Ising transition driven by frustration in a 2D classical model with continuous symmetry

We study the thermal properties of the classical antiferromagnetic Heisenberg model with both nearest (J1) and next-nearest (J2) exchange couplings on the square lattice by extensive Monte Carlo simulations. We show that, for J2/J1>1/2, thermal fluctuations give rise to an effective Z2 symmetry leading to a finite-temperature phase transition. We provide strong numerical evidence that this transition is in the 2D Ising universality class, and that T(c)-->0 with an infinite slope when J2/J1-->1/2.     

Passerini reaction – Amine Deprotection – Acyl Migration (PADAM): a convenient strategy for the solid-phase preparation of peptidomimetic compounds

beta-Acylamino-alpha-hydroxyamides and beta-acylamino-alpha-oxoamides, compounds known to be potent protease inhibitors, can be conveniently prepared with a highly convergent strategy involving a Passerini multicomponent reaction between a N-protected alpha-aminoaldehyde, a carboxylic acid and an isocyanide. After N-deprotection and concomitant acyl migration the desired beta-acylamino-alpha-hydroxyamide moiety is obtained and can be further elaborated, for example via oxidation of the secondary alcohol group. In this paper we report the studies that have been carried out in order to transfer this synthetic methodology onto polystyrene resin, using a photocleavable linker and a N-Boc protecting strategy.     

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.     

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].     

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.     

Highly diastereoselective allylic azide formation and isomerization. Synthesis of 3(2'-amino)-beta-lactams

The stereoselective anti SN2' attack of NaN3 to 3-alkenyl-3-bromo-azetidin-2-ones gave a mixture of diastereomeric azides in fast equilibrium. The [3,3]-sigmatropic rearrangement of allylic azides occurred with complete stereocontrol, allowing the equilibrium to be directed preferentially toward the (E)- or (Z)-isomer, useful precursors of 3(2'-amino)-beta-lactams. [reaction: see text]     

Base-promoted cyclization of 1-nitrohydrazones bearing a thioether function

Functionalized 1-nitrohydrazones 5 react with sodium hydride in boiling benzene to afford different types of ring-closed products. The formation of the latter can be ascribed to competitive modes of evolution of first-formed nitrile imines.