Analysis of Non-innocence of Phosphaquinodimethane Ligands when Charge and Aromaticity Come into Play

Several phosphaquinodimethanes and their M(CO)₅ complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH₂ substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8.     

Liquid–crystalline nematic polymers revisited

A new model for nematic polymers is proposed, based on the probability ψ(u,u,t) for a macromolecule to be oriented along direction u while embedded in a u environment created by its neighbours. The potential of the internal forces is written Φ(u,u) accordingly. The free energy contains a contribution ν Φ + k_BT ln ψ where the brackets mean an average over the probability distribution, while ν is the (uniform) polymer number density. An equation is derived for the time-evolution of the order parameter S = uu − I/3, together with an expression for the stress tensor. These two results offer a generalization of the Doi Model in so far as they include a distortional energy, analogue to the Frank elastic energy for low molecular mass nematics. Extending the Maier–Saupe variational procedure, we specify the way that the internal potential Φ(u,u) must be written for it to favour non-zero values of the order parameter, while giving a penalty to situations with gradients of the order parameter. The result is quite different from the potential proposed a decade ago by Marrucci and Greco (their Φ depends on u only), while it has a clear connection with the so-called Landau-de Gennes (LdG) tensor models, which are based on a free-energy depending on the order parameter and its gradients.     

Application de l'approximation polytropique à la turbulence statistique en moyenne de FavreApplication of the polytropic approximation to turbulence statistics using Favre averaging

The application of the polytropic approximation connecting the quantities of corresponding state, to experimental analysis, is clarified. A method of polytropic determination of the exponent χ (variable but non-fluctuating) in each point of the flow is given. This approximation makes it possible the generation of representative signals of fluctuating quantities, like pressure or density. For heated gases, the problem of measurement of the equations terms written with Favre averaging is thus almost solved. Then, measurement of χ allows the determination by the experiment of crucial terms like turbulent fluxes of mass and momentum, and presso correlation. To cite this article: C. Rey, S. Benjeddou, C. R. Mecanique 332 (2004).     

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).     

Orienting properties of discotic nematic liquid crystals in Jeffrey-Hamel flows

The orienting properties of incompressible discotic nematic liquid crystals for creeping flows between converging and diverging planar walls (Jeffrey-Hamel) are analyzed using the Leslie-Ericksen theory. The dependence of director orientation on the reactive parameter and the flow kinematics is presented. Closed form stationary solutions for the director orientation are found when elastic effects are neglected. Stationary numerical solutions for the velocity and director fields using the full Leslie-Ericksen theory are presented. The director field in converging flow is characterized by azimuthal (radial) centerline orientation, by being asymmetric with respect to the azimuthal (radial) direction, and by having an allowed orientation range that spans two half-quadrants (full quadrants). In the limiting case of perfectly flat disk ( –) the flow-induced director orientation in converging flow is the azimuthal direction, while in diverging flow the director rotates by a full n radians. By reducing the vertex angle between the walls to vanishingly small values, converging flow solutions properly reduce to those of flow between parallel plates, but diverging flows are expected to lead to a new instability.     

Towards the Rational Design of Efficient Organic Structure‐Directing Agents for Zeolite Synthesis

Zeolites are crystalline microporous materials with application in diverse fields, especially in catalysis. The ability to prepare zeolites with targeted physicochemical properties for a specific catalytic application is a matter of great interest, because it allows the efficiency of the entire chemical process to be increased (higher product yields, lower undesired by‐products, less energy consumption, and cost savings, etc). Nevertheless, directing the zeolite crystallization towards the material with the desired framework topology, crystal size, or chemical composition is not an easy task, since several variables influence the nucleation and crystallization processes. The combination of accumulated knowledge, rationalization, and innovation has allowed the synthesis of unique zeolitic structures in the last few years. This is especially true in terms of the design of organic and inorganic structure‐directing agents (SDAs). In this Minireview we will present the rationale we have followed in our studies to synthesize new zeolite structures, while putting this in perspective with the advances made by other researchers of the zeolite community.     

Two negative minima of the first normal stress difference in a cellulose‐based cholesteric liquid crystal: Helix uncoiling

The shear rate dependence of material functions such as shear viscosity (η) and the first normal stress difference (N₁) were given and interpreted earlier by Kiss and Porter. Their widely accepted work revealed the possibility of having a negative minimum of N₁ for polymeric liquid crystals. In this work, we disclose for the first time the evidence of two negative N₁ minima on a sheared cellulosic lyotropic system. The lower shear rate minimum is ascribed to the uncoiling of the cholesteric helix, as theoretically predicted earlier. Our findings contribute also to the understanding of the other minimum already reported in the literature and attributed to the nematic director tumbling mode. Moreover, the elastic change that the LC‐HPC sample undergoes during the helix unwinding of the cholesteric structure is also by means of oscillatory measurements. This study is a contribution for the understanding of the structure‐properties relationship linked with the complex rheological behavior of chiral nematic cellulose‐based systems and may help to improve their further processing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 821–830