Ferrocenylethynyl‐Terminated Azobenzenes: Synthesis,Electrochemical, and Photoisomerization Studies

Ferrocenylethynyl‐terminated derivatives 8 – 12 have been synthesized and characterized by electrochemistry and UV/Vis spectroscopy. The electrochemical and photophysical studies indicate that the electronic communication in ferrocenylethynyl‐substituted derivatives is strongly influenced by the substituted position of the ferrocenylethynyl moiety. In situ electrochemical oxidation or chemical oxidation caused a characteristically weak ligand‐to‐metal charge‐transfer (LMCT) band to appear at 700–1000 nm. Subsequent electrochemical reduction or chemical reduction recovered the most of the original curve and the color of the solution as well. Among the derivatives, compound 8 exhibits the highest cis/trans molar ratio (64:36) in the photostationary state (PSS) upon light irradiation at 365 nm. Compound 8 exhibits excellent fatigue resistance and reversibility under several repeated reversible isomerization cycles.     

Sorting out the value of spectroscopic tools to assess the Colletotrichum acutatum impact in olive cultivars with different susceptibilities

The olive tree (Olea europaea L.) can be affected by Colletotrichum acutatum, causing a loss of yield and quality of the final products, whilst the incidence of this fungal infection depends on several factors, including cultivar susceptibility. Thus, the effect of C. acutatum infection in cultivars displaying different susceptibilities to this fungal disease (‘Galega Vulgar’ ‐ susceptible, ‘Cobrançosa’ ‐ moderately susceptible, ‘Picual’ ‐ tolerant) has been assessed through spectrophotometric methods and HPLC, while the FTIR spectra of the cuticles have been concomitantly registered, resorting to the ATR accessory. With the support of multivariate analysis, these spectra allowed to discriminate olives with distinct infection times, besides retrieving evidences concerning the different susceptibility of each cultivar, while these observations were reinforced by the spectrophotometric and chromatographic methods. Furthermore, the assessment of the phenolic profile evidenced individual compounds in the distinct cultivars, so as their variations in response to the fungal infection.     

Soluble Congeners of Prior Insoluble Shape-Persistent Imine Cages

One of the most applied reaction types to synthesize shape-persistent organic cage compounds is the imine condensation reaction and it is assumed that the formed cages are thermodynamically controlled products due to the reversibility of the imine condensation. However, most of the synthesized imine cages reported are formed as precipitate from the reaction mixture and therefore rather may be kinetically controlled products. There are even examples in literature, where resulting cages are not soluble at all in common organic solvents to characterize or study their formation by NMR spectroscopy in solution. Here, a triptycene triamine containing three solubilizing n-hexyloxy chains has been used to synthesize soluble congeners of prior insoluble cages. This allowed us to study the formation as well as the reversibility of cage formation in solution by investigating exchange of building blocks between the cages and deuterated derivatives thereof.     

Application de l'approximation polytropique à la Simulation Numérique Directe de gaz chaudsApplication of the polytropique approximation to Direct Numerical Simulation of heated gases

As alternative to the usual assumptions of Boussinesq, we propose, for heated gases, a new approximation called polytropic approximation. With this approximation the quantities of corresponding state are related by a polytropic law of exponent χ of which we neglect the variability in space-time derivations in the equations governing the flow considered. As application, we used this new proposition to solve numerically a heated gas flow in an annular cavity of rotor-stator type. We expose here the numerical method and some results of the polytropic approximation with comparison to results of Boussinesq approximations. To cite this article: S. Benjeddou et al., C. R. Mecanique 332 (2003).     

Numerical solution of Navier–Stokes equations using multiquadric radial basis function networks

A numerical method based on radial basis function networks (RBFNs) for solving steady incompressible viscous flow problems (including Boussinesq materials) is presented in this paper. The method uses a ‘universal approximator’ based on neural network methodology to represent the solutions. The method is easy to implement and does not require any kind of ‘finite element‐type’ discretization of the domain and its boundary. Instead, two sets of random points distributed throughout the domain and on the boundary are required. The first set defines the centres of the RBFNs and the second defines the collocation points. The two sets of points can be different; however, experience shows that if the two sets are the same better results are obtained. In this work the two sets are identical and hence commonly referred to as the set of centres. Planar Poiseuille, driven cavity and natural convection flows are simulated to verify the method. The numerical solutions obtained using only relatively low densities of centres are in good agreement with analytical and benchmark solutions available in the literature. With uniformly distributed centres, the method achieves Reynolds number Re = 100 000 for the Poiseuille flow (assuming that laminar flow can be maintained) using the density of , Re = 400 for the driven cavity flow with a density of and Rayleigh number Ra = 1 000 000 for the natural convection flow with a density of . Copyright © 2001 John Wiley & Sons, Ltd.     

Orbits Homoclinic to Exponentially Small Periodic Orbits for a Class of Reversible Systems. Application to Water Waves

In this paper a class of reversible analytic vector fields is investigated near an equilibrium. For these vector fields, the part of the spectrum of the differential at the equilibrium which lies near the imaginary axis comes from the perturbation of a double eigenvalue 0 and two simple eigenvalues , . In the first part of this paper, we study the 4-dimensional problem. The existence of a family of solutions homoclinic to periodic orbits of size less than μ^N for any fixed N, where μ is the bifurcation parameter, is known for vector fields. Using the analyticity of the vector field, we prove here the existence of solutions homoclinic to a periodic orbit the size of which is exponentially small ( of order . This result receives its significance from the still unsolved question of whether there exist solutions that are homoclinic to the equilibrium or whether the amplitudes of the oscillations at infinity have a positive infimum. In the second part of this paper we prove that the exponential estimates still hold in infinite dimensions. This result cannot be simply obtained from the study of the 4-dimensional analysis by a center-manifold reduction since this result is based on analyticity of the vector field. One example of such a vector field in infinite dimensions occurs when describing the irrotational flow of an inviscid fluid layer under the influence of gravity and small surface tension (Bond number ) for a Froude number F close to 1. In this context a homoclinic solution to a periodic orbit is called a generalized solitary wave. Our work shows that there exist generalized solitary waves with exponentially small oscillations at infinity. More precisely, we prove that for each F close enough to 1, there exist two reversible solutions homoclinic to a periodic orbit, the size of which is less than , l being any number between 0 and π and satisfying . (Accepted October 2, 1995)