Les harraga algériens

Des Algériens, principalement des jeunes hommes, tentent de quitter leur pays, sans passeport ni visa, sur des barques, au péril de leur vie. En dialecte maghrébin, on nomme ces candidats à l’émigration harraga (les “brûleurs”), car ils “brûlent” les frontières et les étapes nécessaires à une migration légale. En outre, s’ils arrivent en Europe, ils détruisent, ils “brûlent” leurs papiers d’identité pour tenter d’échapper à l’expulsion. Après les hittistes des années 1980 et ceux qui ont rejoint les groupes islamistes armés durant le conflit des années 1990, les harraga sont érigés au rang de figure symbolisant le désespoir de la jeunesse algérienne durant les années 2000. Ils sont invoqués comme preuve ultime des dysfonctionnements qui touchent le pays. (Premier paragraphe

Необходимость общих подходов в применении мер уголовной ответственности за компьютерные преступления в Республике Беларусь, Российской Федерации и Украине

Материалы III междунар. науч. конф., 22-23 мая 2003 г

Synthesis and properties of bis-porphyrin molecular tweezers: effects of spacer flexibility on binding and supramolecular chirogenesis

Ditopic binding of various dinitrogen compounds to three bisporphyrin molecular tweezers with spacers of varying conformational rigidity, incorporating the planar enediyne (1), the helical stiff stilbene (2), or the semi-rigid glycoluril motif fused to the porphyrins (3), are compared. Binding constants Ka = 104–106 M?1 reveal subtle differences between these tweezers, that are discussed in terms of porphyrin dislocation modes. Exciton coupled circular dichroism (ECCD) of complexes with chiral dinitrogen guests provides experimental evidence for the conformational properties of the tweezers. The results are further supported and rationalized by conformational analysis

Concerted and stepwise solvolytic elimination and substitution reactions: Stereochemistry and substituent

Abstract: Solvolysis of the R,R and R,S isomers 2a-X and 2b-X, respectively, (X ) I, Br, OBs) in 25 vol % acetonitrile in water gives the elimination products 4, 5a, and 5b along with the substitution products 2a-OH, 2b-OH, 2a-NHCOMe, and 2b-NHCOMe. The rates of elimination (k E ) increase with increasing acidity of the -hydrogen of the substrate as expressed by a Brønsted parameter of R ) 0.08 and 0.07 for the iodides and the bromides, respectively. In contrast, the brosylates, which give much smaller fractions of the stable alkenes, exhibit a negatiVe Brønsted parameter for the elimination, R ) -0.10. This shows that the brosylates, in contrast to the halides, do not give elimination exclusively by a solvent-promoted E1cB reaction or an E2 reaction with a large component of hydron transfer in the transition state and indicates a large amount of reaction through carbocation intermediates to give stable alkenes

Design of oxophilic metalloporphyrins : an experimental and DFT study of methanol binding

By systematic measurements we have evaluated a series of tetraphenyl metalloporphyrins and halogenated tetraphenyl metalloporphyrin derivatives for binding to ligands with oxygen containing functional groups, using methanol, acetic acid and acetone as examples. Experimental binding constants identified three metalloporphyrins with good binding to all three ligands: MgTPFPP, MgTPPBr8 and ZnTPPBr8 as well as a range of porphyrins binding to select ligands. Based on these results the optimal porphyrins can be selected for the desired binding interactions. We also show how to use DFT calculations to evaluate the potential binding between a metalloporphyrin and a ligand, which is deduced from free energies of binding ΔG, charge transfer ΔQ, and change of metal spin state. Computations on unsubstituted porphyrins in lieu of tetraphenyl porphyrin systems yield reliable predictions of binding interactions with good correlation to the corresponding experimental data. The calculations have also yielded interesting insights into the effect of halogenation in the β-position on the binding to ligands with oxygen containing functional groups

An unexpected triethylsilane-triggered rearrangement of thioaurones to thioflavonols under SPPS conditions

Thioaurones are converted to a mixture of thiaindenes and thioflavonols when exposed to reaction conditions employed in SPPS, that is, treatment with trifluoroacetic acid in the presence of triethylsilane

Conformational restriction of flexible molecules in solution by a semirigid bis-porphyrin molecular tweezer

A semirigid bis-porphyrin molecular clip with a glycoluril backbone has been synthesized. The clip provides an adaptable molecular cavity for binding of diamines. Binding constants for diamines of 104–107 M−1 are orders of magnitude higher than those for monoamines of 103 M−1, indicating a preference to bidentate binding. NMR studies confirmed that binding of bidentate guests occurs inside the clip. Short- and medium-size acyclic molecular guests are locked into a single, extended conformation, and also guests with longer flexible chains exhibit considerably less conformational mobility than when free in solution. The size of the cavity adapts to the guest size, as indicated by modelling studies and self diffusion constants of the complexes