Radical and Radical–Ionic Multicomponent Processes

All in one pot! Radical, radical–ionic, and radical–organometallic MCR are highly convergent processes, representing a useful pathway to molecular and structural diversity (see scheme). This concept article highlights recent developments in the field and shows the potential of the strategy for the economical elaboration of various kinds of organic substrates.

     

3D harnessing of light with 2.5D photonic crystals

It is emphasized that two‐dimensional photonic crystals (2D PC) have not only a great potential for the development of 2D nanophotonics in the inplane waveguided configuration, but that they may also open the way to other brilliant developments, with an extension to out‐of‐plane operation, along a 2.5D nanophotonics approach. In this 2.5D approach, a 1D–2D high index contrast lateral structuration is combined with a 1D high index contrast vertical structuration, using multilayer membrane stacks including 1D–2D photonic crystal membranes, thus resulting in so‐called 2.5D PC. As a specific illustration of recent achievements along this approach, new families of VCSEL structures are presented.     

Synthesis and characterization of copper oxide (I) nanoparticles produced by pulsed sonoelectrochemistry

Cu(2)O nanopowders have been prepared by ultrasound-assisted electrochemistry with a potentiostatic set-up. Their composition has been determined by X-ray diffraction and energy dispersive X-ray spectroscopy. Transmission electron microscopy and centrifugation analyses indicate that the nanopowders consist of agglomerates of variable nanometric diameter grain. Most of particles have a diameter of 8 nm whatever the electrodeposition potential. The influence of the parameters of electrochemical and ultrasonic pulses on the particle diameter was also studied. The specific surface areas determined by Brunauer-Emmet-Teller (BET) model are very high with a value close to 2000 m(2)g(-1).     

Etudes sur les composés organométalliques. Partie XXI. Contribution à l'étude de la décomposition du tétracyclohexyltitane

Studies on Organometallic Compounds. Contribution to the Study of Thermal Decomposition of Tetracyclohexyltitanium Thermal decomposition of tetracyclohexyltitanium proceeds in a different manner for the solid compound and for etheral solution. We propose an explanation of the decomposition mechanisms based on radical reactivities and compare our results with previous literature data.     

Low-frequency Raman spectra of sub- and supercritical CO2: qualitative analysis of the diffusion coefficient behavior

We report the results of the low-frequency Raman experiments on CO(2) which were carried out in a wide density range, along the liquid-gas coexistence curve in a temperature range of 293-303 K, and on the critical isochore of 94.4 cm(3) mol(-1) in a temperature range of 304-315 K. In our approach, the qualitative behavior of the diffusion coefficient D is predicted, assuming the following: first, that the low-frequency Raman spectra can be interpreted in terms of the translation rotation motions; second, that the random force could be replaced by the total force to calculate the friction coefficient; and finally, that the Einstein frequency is associated with the position of the maximum of the low-frequency Raman spectrum. The results show that the diffusion coefficient increases along the coexistence curve, and its values are almost constant on the critical isochore. The predicted values reproduce qualitatively those obtained by other techniques. The values of D were also calculated by molecular-dynamics simulation and they qualitatively reproduce the behavior of D.     

Mixed 1D-2D inorganic polymeric zinc ferrocenylphosphonate: crystal structure and electrochemical study

Needs for ferrocene immobilization on robust host structures are considerable since derivative materials may find applications in medical areas, optical devices, or catalysis. Synthesis of phosphonate functionalized ferrocene allowed its subsequent inorganic polymerization with a zinc salt. The crystallographic structure of the compound obtained, Zn(HO(3)PFc)(2).2H(2)O, shows a unique two-dimensional ferrocene arrangement anchored on a one-dimensional Zn-O-P-O-Zn backbone. The ferrocene packing in the title compound is very similar to the packing found in molecular ferrocene. The electroactivity of Zn(HO(3)PFc)(2).2H(2)O is thoroughly studied. It shows a reversible surface oxidation of ferrocene. M?ssbauer spectroscopy for the oxidized compound shows an isomer shift of IS(2b) = 0.432 mm x s(-1) and a quadrupolar splitting of QS(2b) = 0.205 mm x s(-1), which is consistent with a stable S = 1/2 ferrocenium state. The magnetic susceptibility study, M?ssbauer spectroscopy, and galvanostatic titration show that only the ferrocene moieties present at the surface of the crystallites are reversibly oxidized. This observation is reinforced by a complex impedance study showing mainly resistive behavior and conductivity measurements indicating weak, thermally assisted, conductivity. The general properties of this compound demonstrate that phosphonato functionalization may be a useful approach for all fields concerned by immobilization of ferrocene.     

High-speed narrow-bore capillary gas chromatography in combination with a fast double-focusing mass spectrometer

In this work the application of high-speed narrow-bore capillary GC in combination with a fast scanning double focusing magnetic sector mass spectrometer is evaluated. Special emphasis is placed upon detection limits and scan speed in the full scan mode and in the selected ion monitoring mode (SIM). In the full scan mode, up to 20 scans per second could be obtained. The detection limits are in the low picogram range in the full scan mode and improve even to 5 to 50 fg in the SIM mode, depending on the sample complexity and mass resolving power. It will be illustrated that by increasing the resolution in the SIM mode, interferences from ions of the same nominal mass-to-charge ratio as the ions of interest are significantly reduced. Chemical background noise can therefore be largely eliminated, thus enhancing the signal-to-noise ratio.     

La formation de sels augmente-t-elle la fréquence des dédoublements spontanés?

The resolution by entrainment which allows the pure enantiomers to be obtained by direct crystallization of the racemate is possible only when the racemate is a conglomerate (eutectic mixture). Spontaneous resolutions exist to an extent less than 10% of the crystalline racemates. Considering a family of racemic salts formed by a racemic acid or racemic base and a racemic or an achiral counterion, we show by a statistical analysis, which has required the preparation of more than 500 salts, that the probability of finding spontaneous resolution is 2 or 3 times greater than in the family of covalent racemates. The preparation of some phosphonic acids, which could be useful as new resolving agents is described.