonate-like structure, similar to the undoped surface, while on the (1 0 0) surface direct formation of CO₂ is observed, in contrast to the undoped surface. The Au dopant weakens the bond of the surrounding oxygen atoms to the oxide making it a better oxidant, facilitating CO oxidation.     

Simulation of RAFT Dispersion Polymerization in Supercritical Carbon Dioxide

The RAFT radical polymerization of vinyl monomers in supercritical carbon dioxide was modeled using the Predici® simulation package. The sensitivity of polymerization responses on formulation and process variables was analyzed. The simulations were carried out using kinetic and physical parameters corresponding to the polymerization of methyl methacrylate in supercritical carbon dioxide, using AIBN as initiator, at 65 °C and 200 bar, and using values of the addition and fragmentation kinetic rate constants of a “typical” RAFT agent, as reference conditions. This is the first report in the literature addressing the modeling or simulation of RAFT polymerization in supercritical carbon dioxide.

     

Temperature-Controlled Stereodivergent Synthesis of 2,2′-Biflavanones Promoted by Samarium Diiodide

In this work, the first example of a radical stereodivergent reaction directed towards the stereoselective synthesis of both (R*,R*)- and (R*,S*)-2,2′-biflavanones promoted by samarium diiodide is reported. Control experiments showed that the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate a variety of 2,2′-biflavanones bearing different substitution patterns at the aromatic ring in good-to-quantitative yields, being both stereoisomers of the desired compounds obtained with total or high control of selectivity. A mechanism that explains both the generation of the corresponding 2,2′-biflavanones and the selectivity is also discussed. The structure and stereochemistry determination of each isomer was unequivocally elucidated by single-crystal X-ray diffraction experiments.