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.     

Laser beam brightness of apertured optical resonators

We model the fundamental mode of a circularly symmetric plano-concave resonator where one mirror is apertured by a super-Gaussian aperture, while the other is apertured by a π/2 phase aperture. The aim of the paper is to find the best values of the apertured cavity parameters allowing the highest output beam brightness. For that we take into account loss level, fundamental mode volume and beam quality factor M². We demonstrate that for a given loss level, the phase aperture is able to increase the laser beam brightness, with a rate of about 60% when its diameter is properly chosen.     

Preparation of Al2O3–ZrO2 mixed supports; their characteristics and hydrothermal stability

Al₂O₃–ZrO₂ mixed supports have been synthesised using a colloidal solution of ZrO(OH)₂ or a Zr(IV) propoxide solution in organic medium. Zirconia content in these samples was about 10% (36% of the theoretic monolayer). The hydrothermal stability (alumina→boehmite transformation at 230 °C, about 10 bar pressure, in the presence of water vapour) of these supports was then investigated by XRD. The presence of the zirconia over the alumina decrease the quantity of boehmite formed after the hydrothermal treatment. The dispersion of zirconia and the stability in hydrothermal conditions of the final support are function of the preparation method.     

Gravity-Mediated Modifications of the Dispersion Relation in Nontrivial Backgrounds

Radiative corrections evaluated in nontrivial backgrounds lead to dispersion relations which effectively break the local Lorentz symmetry even if Lorentz invariance holds at a fundamental level. We report on progress made toward the calculation of radiative corrections which are induced by gravity. These should be relevant when approaching Planck scale. We first present the properties of the self-energy of a scalar particle traveling in a thermal graviton bath. We then discuss the possibility of performing the corresponding calculation in a curved background. We give the connection between two different approaches to the dispersion relation, based on the self-energy and the effective action, and we emphasize the need for the closed-time-path formalism in curved backgrounds.     

Stochastic graph partitioning: quadratic versus SOCP formulations

We consider a variant of the graph partitioning problem involving knapsack constraints with Gaussian random coefficients. In this new variant, under this assumption of probability distribution, the problem can be traditionally formulated as a binary SOCP for which the continuous relaxation is convex. In this paper, we reformulate the problem as a binary quadratic constrained program for which the continuous relaxation is not necessarily convex. We propose several linearization techniques for latter: the classical linearization proposed by Fortet (Trabajos de Estadistica 11(2):111–118, 1960) and the linearization proposed by Sherali and Smith (Optim Lett 1(1):33–47, 2007). In addition to the basic implementation of the latter, we propose an improvement which includes, in the computation, constraints coming from the SOCP formulation. Numerical results show that an improvement of Sherali–Smith’s linearization outperforms largely the binary SOCP program and the classical linearization when investigated in a branch-and-bound approach.