Direct in situ synthesis of cationic N-heterocyclic carbene iridium and rhodium complexes from neat ionic liquid: Application in catalytic dehydrogenation of cyclooctadiene

A direct synthetic route to cationic N-heterocyclic carbene (NHC) complexes of rhodium and iridium from neat dialkyl-imidazolium ionic liquids (ILs) has been found. The method uses complexes bearing basic anionic ligands, [M(COD)(PPh₃)X], X = OEt, MeCO₂, which react with the inactivated imidazolium cation in the absence of external bases yielding one M-NHC moiety and the free protonated base. This new one-pot synthesis leaving pure, catalytically active IL solutions is faster, cleaner and more efficient than traditional syntheses of such NHC complexes. The observed reactivity also gives insight into NHC incorporation of rhodium and iridium catalyzed reactions performed in common dialkyl-imidazolium ILs.The complexes synthesised in this manner are compared with their bis-phosphine analogues in terms of activity for catalytic dehydrogenation of 1,5-cyclooctadiene and 1,3-cyclooctadiene in neat [BMIM][NTf₂] as solvent. Even at high temperature, no ligand exchange reaction is observed with [(COD)M(PPh₃)₂] [NTf₂] catalysts. As expected, the yields of all the reactions were low, iridium was much more active in C-H activation than rhodium and the NHC ligands were more stable than triphenylphosphine. For all catalysts, the isomerisation of 1,5-cyclooctadiene is the major reaction. However, the phosphine-NHC complex of iridium seems to be more selective for dehydrogenation than its bis-phosphine counterpart, which is more active in transfer-hydrogenation and less stable under the applied conditions. Different reaction conditions were tried in order to optimise selectivity for dehydrogenation over isomerisation and transfer-hydrogenation. Surprisingly, with 1,3-cyclooctadiene as substrate selectivity for dehydrogenation is much higher than with 1,5-cyclooctadiene for all catalysts.     

Electron quantum optics in ballistic chiral conductors

The edge channels of the quantum Hall effect provide one dimensional chiral and ballistic wires along which electrons can be guided in an optics‐like setup. Electronic propagation can then be analyzed using concepts and tools derived from optics. After a brief review of electron optics experiments performed using stationary current sources which continuously emit electrons in the conductor, this paper focuses on triggered sources, which can generate on‐demand a single particle state. It first outlines the electron optics formalism and its analogies and differences with photon optics and then turns to the presentation of single electron emitters and their characterization through the measurements of the average electrical current and its correlations. This is followed by a discussion of electron quantum optics experiments in the Hanbury‐Brown and Twiss geometry where two‐particle interferences occur. Finally, Coulomb interactions effects and their influence on single electron states are considered.     

Synthesis of hematite/silica/polymer composite colloids with a tunable morphology

Hematite/SiO₂/polystyrene colloidal particles were synthesized through emulsion polymerization, in the presence of seeds coated with 3-methacryloxypropyltrimethoxysilane (MPS). Scanning and transmission electron microscopy studies indicate that flying saucer-like particles can be prepared by taking advantage of the coalescence phenomenon which occurs between growing polymer nodules when the MPS surface density of the coupling agent is high. By decreasing this density, multipod-like and raspberry-like composite particles were obtained, depending on the concentration of monomer.     

A new cyclopamine glucuronide prodrug with improved kinetics of drug release

We prepared a new glucuronide prodrug of cyclopamine designed to target selectively the Hedgehog signalling pathway of cancer cells. This prodrug includes a novel self-immolative linker bearing a hydrophilic side chain that can be easily introduced via"click chemistry". With this design, the prodrug exhibits reduced toxicity compared to the free drug on U87 glioblastoma cells. However, in the presence of β-glucuronidase, the prodrug conducts to the quick release of cyclopamine thereby restoring its antiproliferative activity.     

A round robin exercise in archaeometry: analysis of a blind sample reproducing a seventeenth century pharmaceutical ointment

Chemical analysis of ancient residues of pharmaceutical or cosmetic preparations such as balms or ointments is made problematic by the high complexity of these mixtures, composed of organic and inorganic materials. Consequently, a multi-analytical approach and special caution in the interpretation of the results are necessary. In order to contribute to the improvement of analytical strategies for the characterization of complex residues and to reconstruct ancient medical practices, a replica of a pharmaceutical formulation of the seventeenth century was prepared in the laboratory according to a historically documented recipe. In a round robin exercise, a portion of the preparation was analysed as a blind sample by 11 laboratories using various analytical techniques. These included spectroscopic, chromatographic and mass spectrometric methods. None of the laboratories was able to completely reconstruct the complex formulation, but each of them gave partial positive results. The round robin exercise has demonstrated that the application of a multi-analytical approach can permit a complete and reliable reconstruction of the composition. Finally, on the basis of the results, an analytical protocol for the study of residues of ancient medical and pharmaceutical preparations has been outlined.     

Supercontinuum generation by nanosecond dual-pumping near the two zero-dispersion wavelengths of a photonic crystal fiber

Supercontinuum generation by dual-wavelength nanosecond pumping in the vicinity of both zero-dispersion wavelengths of a photonic crystal fiber (PCF) is experimentally demonstrated. It is shown in particular that two pumps at 1535 nm and 767 nm simultaneously pumping near the two zero-dispersion wavelengths of a specially designed PCF yields a combined visible and infrared supercontinuum spectrum spanning from 0.55 μm to 1.9 μm. We discuss the generation mechanisms underlying the continuum formation in terms of modulation instability and cascaded Raman generation.     

Mechanism selection for regiocontrol in base-assisted, palladium-catalysed direct C-H coupling with halides: first approach for oxazole- and thiazole-4-carboxylates

Both base-assisted non-concerted metallation-deprotonation (nCMD) and concerted metallation-deprotonation (CMD) have been identified as two potent operating mechanisms in palladium-catalysed direct C-H coupling of oxazole and thiazole-4-carboxylate esters with halides through base- and solvent-effect experiments. Novel C2- and C5-selective CMD direct arylation procedures in oxazole- and thiazole-4-carboxylate series were then designed by controlling the balance between electronic and steric factors. Notably, charge interactions between the palladium catalyst and substrate were identified as a parameter for controlling selectivity and reducing the impact of steric factors in the CMD reaction.     

Synthesis of Planar Five‐Connected Nodal Ligands

The fiveway junction : The synthesis of ligands with five symmetrically diverging binding sites is described and their assembly into large spherical structures (such as that shown here) investigated.