Réactivité photochimique des dialkylamino-2 cyclohexène-2 ones et des sels d'ammonium correspondants

Photolysis of 2-dialkylamino-2-cyclohexenones leads to α-ketoazetidines. The reactivity of 3-methyl-2-dialkylamino-2-cyclohexenones and the effect of the nature of the dialkylamino groups on the photocyclization are discussed. Photolysis of the corresponding ammonium salts in hydroxylic solvents led only to adduct formation.     

Tandem mass spectrometry characteristics of polyester anions and cations formed by electrospray ionization

Electrospray ionization of polyesters composed of isophthalic acid and neopentyl glycol produces carboxylate anions in negative mode and mainly sodium ion adducts in positive mode. A tandem mass spectrometry (MS/MS) study of these ions in a quadrupole ion trap shows that the collisionally activated dissociation pathways of the anions are simpler than those of the corresponding cations. Charge-remote fragmentations predominate in both cases, but the spectra obtained in negative mode are devoid of the complicating cation exchange observed in positive mode. MS/MS of the Na(+) adducts gives rise to a greater number of fragments but not necessarily more structural information. In either positive or negative mode, polyester oligomers with different end groups fragment by similar mechanisms. The observed fragments are consistent with rearrangements initiated by the end groups. Single-stage ESI mass spectra also are more complex in positive mode because of extensive H/Na substitutions; this is also true for matrix-assisted laser desorption ionization (MALDI) mass spectra. Hence, formation and analysis of anions might be the method of choice for determining block length, end group structure and copolymer sequence, provided the polyester contains at least one carboxylic acid end group that is ionizable to anions.     

Molecular functionalization of tantalum oxide surface towards development of apatite growth

We have studied the apatite growth dynamics on tantalum oxide surfaces. This nucleation is obtained via an organosilane intermediate layer between the apatite and the substrate surface. Four organosilane layers (differing by their terminal functionality) were investigated. Their characterization with atomic force microscopy and other techniques such as X-ray photoelectron spectroscopy (XPS) and wetting measurements highlighted the influence of the organosilane terminal groups on the apatite growth rates. Results revealed that apatite is indeed growing faster on phosphate terminal groups than on the three other groups studied (vinyl, hydroxyl and carboxyl).