The onset of the tetrabonded structure in liquid water

Water properties are dominated by the hydrogen bond interaction that gives rise in the stable liquid phase to the formation of a dynamical network. The latter drives the water thermodynamics and is at the origin of its well known anomalies. The HB structural geometry and its changes remain uncertain and still are challenging research subjects. A key question is the role and effects of the HB tetrahedral structure on the local arrangement of neighboring molecules in water. Here the hydrogen dynamics in bulk water is studied through the combined use of Neutron Compton Scattering and NMR techniques. Results are discussed in the framework of previous studies performed in a wide temperature range, in the liquid, solid, and amorphous states. For the first time this combined studies provide an experimental evidence of the onset of the water tetrahedral network at T~315 K, originally proposed in previous studies of transport coefficients and thermodynamical data; below this temperature the local order in water changes and the lifetime of local hydrogen bond network becomes long enough to gradually develop the characteristic tetrahedral network of water.     

Probabilistic Study of Rainfall-Triggered Instabilities in Randomly Heterogeneous Unsaturated Finite Slopes

Transport in Porous Media - Water infiltration destabilises unsaturated soil slopes by reducing matric suction, which produces a decrease of material cohesion. If the porosity of the soil is...     

A reduction method to quasilinear hyperbolic systems of multicomponent field PDEs with application to wave interaction

A reduction method is worked out for determining a class of exact solutions with inherent wave features to quasilinear hyperbolic homogeneous systems of N>2 first-order autonomous PDEs. A crucial point of the present approach is that in the process the original set of field equations induces the hyperbolicity of an auxiliary 2×2 subsystem and connection between the respective characteristic velocities can be established. The integration of this auxiliary subsystem via the hodograph method and through the use of the Riemann invariants provides the searched solutions to the full governing system. These solutions also represent invariant solutions associated with groups of translation of space/time coordinates and involving arbitrary functions that can be used for studying non-linear wave interaction. Within such a theoretical framework the two-dimensional motion of an adiabatic fluid is considered. For appropriate model pressure-entropy-density laws, we determine a solution to the governing system of equations which describes in the 2+1 space two non-linear waves which were initiated as plane waves, interact strongly on colliding but emerge with unaffected profile from the interaction region. These model material laws include the classical pressure-entropy-density law which is usually adopted for a polytropic fluid.     

A relax-and-cut framework for Gomory mixed-integer cuts

Gomory mixed-integer cuts (GMICs) are widely used in modern branch-and-cut codes for the solution of mixed-integer programs. Typically, GMICs are iteratively generated from the optimal basis of the current linear programming (LP) relaxation, and immediately added to the LP before the next round of cuts is generated. Unfortunately, this approach is prone to instability. In this paper we analyze a different scheme for the generation of rank-1 GMICs read from a basis of the original LP—the one before the addition of any cut. We adopt a relax-and-cut approach where the generated GMICs are not added to the current LP, but immediately relaxed in a Lagrangian fashion. Various elaborations of the basic idea are presented, that lead to very fast—yet accurate—variants of the basic scheme. Very encouraging computational results are presented, with a comparison with alternative techniques from the literature also aimed at improving the GMIC quality. We also show how our method can be integrated with other cut generators, and successfully used in a cut-and-branch enumerative framework.     

Texture transitions in binary mixtures of 6OBAC with compounds of its homologous series

Recently the authors have observed in compounds of the 4,n-alkyloxybenzoic acid series, with the homologous index n ranging from 6 to 9, a texture transition in the nematic range which subdivides the nematic phase in two sub-phases displaying different textures in polarised light analysis. To investigate a persistence of texture transitions in nematic phases, we prepared binary mixtures of 4,6-alkyloxybenzoic acid (6OBAC) with other members (7-, 8-, 9-, 12-, 16OBAC) of its homologous series. Binary mixtures exhibit a broadening in the temperature ranges of both smectic and nematic phases. A nematic temperature range of 75°C is observed. In the nematic phase, in spite of the microscopic disorder introduced by mixing two components, the polarised light optics analysis of the liquid crystal cells reveals a texture transition. In the case of the binary mixture of 6OBAC with 12OBAC and with 16OBAC, that is of compounds with monomers of rather different lengths, the texture transition temperature is not homogeneous in the cell, probably due to a local variation in the relative concentrations of compounds.     

Measuring financial risk and portfolio optimization with a non-Gaussian multivariate model

In this paper, we propose a multivariate market model with returns assumed to follow a multivariate normal tempered stable distribution. This distribution, defined by a mixture of the multivariate normal distribution and the tempered stable subordinator, is consistent with two stylized facts that have been observed for asset distributions: fat-tails and an asymmetric dependence structure. Assuming infinitely divisible distributions, we derive closed-form solutions for two important measures used by portfolio managers in portfolio construction: the marginal VaR and the marginal AVaR. We illustrate the proposed model using stocks comprising the Dow Jones Industrial Average, first statistically validating the model based on goodness-of-fit tests and then demonstrating how the marginal VaR and marginal AVaR can be used for portfolio optimization using the model. Based on the empirical evidence presented in this paper, our framework offers more realistic portfolio risk measures and a more tractable method for portfolio optimization.     

Isomerization and rearrangement of (E)‐ and (Z)‐phenylhydrazones of 3‐benzoyl‐5‐phenyl‐1,2,4‐oxadiazole: evidence for a ‘new’ type of acid‐catalysis by copper(II) salts in mononuclear rearrangement of heterocycles

A kinetic investigation in methanol of the title reaction has evidenced the occurrence of two processes: the 1‐ E 1‐ Z isomerization and the rearrangement of the (Z)‐isomer into the relevant 4‐benzoylamino‐2,5‐diphenyl‐1,2,3‐triazole ( 1‐ Z → T ). The latter reaction is in line with the ability of the (Z)‐phenylhydrazones of 3‐benzoyl‐1,2,4‐oxadiazoles to undergo the so called mononuclear rearrangement of heterocycles (MRH). The occurrence of both the examined reactions is dependent on a Lewis‐acid‐catalysis. The obtained results have shown the possibility of a ‘new’ type of acid‐catalysis (bifunctional catalysis by Lewis salts) in the MRH. This catalysis operates through a completely different mechanism with respect to the one recently observed, and deeply investigated, in the presence of protic acids for the (Z)‐phenylhydrazone of 5‐amino‐3‐benzoyl‐1,2,4‐oxadiazole, in both dioxane/water and toluene, for which the catalytic process was dependent on the protonation of N(4) ring‐nitrogen of the 1,2,4‐oxadiazole. As a matter of fact, the copper salts seem able to interact with the >C?N? NH? C₆H₅ moiety, yielding adducts which, in some cases, are prone to both isomerize and rearrange. Therefore, a similar behaviour in some manner parallel to that already observed in benzene in the presence of aliphatic amines (base‐catalysis) has been evidenced. Copyright © 2008 John Wiley & Sons, Ltd.     

Thermal decomposition processes in aromatic-aliphatic polyamides investigated by mass spectrometry

The thermal decomposition processes of some aromatic-aliphatic polymides, derived from terephthalic acid and aliphatic diamines, were studied by flash Pyrolysis-GCMS and by direct Pyrolysis-Mass Spectrometry, using both Chemical lonization and Electron Impact modes. The results indicate that the primary thermal decomposition proceeds via a β-CH hydrogen transfer process, with formation of pyrolysis products containing amide and olefin end-groups. Nitrile end-groups are also formed by dehydration of the amide groups formed in the primary decompostion process.     

Multiwalled carbon nanotubes in donor-acceptor nanohybrids-towards long-lived electron transfer products

Novel multiwalled carbon nanotube/metalloporphyrin nanohybrids are devised and probed as versatile donor-acceptor hybrids.