Toward reactant encapsulation for substrate-selectivity

A synthetic tris-(bis-(aminomethyl)pyridine) receptor was prepared in excellent yields via reversible imine condensation strategy. Catalytic activity in Henry reactions of the corresponding copper(II) complex was studied. Capitalizing on previous works by Anslyn with related receptors, the dramatic increase in basicity induced by this type of complex on diketo-derivatives was used to perform a nucleophilic addition of a deprotonated substrate onto an electrophile within the cavity. Hence, a Lewis acid stabilized nitronate was reacted with various aldehydes. A notable preference for small reactants easily accommodated in the cavity over encumbered ones was observed, thus representing an example of substrate-selectivity.     

Travelling wave mathematical analysis and efficient numerical resolution for a one-dimensional model of solid propellant combustion

We investigate a model of solid propellant combustion involving surface pyrolysis coupled to finite activation energy gas-phase combustion. Existence and uniqueness of a travelling wave solution are established by extending dynamical system tools classically used for premixed flames, dealing with the additional difficulty arising from the surface regression and pyrolysis. An efficient shooting method allows to solve the problem in phase space without resorting to space discretisation nor fixed-point Newton iterations. The results are compared to solutions from a CFD code developed at ONERA, assessing the efficiency and potential of the method, and the impact of the modelling assumptions is evaluated through parametric studies.     

Synthesis,Photophysics and Nonlinear Optical Properties of Stilbenoid Pyrimidine‐Based Dyes Bearing Methylenepyran Donor Groups

The nonlinear properties and the photophysical behavior of two π‐conjugated chromophores that incorporate an electron‐deficient pyrimidine core (A) and γ‐methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes’ scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end‐groups. This latter structural parameter also has a strong influence on the excited‐state dynamics, which leads to a very efficient fluorescence quenching.     

Carbon/carbon supercapacitors

Supercapacitors, or electrochemical capacitors, are a power storage system applied for harvesting energy and delivering pulses during short periods of time. The commercially available technology is based on charging an electrical double-layer (EDL), and using high surface area carbon electrodes in an organic electrolyte. This review first presents the state-of-the-art on EDL capacitors, with the objective to better understand their operating principles and to improve their performance. In particular, it is shown that capacitance might be enhanced for carbons having subnanometric pores where ions of the electrolyte are distorted and partly desolvated. Then, strategies for using environment friendly aqueous electrolytes are presented. In this case, the capacitance can be enhanced through pseudo-faradaic contributions involving i) surface functional groups on carbons, ii) hydrogen electrosorption, and iii) redox reactions at the electrode/electrolyte interface. The most promising system is based on the use of aqueous alkali sulfate as electrolyte allowing voltages as high as 2 V to be reached, due to the high overpotential for di-hydrogen evolution at the negative electrode.     

Improved Asymmetric Synthesis of 8-Arylmenthols

A two-step synthesis of a set of arylmenthones 3 from R(+)-pulegone 2 via their silylenolethers 4 is proposed leading in high yields to 8-arylmenthols 1.