Template burning inside TS-1 and Fe-MFI molecular sieves: an in situ XRPD study

The high X-ray flux available at the European Synchrotron Radiation Facility (ESRF), combined with the use of a suitably designed area detector setup, allowed us to follow in real time the structural changes occurring during the template burning processes inside TS-1 and Fe-silicalite MFI zeolites with a X-ray powder diffraction technique (XRPD). Rietveld analysis of the XRPD patterns collected in the 350-1000 K interval, integrated each 15 K, yields to the determination of the template overall occupancy factor versus T with an accuracy comparable with that obtained by thermogravimetric measurements, routinely employed for this purpose. The evolution of the structural parameters (V, a, b, c, site occupancy factor of the template molecule) vs T has been obtained. These data allow us to have, for the first time, a complete view of the structural rearrangements induced by the template burning process on the zeolitic framework. The differences caused by the different heteroatom inserted in the MFI lattice (Ti or Fe) are discussed. For both TS-1 and Fe-MFI, the kinetics of the reaction were investigated, to obtain the activation energy of the calcinations process employing the nonisothermal data according to the theory recently proposed by Kennedy and Clark [Thermochim. Acta, 1997, 307, 27-35]. For TS-1 only, the time-resolved template burning experiment has been repeated in isothermal conditions at four different temperatures, to obtain the activation energy from isothermal data, according to the standard procedure. Comparison between Arrhenius plots obtained from isothermal and nonisothermal data demonstrates that the Kennedy and Clark method can be also applied to complex materials such as the MFI zeolites. This approach, when applied to time-resolved XRPD studies, is much less time consuming (requesting, in principle, one single nonisothermal run) with respect to the classic approach, which requests at least three isothermal runs. Moreover, it allows a remarkably lower associated error (151 +/- 11 versus 146 +/- 30 kJ mol(-)(1)) due to the much higher number of experimental points employed to perform the linear fit.     

DFT Investigation of H2 activation by [M(NHPnPr3)('S3')] (M = Ni, Pd). Insight into key factors relevant to the design of hydrogenase functional models

Density functional theory has been used to investigate the reaction between H(2) and [Ni(NHPnPr(3))('S3')] or [Pd(NHPnPr(3))('S3')], where 'S3' = bis(2-sulfanylphenyl)sulfide(2-), which are among the few synthetic complexes featuring a metal coordination environment similar to that observed in the [NiFe] hydrogenase active site and capable of catalyzing H(2) heterolytic cleavage. Results allowed us to unravel the reaction mechanism, which is consistent with an oxidative addition-hydrogen migration pathway for [Ni(NHPnPr(3))('S3')], whereas metathesis is also possible with [Pd(NHPnPr(3))('S3')]. Unexpectedly, H(2) binding and activation implies structural reorganization of the metal coordination environment. It turns out that the structural rearrangement in [Ni(NHPnPr(3))('S3')] and [Pd(NHPnPr(3))('S3')] can take place due to the peculiar structural features of the Ni and Pd ligands, explaining the remarkable catalytic properties. However, the structural reorganization is the most unfavorable step along the H(2) cleavage pathway (DeltaG > 100 kJ mol(-1)), an observation that is relevant for the design and synthesis of novel biomimetic catalysts.     

Solute-solvent interactions and chiral induction in liquid crystals

The induction of a cholesteric phase by doping an achiral nematic liquid crystal with an enantiopure solute is a phenomenon that, as in all general supramolecular phenomena of chiral amplification, depends in a subtle way on intermolecular interactions. The micrometric helical deformation of the phase director in the cholesteric phase is generated by the interplay of anisotropy and chirality of probe-medium interactions. In the case of a flexible chiral dopant, the solvent can influence the twisting power in two ways, difficult to disentangle: it is responsible for the solute orientational order, an essential ingredient for the emergence of phase chirality; but also it can affect the dopant conformational distribution and then the chirality of the structures present in the solution. In this work we have investigated methyl phenyl sulfoxide, a flexible, chiral molecule that, when dissolved in different nematics, can produce cholesteric phases of opposite handedness. This peculiar, intriguing sensitivity to the environment makes MPS a suitable probe for a thorough investigation of the effects of solute-solvent interactions on chiral induction in liquid crystals. NMR experiments in various nematic solvents have been performed in addition to twisting power measurements. From the analysis of partially averaged 1H-1H and 13C-1H dipolar couplings, the effects of solvent on solute conformation and orientational order are disentangled, and this information is combined with the modeling of the chirality of intermolecular interactions, within a molecular field theory. The integration of different techniques allows an unprecedented insight into the role of solvent in mediating the chirality transfer from molecule to phase.     

Direct gravimetric measurements of the mass of the antarctic aerosol collected by high volume sampler: PM10 summer seasonal variation at Terra Nova Bay

An on-site procedure was set up for direct gravimetric measurement of the mass of aerosol collected using high volume impactors (aerodynamic size cut point of 10 microm, PM10); this knowledge has hitherto been unavailable. Using a computerized microbalance in a clean chemistry laboratory, under controlled temperature (+/-0.5 degrees C) and relative humidity (+/-1%), continuous, long time filter mass measurements (hours) were carried out before and after exposure, after a 48 h minimun equilibration at the laboratory conditions. The effect of the electrostatic charge was exhausted in 30-60 min, after which stable measurements were obtained. Measurements of filters exposed for 7-11 days (1.13 m3 min(-1)) in a coastal site near Terra Nova Bay (December 2000 - February 2001), gave results for aerosol mass in the order of 10-20 mg (SD approximately 2 mg), corresponding to atmospheric concentrations of 0.52-1.27 microg m(-3). Data show a seasonal behaviour in the PM10 content with an increase during December - early January, followed by a net decrease. The above results compare well with estimates obtained from proxy data for the Antarctic Peninsula (0.30 microg m(-3)), the Ronne Ice Shelf (1.49 microg m(-3)), and the South Pole (0.18 microg m(-3), summer 1974-1975, and 0.37 microg m(-3), average summer seasons 1975-1976 and 1977-1978), and from direct gravimetric measurements recently obtained from medium volume samplers at McMurdo station (downwind 3.39 microg m(-3), upwind 4.15 microg m(-3)) and at King George Island (2.5 microg m(-3), summer, particle diameter <20 microm). This finding opens the way to the direct measurement of the chemical composition of the Antarctic aerosol and, in turn, to a better knowledge of the snow/air relationships as required for the reconstruction of the chemical composition of past atmospheres from deep ice core data.     

Diffusion and viscosity of a calamitic liquid crystal model studied by computer simulation

We report a molecular dynamics simulation study on an ensemble of rod-like particles, each composed of nine soft spheres held rigidly along a line. We have calculated translational mean square displacements and velocity autocorrelation functions in the fluid phases exhibited by the model, i.e., smectic A, nematic and isotropic. These quantities have then been used to compute diffusion coefficients. In addition, we have calculated viscosities in the nematic and isotropic phases. Despite its crude nature, the model is capable of providing a faithful reproduction of many features of the transport behavior observed in real liquid-crystalline materials. The simulation results have been compared with the predictions of the modified affine transformation theory, finding only a fair agreement.     

Regularity at the boundary for v onQ-pseudoconvex domainsonQ-pseudoconvex domains

Solvability for with regularity at the boundary of a domain Ω ⊂⊂ ℂ ⁿ for forms of any degreek≥1 was characterized by pseudoconvexity of ϖΩ in [16]. It is proved here thatq-pseudoconvexity suffices to guarantee solvability of forms of degreek≥q+1. The method relies on theL ² estimates in [13], and on their Sobolev version in [15] and [16].     

Prime Divisors of Shifted Factorials

For any positive integer n we let P(n) be the largest primefactor of n. We improve and generalize several results of P.Erds and C. Stewart on P(n!+1). In particular, we show thatlim sup_ninfin; P(n!+1)/n2.5, which improves their lower boundof lim sup_ninfin; P(n!+1)/n2. 2000 Mathematics Subject Classification11A05, 11A07, 11J86.     

Fibonacci numbers that are not sums of two prime powers

In this paper, we construct an infinite arithmetic progression of positive integers such that if , then the th Fibonacci number is not a sum of two prime powers.

     

Self-healing generation of spatial solitons in liquid crystals

We demonstrate that, in suitably designed cells with undoped nematic liquid crystals, extraordinary-wave spatial solitons can be excited at every applied voltage without adjustments in the input polarization. Their walk-off, hence direction of propagation, is externally controlled over angles as large as 7 degrees. The results pave the way not only to polarization-forgiving generation but also to voltage readdressing of these extraordinary-wave nematicons.