Synthese de benzodioxines-1,4 disubstitutes sur l'heterocycle

The dianion of benzodioxin 2- carboxylic acid can be prepared and reacts with carbonyl compounds to give 2,3- disubstituted 1,4- benzodioxines.     

Hydrogenolysis of lignins : nickel boride catalyst

Nickel boride generated within the wood structure allows the selective hydrogenolysis of wood meals. 4-n-Ethylguaiacol and 4-n-Ethylsyringol are prepared with interesting yields.     

On DRC‐covering of Kn by cycles

This paper considers the cycle covering of complete graphs motivated by the design of survivable WDM networks, where the requests are routed on INF‐networks which are protected independently from each other. The problem can be stated as follows: for a given graph G, find a cycle covering of the edge set of K_n, where V(K_n) = V(G), such that each cycle in the covering satisfies the disjoint routing constraint (DRC7rpar;, relatively to G, which can be stated as follows: to each edge of K_n we associate in G a path and all the paths associated to the edges of a cycle of the covering must be vertex disjoint. Here we consider the case where G = C_n, a ring of size n and we want to minimize the number of cycles in the covering. We give optimal solutions for the problem as well as for variations of the problem, namely, its directed version and the case when the cycle length is fixed to 4. © 2003 Wiley Periodicals, Inc. J Combin Designs 11: 100–112, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10040     

Molecular dynamics simulations of electron-alkali cation pairs in bulk water

The structural, dynamic, and thermodynamic properties of an excess electron interacting with an alkali cation (Na+, K+, Li+) in bulk water were investigated by means of a mixed quantum-classical molecular dynamics simulation technique. This study includes a reparametrization of the electron-cation pseudopotentials. The free energy calculations for all three systems show that a contact electron-cation pair can be observed, which is either as stable as the dissociated pair (Li+) or more stable by only a few kT (Na+, K+). Given that the dissociation barrier is also quite small, we suggest that the average cation-electron distance in the experiments at room temperature will not depend on this free energy profile but rather on the minimization of the Coulombic repulsive interaction between like charges in the solvent medium. This enables us to compare the present molecular dynamics simulations with the spectroscopic data obtained for different ionic strengths. The overall trend of the UV-vis hydrated absorption spectra, namely, the shift toward shorter wavelengths at high ionic strengths, is fairly well reproduced. This confirms our hypothesis of statistical distribution of the cations and solvated electrons.     

A Computational and Experimental Approach Linking Disorder,High‐Pressure Behavior,and Mechanical Properties in UiO Frameworks

Whilst many metal–organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO‐topology Zr‐MOFs, the planar UiO‐67 ([Zr₆O₄(OH)₄(bpdc)₆], bpdc: 4,4′‐biphenyl dicarboxylate) and UiO‐abdc ([Zr₆O₄(OH)₄(abdc)₆], abdc: 4,4′‐azobenzene dicarboxylate) by single‐crystal nanoindentation, high‐pressure X‐ray diffraction, density functional theory calculations, and first‐principles molecular dynamics. On increasing pressure, both UiO‐67 and UiO‐abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo‐linker of UiO‐abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO‐67, characterized by a large elastic modulus. The use of non‐linear linkers in the synthesis of UiO‐MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range.     

How Can a Hydrophobic MOF be Water‐Unstable? Insight into the Hydration Mechanism of IRMOFs

We report an ab initio molecular dynamics study of the hydration process in a model IRMOF material. At low water content (one molecule per unit cell), water physisorption is observed on the zinc cation but the free?bound equilibrium strongly favors the free state. This is consistent with the hydrophobic nature of the host matrix and its type‐V isotherm observed in a classical Monte Carlo simulation. At higher loading, a water cluster can be formed at the Zn₄O site and this is shown to stabilize the water‐bound state. This structure rapidly transforms into a linker‐displaced state, where water has fully displaced one arm of a linker and which corresponds to the loss of the material’s fully ordered structure. Thus an overall hydrophobic MOF material can also become water unstable, a feature that has not been fully understood until now.     

Kinematic Fields and Acoustic Emission Observations Associated with the Portevin Le Châtelier Effect on an Al–Mg Alloy

This paper presents experimental tensile test results obtained on flat aluminum magnesium alloy samples on a hard machine. The mechanical response, kinematic fields and acoustic emissions were simultaneously obtained in an experimental setup. Propagation instabilities associated with the Portevin–Le-Chatelier effect were observed as localized intense strain increment bands. Depending on the strain rate, A, B or C types were studied on the basis of stress drops, acoustic emission and strain fields. Then the band characteristics (position, orientation, width, thickness reduction, intensity, acoustic emission, principal strain direction) were presented in various strain rate conditions.