Preparation of USY zeolite VOx supported catalysts from V(AcAc)3 and NH4VO3. Catalytic properties for the dehydrogenation of n-butane in oxygen-free atmosphere

The preparation of different samples of vanadia supported on ultrastable zeolite (VO(x)/USY) is discussed. The samples were prepared in order to obtain highly dispersed V-species, avoiding the formation of crystalline vanadia and the destruction of the zeolite framework. Two methods were employed for preparing VO(x)/USY samples: an organic route using V(AcAc)3 and an inorganic route using NH4VO3. The characterization of the samples was performed with XRD, TPR, NH3-TPD, and N2 isotherms. From these results it is concluded that when VO(x) is supported on the surface of USY from acidic aqueous solution of ammonium metavanadate, the destruction of the zeolite framework is accomplished. For higher pH values in the impregnating solution, undesired V2O5 is formed on the USY surface. On the other hand, VO(x)/USY prepared from the organic precursor shows no destruction of the USY structure. In addition, highly dispersed VO(x) are formed, though for relatively high V loadings (6%) an obstruction of the zeolite windows takes place. The samples are tested as catalysts for gas phase dehydrogenation of n-butane to olefins. The catalysts prepared from NH4VO3 are almost inactive for the reaction. On the other hand, both samples prepared from V(AcAc)3 present initial conversion levels in the 8-12% range. However, the selectivity depends on the V loading, the catalysts with 6% loading being the most selective (75%). The catalytic patterns of the samples (activity and selectivity) are in agreement with the physicochemical features of the VO(x)/USY surface.     

Solvent dependent conformational isomerism and ligand oxidation of novel Ru(II) cyclen complexes

The synthesis of cis-[Ru(II)(cyclen)(L)(x)](n+) (cyclen = 1,4,7,10-tetraazacyclododecane and L = 2,2'-bipyridine (bpy), phenanthroline (phen) or 4-cyanopyridinium (4-NCpyH(+))) is reported. The freshly prepared complexes are stable in aprotic solvents and cyclen undergoes oxidative dehydrogenation reaction at high pH. These compounds also present solvent dependent conformational isomerization.     

Gas chromatographic quantification of amino acid enantiomers in food matrices by their N(O,S)-ethoxycarbonyl heptafluorobutyl ester derivatives

Several amino acid enantiomer derivatives were prepared with different chloroformates and analysed by gas chromatography (GC) on a Chirasil-L-Val GC column, at a temperature below 200 degrees C. Among them the N(O,S)-ethoxycarbonyl heptafluorobutyl esters presented the best compromise between short retention times, high yield responses and good resolution for almost all the tested amino acids. These derivatives proved to be suited for quantification of amino acids in aqueous media, with L-p-chlorophenylalanine as internal standard. The developed procedure was applied to several food samples for determination of their free amino acid profiles.     

The 7-nitroindole nucleoside as a photochemical precursor of 2'-deoxyribonolactone: access to DNA fragments containing this oxidative abasic lesion

On the basis of molecular modeling studies, the 7-nitroindole nucleoside 1 was selected as a suitable photochemical precursor for photochemical generation of the C1' deoxyribosyl radical under irradiation, which led to 2'-deoxyribonolactone. The nitro-indole nucleoside derivatives 1a and 1b were prepared and their conformation was determined by X-ray crystallography and NMR spectroscopy. The photoreaction of these nucleosides gave the corresponding deoxyribonolactone derivatives efficiently, with release of 7-nitrosoindole. This reaction was successfully applied to synthesis of oligonucleotides containing the deoxyribonolactone lesion.     

A thieno-2H-chromene alpha-amino acid derivative: synthesis and photochromic properties

[structure: see text] A new photochromic thieno-2H-chromene alpha-amino acid derivative was prepared by C-N palladium-catalyzed cross-coupling of a bromothieno-2H-chromene with the aminated aromatic side chain of the methyl ester of a N,N-diprotected amino acid. Its good photochromic properties demonstrated by flash photolysis and continuous irradiation indicate a possible application in ophthalmic lenses. It may also be inserted into peptides to give photoinduced reversible structural changes.