Structure d'alcaloïdes indoliques doubles d'un type nouveau

The Structure of bis-indoline alkaloids of a novel type The structure of folicangine 4 , a bis-indoline alkaloid from the leaves of Voacanga africana, is obtained by correlation with voafolidine 3a and isovoafolidine 3b . It requires an ether bridge between the two parts of the molecule, as in subsessiline (amataine 5a ). Subsessiline-lactone, from the leaves of Voacanga thouarsii has structure 5b proved by correlation with 5a . The CD. curves of double-indole alkaloids of vobtusine type are given (Table 3).     

First observation in the gas phase of the ultrafast electronic relaxation pathways of the S(2) states of heme and hemin

The time evolution of electronically excited heme (iron II protoporphyrin IX, [Fe(II) PP]) and its associated salt hemin (iron III protoporphyrin IX chloride, [Fe(III) PP-Cl]), has been investigated for the first time in the gas phase by femtosecond pump-probe spectroscopy. The porphyrins were excited at 400 nm in the S(2) state (Soret band) and their relaxation dynamics was probed by multiphoton ionization at 800 nm. This time evolution was compared with that of the excited state of zinc protoporphyrin IX [Zn PP] whose S(2) excited state likely decays to the long lived S(1) state through a conical intersection, in less than 100 fs. Instead, for [Fe(II) PP] and [Fe(III) PP-Cl], the key relaxation step from S(2) is interpreted as an ultrafast charge transfer from the porphyrin excited orbital π* to a vacant d orbital on the iron atom (ligand to metal charge transfer, LMCT). This intermediate LMCT state then relaxes to the ground state within 250 fs. Through this work a new, serendipitous, preparation step was found for Fe(II) porphyrins, in the gas phase.     

Synthesis, characterization and comparison of group 14 pyrrolides and indolides Ph3MX (M = Si, Ge, Sn; X = C4H4N, C8H6N)

The biologically important heterocycles pyrrole, C₄H₄N, and indole, C₈H₆N, ought to be useful as reagents in organic synthesis. Unfortunately, working with them has proved to be difficult because they tend to self-polymerize in solution, especially in the presence of acid catalysts. When the self-polymerization can be controlled, however, the pyrrole and indole units should provide an important route to selective N-metal binding, particularly when these ligands are activated by alkyl-lithium reagents. Using this approach, a general synthesis of the group 14 pyrrolides and indolides, Ph₃MX (M = Si, Ge, Sn; X = C₄H₄N, C₈H₆N), has been developed and the results are reported here. The compounds are formed as high-melting, white crystalline solids and have been characterized by ¹³C-, ²⁹Si- and ¹¹⁹Sn-NMR, Raman and electron-impact mass spectroscopy as well as elemental analysis. A single-crystal X-ray study of Ph₃Si(C₄H₄N) has shown that the compound is disordered in the tetragonal lattice, even at low temperature (100 K).     

Fragmentations induced by ion-atom reactions

Fragmentation of electron-impact-generated organic molecular cations, submitted to low-energy collisions with hydrogen in a MS/MS/MS multiquadrupole mass spectrometer, was promoted or significantly increased in the presence of atomic hydrogen generated from a microwave discharge. Loss of hydrogen alpha to a heteroatom and bond cleavage alpha to a carbonyl group are the major H-induced fragmentation pathways.     

Nanostructure of Solid Precipitates Obtained by Expansion of Polystyrene-block-Polybutadiene Solutions in Near Critical Propane: Block Ratio and Micellar Solution Effects

In contrast to incompressible liquid solutions, compressible near-critical solutions of block copolymers allow for controlling rapid structure transformations with pressure alone. For example, when dissolved in near-critical propane, polystyrene-block-polybutadiene can form a random molecular solution at high pressures, a micellar solution at moderate pressures, and a solvent-free precipitate at low pressures. In contrast to the unstructured virgin copolymer, such a propane-treated precipitate rapidly self assembles toward structures characteristic of equilibrated block copolymers, such as lamellae, spheres or cylinders, which depend on the block ratio rather than on the decompression rate or temperature, at least within the rate and temperature ranges investigated in this work. At lower temperatures, however, say below 40 °C, glass transition of the styrene-butadiene diblocks can inhibit independent structure formation while crystallization of their hydrogenated-butadiene analogs can preserve the micellar-solution structure.     

Catalytic Enantioselective Synthesis of Functionalized Cyclopropanes from α-Substituted Allyl Sulfones with Donor-Acceptor or Diacceptor Diazo Reagents

The catalytic asymmetric synthesis of highly functionalized cyclopropanes from α-substituted allyl sulfones and silanes is reported. The reaction, using α-aryl diazoacetates or diacceptor diazo reagents, catalyzed by a chiral rhodium complex (Rh₂((S)-BTPCP)₄), furnished the corresponding cyclopropanes in moderate to high yields (27–97 %), high diastereoselectivities (68 : 32 to 20 : 1 d.r.) and moderate to excellent ee (40–99 %). This methodology offers a privileged access to an underexplored class of enantioenriched cyclopropanes with a high level of functionality, an asset for further post-functionalization and their incorporation into more complex structure.     

Space correlation measurements in a forced shear layer with wall injection

Comprehension of wall-injection flow in a channel in the presence of different geometric discontinuities is necessary as part of the general investigations concerning combustion instabilities of solid propellant rocket motors. In order to characterise the aerodynamic flow field and to evaluate the influence of an obstacle inside a porous channel in such a case, experimental studies were conducted on a 1/40 scale model of the new ARIANE V motor. In fact, the flow is only induced by wall-injection and the presence of an obstacle creates a particular shear layer development in the obstacle wake. Particular attention was given to the unstable dynamic conditions of the shear layer. A thermal seeding of the shear layer was made in order to qualify the heat transfer therein, and especially to emphasise the turbulent structure development. Transverse and longitudinal spatial correlations were measured to characterise turbulence scales in the shear layer. At the origin of the shear layer, the decay of turbulence memory is found to be similar to that observed in a forced flow boundary layer, but the injecting wall modifies the change in structures. The wall flow is found to preserve the turbulent structures in such a way that the turbulence memory predominates in a longitudinal direction.List of Symbols f frequency (Hz) - h channel height (m) - h _v obstacle height (m) - L mean dimension of large structures (m) - P pressure (Pa) - m mass flow rate (kg/s) - r distance between probes in X direction (m) - r ^+(–) distance between probes in Y direction (m) - u longitudinal velocity in X direction (m/s) - v transversal velocity in Y direction (m/s) - T temperature (K) - x,y,z axis system (m) - t = T-T _amb (K) - v kinematic viscosity (mVs) - density (kg/m³) - characteristic porous size (urn) - _u longitudinal rms (m/s) - I _u dynamic turbulence intensity _u /u _max - I _T thermal turbulence intensity - M Mach number u/a - Re _w wall Reynolds number v _w h/v - Re _c longitudinal Reynolds number u _c h/v - R _uT thermal dynamic correlation coefficient - St Strouhal number fh/u - X,Y,Z axis system normalised by the channel height h - X _S longitudinal position of the obstacle - X X-X _S - amb ambient reference - c flowing cavity - fav head end - l lateral direction - g longitudinal direction max maximum at a longitudinal position - w wall The authors thank the CNES for its financial support, and in particular E. Robert and R. Bee.     

Fourier transform spectroscopy around 3 μm with a broad difference frequency comb

We characterize a new mid-infrared frequency comb generator based on difference frequency generation around 3.1 μm. High power per comb mode (>10^?7 W/mode) is obtained over a broad spectral span (>750 nm, >790 cm^?1). The source is used for direct absorption spectroscopy with a Michelson-based Fourier transform interferometer.