Synthesis of the all-cis-trimethyldecalin fragment of unusual terpenes by radical-mediated protonolysis of an alkylboron derivative

The synthesis of an enantiopure building-block with a contiguous all-cis-trimethyldecalin motif embedded in unusual terpenes is described. Starting from the Wieland–Miescher ketone, the key step is a one-pot hydroboration of an exocyclic methylene double bond promoted by disiamylborane and radical-mediated protonolysis of the corresponding alkylborane using 4-tert-butylcatechol.     

A branch-and-cut-and-price approach for the pickup and delivery problem with shuttle routes

The Pickup and Delivery Problem with Shuttle routes (PDPS) is a special case of the Pickup and Delivery Problem with Time Windows (PDPTW) where the trips between the pickup points and the delivery points can be decomposed into two legs. The first leg visits only pickup points and ends at some delivery point. The second leg is a direct trip – called a shuttle – between two delivery points. This optimization problem has practical applications in the transportation of people between a large set of pickup points and a restricted set of delivery points.     

Vinylogous Urethane Vitrimers

Vitrimers are a new class of polymeric materials with very attractive properties, since they can be reworked to any shape while being at the same time permanently cross‐linked. As an alternative to the use of transesterification chemistry, we explore catalyst‐free transamination of vinylogous urethanes as an exchange reaction for vitrimers. First, a kinetic study on model compounds reveals the occurrence of transamination of vinylogous urethanes in a good temperature window without side reactions. Next, poly(vinylogous urethane) networks with a storage modulus of ≈2.4 GPa and a glass transition temperature above 80 °C are prepared by bulk polymerization of cyclohexane dimethanol bisacetoacetate, m‐xylylene diamine, and tris(2‐aminoethyl)amine. The vitrimer nature of these networks is examined by solubility, stress‐relaxation, and creep experiments. Relaxation times as short as 85 s at 170 °C are observed without making use of any catalyst. In addition, the networks are recyclable up to four times by consecutive grinding/compression molding cycles without significant mechanical or chemical degradation.     

New bounds and estimates for porous media with rigid perfectly plastic matrixNouvelles bornes et estimations pour les milieux poreux à matrice rigide parfaitement plastique

We derive new rigorous bounds and self-consistent estimates for the effective yield surface of porous media with a rigid perfectly plastic matrix and a microstructure similar to Hashin's composite spheres assemblage. These results arise from a homogenisation technique that combines a pattern-based modelling for linear composite materials and a variational formulation for nonlinear media. To cite this article: N. Bilger et al., C. R. Mecanique 330 (2002) 127–132.     

Effect of nano/micro‐mixed ceramic fillers on the dielectric and thermal properties of epoxy polymer composites

Nano/micro ceramic‐filled epoxy composite materials have been processed with various percentage additions of SiO₂, Al₂O₃ ceramic fillers as reinforcements selected from the nano and micro origin sources. Different types of filler combinations, viz. only nano, only micro, nano/micro, and micro/micro particles, were designed to investigate their influence on the thermal expansion, thermal conductivity, and dielectric properties of epoxy polymers. Thermal expansion studies were conducted using thermomechanical analysis that revealed a two‐step expansion pattern consecutively before and after vitreous transition temperatures. The presence of micro fillers have shown vitreous transition temperature in the range 70–80°C compared with that of nano structured composites in which the same was observed as ~90°C. Similarly, the bulk thermal conductivity is found to increase with increasing percentage of micron‐size Al₂O₃. It was established that the addition of micro fillers lead to epoxy composite materials that exhibited lower thermal expansion and higher thermal conductivity compared with nano fillers. Moreover, nano fillers have a significantly decisive role in having low bulk dielectric permittivity. In this study, epoxy composites with a thermal expansion coefficient of 2.5 × 10^?5/K, thermal conductivity of 1.18 W/m · K and dielectric permittivity in the range 4–5 at 1 kHz have been obtained. The study confirms that although the micro fillers seem to exhibit good thermal conductivity and low expansion coefficient, the nano‐size ceramic fillers are candidate as cofillers for low dielectric permittivity. However, a suitable proportion of nano/micro‐mixed fillers is necessary for achieving epoxy composites with promising thermal conductivity, controlled coefficient of thermal expansion and dielectric permittivity. Copyright © 2013 John Wiley & Sons, Ltd.     

Repairing the Thiol‐Ene Coupling Reaction

Thiol‐ene coupling (TEC) reactions emerged as one of the most useful processes for coupling different molecular units under reaction mild conditions. However, TEC reactions involving weak C? H bonds (allylic and benzylic fragments) are difficult to run and often low yielding. Mechanistic studies demonstrate that hydrogen‐atom transfer processes at allylic and benzylic positions are responsible for the lack of efficiency of the radical‐chain process. These competing reactions cannot be prevented, but reported herein is a method to repair the chain process by running the reaction in the presence of triethylborane and catechol. Under these reaction conditions, a unique repair mechanism leads to an efficient chain reaction, which is demonstrated with a broad range of anomeric O‐allyl sugar derivatives including mono‐, di‐, and tetrasaccharides bearing various functionalities and protecting groups.     

Dispersible Carbon Nanotubes

A method is proposed to produce nanoparticles dispersible and recyclable in any class of solvents, and the concept is illustrated with the carbon nanotubes. Classically, dispersions of CNTs can be achieved through steric stabilization induced by adsorbed or grafted polymer chains. Yet, the surface modification of CNTs surfaces is irreversible, and the chemical nature of the polymer chains imposes the range of solvents in which CNTs can be dispersed. To address this limitation, supramolecular bonds can be used to attach and to detach polymer chains from the surface of CNTs. The reversibility of supramolecular bonds offers an easy way to recycle CNTs as well as the possibility to disperse the same functional CNTs in any type of solvent, by simply adapting the chemical nature of the stabilizing chains to the dispersing medium. The concept of supramolecular functionalization can be applied to other particles, for example, silica or metal oxides, as well as to dispersing in polymer melts, films or coatings.     

Dynamics of spray and swirling flame under acoustic oscillations : A joint experimental and LES investigation

The dynamics of spray swirling flames is investigated by combining experiments on a single sector generic combustor and large eddy simulations of the same configuration. Measurements and calculations correspond to a self-sustained limit cycle operation where combustion coupled by an axial quarter wave acoustic mode induces large amplitude oscillations of pressure in the system. A detailed analysis of the mechanisms controlling the process is carried out first by comparing the measured and calculated spray and flame dynamics. Considering in a second stage that the spray and flame are compact with respect to the acoustic wavelength the analysis can be simplified by defining state variables that are obtained by taking averages over the combustor cross section and representing the behavior of these average quantities as a function of the axial coordinate and time. This reveals a first region in which essentially convective processes prevail. The convective heat release rate then couples further downstream with the pressure field giving rise to positive Rayleigh source terms which feed energy in the axial acoustic mode. In the convective region, the swirl number features oscillations around its mean value with an impact on the flow aerodynamics and flame radial displacement. Fluctuations in the fuel flow rate are initiated at the injector exhaust and likewise convected downstream. The total mass flow rate that exhibits strong convective disturbances is dominated further downstream by the acoustic motion. This information provides new insights on the convective-acoustic coupling that controls the heat release rate disturbances and reveals the time delays governing the combustion oscillation process.     

Burstiness and spreading on temporal networks

We discuss how spreading processes on temporal networks are impacted by the shape of their inter-event time distributions. Through simple mathematical arguments and toy examples, we find that the key factor is the ordering in which events take place, a property that tends to be affected by the bulk of the distributions and not only by their tail, as usually considered in the literature. We show that a detailed modeling of the temporal patterns observed in complex networks can change dramatically the properties of a spreading process, such as the ergodicity of a random walk process or the persistence of an epidemic.