Aged titania nanoparticles: the simultaneous control of local and long-range properties

TiO(2) nanoparticles are obtained by combining a sol-gel preparative route with hydrothermal aging steps, performed in mild conditions, of varying time lengths. Both aged and un-aged samples are thermally treated at 300 and 600 degrees C, for the same length of time. The crystal structures, the phase composition, and crystallite sizes are analyzed by powder X-ray diffraction. Raman spectra of anatase nanocrystals with average sizes of 7-10 nm are reported and the correlation between the Raman band shape of the main feature at 144 cm(-1) and the crystallite size is discussed. Nitrogen physisorption by Brunauer-Emmett-Teller (BET) method is adopted to evaluate the particles surface area and mesopore size and size distribution. The role played by the hydrothermal step in affecting the physicochemical properties of the powders is discussed also with respect to the H(2)O/TiO(2) interactions as apparent from Raman spectroscopy investigations of the O-H stretching range (3000-3800 cm(-1)).     

Conformational analysis of hydrazones. 1H dynamic nuclear magnetic resonance and solvent effects in aryl- and 2-furylaldehyde ethylaminoacetylhydrazones

Aryl- and 2-furylaldehyde ethylaminoacetylhydrazones were examined in different solvents and over a wide temperature range with ¹H NMR in order to study their conformational properties. Nearly equal amounts of the E/Z isomers, relative to the C?N bond, are present, even when the solvents and the substituents on the aldimino carbon produce small changes in the isomeric mixture. The activation parameters of the thermal isomerization process were measured, and the results are in the line with a lateral-shift type mechanism, also supported by theoretical calculations on a model compound. No other internal process was noted from the low-temperature spectral behaviour, and this was interpreted in terms of a highly biased equilibrium concerning the rotation around the C(O)? N bond. Chemical shifts obtained in different solvents also enable the most stable arrangement of the whole molecule of these compounds to be postulated.     

3-Sasakian manifolds, 3-cosymplectic manifolds and Darboux theorem

We present a compared analysis of some properties of 3-Sasakian and 3-cosymplectic manifolds. We construct a canonical connection on an almost 3-contact metric manifold which generalises the Tanaka–Webster connection of a contact metric manifold and we use this connection to show that a 3-Sasakian manifold does not admit any Darboux-like coordinate system. Moreover, we prove that any 3-cosymplectic manifold is Ricci-flat and admits a Darboux coordinate system if and only if it is flat.     

Interaction of rotationally aligned and of oriented molecules in gas phase and at surfaces

Recent developments concerning the generation of molecular beams containing oriented/aligned molecules will be reviewed and applications of such tools to the study of elementary processes occurring both in homogeneous and heterogeneous phases will be presented. First we will discuss the case of symmetric top molecules oriented by hexapoles. Here the molecular polarization is obtained by the use of an external field and allows to control which end of the molecular projectile is going to collide with the target. Then we will review the so-called collisional alignment, a molecular polarization phenomenon occurring in supersonic expansions of gaseous mixtures. The key feature, in this case, is the velocity dependence of the alignment degree, which allows the use of mechanical devices to filter out of the beam the molecules having either a random (statistical) or a preferential (non-statistical) spatial distribution of their rotational angular momentum J with respect to the molecular beam axis. The physical mechanisms underlying the collisional alignment will be resumed and some relevant gas-phase experiments demonstrating its occurrence will be illustrated. Application of such methodologies to the investigation of the stereodynamics of elementary processes occurring in gas-surface interaction will be presented and discussed for both weakly and strongly interacting systems.     

A Six-Pulse PASS MAS-NMR Technique Solved by a Phasor Method

The PASS MAS-NMR technique is capable of recovering full intensities of the central resonances of a spectrum by phase adjusting the spinning sidebands. This variant of the original PASS sequence by Dixon uses six π pulses instead of four. The addition of two π pulses provides more flexibility in choosing the spacing between pulses and therefore eliminates pulse overlap and receiver dead-time problems. The nonlinear, underdetermined PASS equations were solved using a graphical phasor method. All PASS sequences were successfully tested. A table of the six pulse delay times for different pitches is presented.