Fast H-vacancy dynamics during alanate decomposition by anelastic spectroscopy. proposition of a model for Ti-enhanced hydrogen transport

A systematic study of the dehydrogenation process of undoped and of catalyzed NaAlH4 by means of anelastic spectroscopy is presented. Evidence is reported of the formation of a highly mobile species during decomposition, which has been identified in off-stoichiometric AlH6-x units, giving rise to fast H vacancy local dynamics. The formation of such stoichiometry defects starts at temperatures much lower in Ti doped than in undoped samples, and concomitantly with the decomposition reaction. The catalyst atoms decrease the energy barrier to be overcome by H to break the bond, thus enhancing the kinetics of the chemical reactions and decreasing the temperature at which the dehydrogenation processes take place. The experimental data show that not all the hydrogen released by the formula units during the evolution of decomposition evolves out of the sample, but part of it remains in the lattice and migrates on a long-range scale within the sample. We identify, in this H mobilized population, the species which induces the fast tetragonal to monoclinic phase transformation accompanying decomposition. A partial spontaneous thermally activated regression of decomposition has also been observed by aging experiments. A model is proposed which accounts for the action of the Ti catalyst and for the atomistic mechanism of decomposition.     

Synthesis and crystallographic characterization of chiral bis-oxazoline-amides. Fine-tunable ligands for Pd-catalyzed asymmetric alkylations

New chiral chelating C2 bis-oxazoline-amide ligands (1) exhibiting a highly flexible molecular structure have been prepared in high yield through a versatile synthetic pathway. Combined crystallographic, variable temperature (VT)-NMR, IR, and ESI-MS studies have been carried out to investigate the nature of the 1-Pd complexes that are effective tools in controlling the stereochemical outcome of Pd-catalyzed allylic alkylations (ee up to 98%).     

Relation between charge ordering and local lattice disorder in manganites studied by EXAFS

We report extended X-ray absorption fine structure measurements at the Mn K absorption edge and in a wide temperature range on La_0.25Ca_0.75MnO₃ samples with a charge ordering transition temperature, T_CO of the Mn³⁺ and Mn⁴⁺ ions around 225 K. The mean Mn-O distances do not show major changes at the transition; however, our results show the presence of an anomalous local lattice disorder and distortion below T_CO, possibly determined by the breaking of the symmetries of the high temperature state, that is the splitting of the Mn-O distances.     

Effects of water freezing on the mechanical properties of nafion membranes

Most of the research efforts on Nafion have been devoted to the study of the perfluorinated ionomer membranes at optimal conditions for the desired applications, such as high temperature and low relative humidity for polymer electrolyte membrane fuel cells (PEM FC). In view of the possible changes induced by the freezing of water in the structure of Nafion and considering that in cold start conditions of a PEM FC device, Nafion needs to work also below 273 K, we measured the Young's modulus (Y) and the elastic energy dissipation (tan δ) in the temperature range between 90 and 470 K and the stress–strain curves between 300 and 173 K. The measurements reported here indicate that the mechanical properties of wet Nafion membrane change dramatically with temperature, that is, from a rubber‐like behavior at room temperature to a brittle behavior below 180 K. Moreover, we observed that the freezing of the nanoconfined water is complete only below 180 K, as indicated by a large increase of the Young's modulus. Between 180 and 300 K, the large values of tan δ suggest the occurrence of friction between the liquid water bound to the walls of the hydrophilic domains and the solid ice residing in the center of channels. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis of syn- and anti-tricyclo [4.1.0.02,4] heptan-5-ones and related compounds

A convenient entry to both title compounds 1 and 2, as well as to cis- and trans-4-iodomethyl-bicyclo [3.1.0]-hexan-2-ones 3and 4 and to 4-methyl-bicyclo [3.1.0]-hex-3-en-2-one 5 involving base-promoted reactions of cis- and -trans-3,4-diiodomethylcyclopentanones 6 and 7 is reported, and the behaviour of 6 and 7 towards different bases. bfv40bp4761b     

On a Marinacci uniqueness theorem for measures

We prove a uniqueness theorem for measures on D-posets.     

A new enantiodivergent synthesis of the Geissman-Waiss lactone

Intramolecular Michael reaction of methyl (R)-6-(tert-butoxycarbonylamino)oxy-4-hydroxy-2-hexenoate, in turn obtained from tert-butyl (R)-3-hydroxy-4-pentenoate, paved the way to the synthesis of both enantiomers of 2-oxa-6-azabicyclo[3.3.0]octan-3-one (the Geissman-Waiss lactone), a precursor for necine bases. Key intermediates in this approach were represented by enantiomeric bicyclic lactones incorporating a [1,2]-oxazinane nucleus, which has been conveniently used to install the pyrrolidine framework of the target compounds through a synthetic scheme featuring the reduction of the nitrogen-oxygen bond and an intramolecular S_N2 reaction.     

Linear and non-linear interactions between static and dynamic bifurcations of damped planar beams

The critical and post-critical behavior of a non-conservative non-linear structure, undergoing statical and dynamical bifurcations, is analyzed. The system consists of a purely flexible planar beam, equipped with a lumped visco-elastic device, loaded by a follower force. A unique integro-differential equation of motion in the transversal displacement, with relevant boundary conditions, is derived. Then, the linear stability diagram of the trivial rectilinear configuration is built-up in the parameter space. Particular emphasis is given to the role of the damping on the critical scenario. The occurrence of different mechanisms of instability is highlighted, namely, of divergence, Hopf, double zero, resonant and non-resonant double Hopf, and divergence-Hopf bifurcation. Attention is then focused on the two latter (codimension-two) bifurcations. A multiple scale analysis is carried-out directly on the continuous model, and the relevant non-linear bifurcation equations in the amplitudes of the two interactive modes are derived. The fixed-points of these equations are numerically evaluated as functions of two bifurcation parameters and some equilibrium paths illustrated. Finally, the bifurcation diagrams, illustrating the system behavior around the critical points of the parameter space, are obtained.