Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

Alkynes are used as building blocks in synthetic and medicinal chemistry, chemical biology, and materials science. Therefore, efficient methods for their synthesis are the subject of intensive research. Herein, we report the direct synthesis of alkynes from readily available carboxylic acids at room temperature under visible‐light irradiation. The combination of an iridium photocatalyst with ethynylbenziodoxolone (EBX) reagents allowed the decarboxylative alkynylation of carboxylic acids in good yields under mild conditions. The method could be applied to silyl‐, aryl‐, and alkyl‐ substituted alkynes. It was particularly successful in the case of α‐amino and α‐oxo acids derived from biomass.     

Routing a mix of conventional,plug-in hybrid,and electric vehicles

We introduce an electric vehicle routing problem combining conventional, plug-in hybrid, and electric vehicles. Electric vehicles are constrained in their service range by their battery capacity, and may require time-consuming recharging operations at some specific locations. Plug-in hybrid vehicles have two engines, an internal combustion engine and an electric engine using a built-in rechargeable battery. These vehicles can avoid visits to recharging stations by switching to fossil fuel. However, this flexibility comes at the price of a generally higher consumption rate and utility cost.To solve this complex problem variant, we design a sophisticated metaheuristic which combines a genetic algorithm with local and large neighborhood search. All route evaluations, within the approach, are based on a layered optimization algorithm which combines labeling techniques and greedy evaluation policies to insert recharging stations visits in a fixed trip and select the fuel types. The metaheuristic is finally hybridized with an integer programming solver, over a set partitioning formulation, so as to recombine high-quality routes from the search history into better solutions. Extensive experimental analyses are conducted, highlighting the good performance of the algorithm and the contribution of each of its main components. Finally, we investigate the impact of fuel and energy cost on fleet composition decisions. Our experiments show that a careful use of a mixed fleet can significantly reduce operational costs in a large variety of price scenarios, in comparison with the use of a fleet composed of a single vehicle class.     

Poincaré-invariant gravitational field and equations of motion of two pointlike objects: The postlinear approximation of general relativity

Using a fast-motion approximation method we obtain the second-order gravitational field and equations of motion for two pointlike objects in algebraically closed form. A regularization procedure is used which is shown to guarantee the consistency of the approximation scheme. The equations of motion are then transformed within the framework of relativistic predictive mechanics into a system of ordinary differential equations.     

Halogenures de tellurenyle—iii: Coupure carbone aromatique-tellure par protodetelluration et carbodetelluration intramoleculaire

In the course of electrophilic cyclisation attempts, o-phenyltellurobenzoyl-chloride did not cyclise to telluroxanthone. but isomerised to 2-chloro tellurobenzophenone through intramolecular carbodetelluration. A breaking of the same C_aromatic-Te bond is also realized by protonolysis. This last reaction leads to a preparative method of synthesis of ditellurosalicylic acid, a starting material for synthesis of benzocondensed tellurium heterocycles.     

A study on exponential-size neighborhoods for the bin packing problem with conflicts

We propose an iterated local search based on several classes of local and large neighborhoods for the bin packing problem with conflicts. This problem, which combines the characteristics of both bin packing and vertex coloring, arises in various application contexts such as logistics and transportation, timetabling, and resource allocation for cloud computing. We introduce \({\mathcal O}(1)\) evaluation procedures for classical local-search moves, polynomial variants of ejection chains and assignment neighborhoods, an adaptive set covering-based neighborhood, and finally a controlled use of 0-cost moves to further diversify the search. The overall method produces solutions of good quality on the classical benchmark instances and scales very well with an increase of problem size. Extensive computational experiments are conducted to measure the respective contribution of each proposed neighborhood. In particular, the 0-cost moves and the large neighborhood based on set covering contribute very significantly to the search. Several research perspectives are open in relation to possible hybridizations with other state-of-the-art mathematical programming heuristics for this problem.     

Slow-light spatial solitons

We numerically and experimentally report the observation of slow-light spatial solitons in a Kerr medium owing to light amplification by stimulated Raman scattering. This was achieved in a CS2 nonlinear planar waveguide that possesses both a strong self-focusing nonlinearity to generate the spatial Raman soliton and a Raman susceptibility sharp enough to induce the slow-light process simultaneously. We show that the Raman Stokes component is optically delayed by more than 120 ps for a 140 ps Raman pulse duration and only 3 cm of propagation length, while propagating as a spatial soliton beam.     

Josephson effect through an isotropic magnetic molecule

We study the Josephson effect through a quantum dot magnet whose spin is isotropic and which is coupled to the dot electron spin via exchange coupling. We calculate the Andreev levels and the supercurrent and examine the intertwined effect of the exchange coupling, Kondo correlation, and superconductivity. The former suppresses Kondo correlations, which triggers phase transitions from the 0 to the pi state, but strong antiferromagnetic coupling restores the 0 state. The asymmetric phase diagram in the exchange coupling suggests that the coupling sign could be determined in experiments.     

Structures and solution dynamics of pseudorotaxanes mediated by alkali-metal cations

Kinetic stability studies of a series of pseudorotaxanes formed from electron-rich crown ethers (hosts and ) and naphthalene diimide (guest ) in the presence of alkali salt templates MX (where M(+) = Li(+) and Na(+), and X(-) = Cl(-), Br(-), I(-), NO(3)(-) and CF(3)SO(3)(-)) were performed by (1)H NMR. The switching between the (bound) host and its linkage isomer host (free) was monitored in solution in the presence and absence of alkali salts, to establish the relative thermodynamic stabilities in the series. We also report here six new crystal structures, for pseudorotaxanes of type: [.], [M(2)..](2+) and [M(2)..](2+). Their solution-phase structures are in good agreement with the solid-state structures determined by X-ray crystallography.     

Approaches to open fullerenes: synthesis and thermal stability of cis-1 bis(isobenzofuran) Diels-Alder adducts of C60

In a quest to form wider openings within the cage of the fullerene C60 through controlled bond-breaking reactions, we have examined the double saturation of adjacent C=C bonds within a six-membered ring of C60. We have investigated the double Diels-Alder cycloaddition of two tethered isobenzofurans to the fullerene C60. We obtained cis-1 adducts in good yields after reacting the methylene- or quinoxaline-tethered bis(isobenzofuran) precursors 2a-k with parent 3,6-dihydro-1,2,4,5-tetrazine (3b). The X-ray structure of the methylene-tethered bis(isobenzofuran)-C60 adduct 4b has been obtained; four-eclipsed substituents are held rigidly by the bicyclic addends. The cis-1 bis(isobenzofuran) bisadducts 4b and 4e-j are kinetically far more stable toward thermal retro-Diels-Alder fragmentation than are mono(isobenzofuran) adducts of C60, in solution and in the solid state as determined by 1H NMR spectroscopy or thermogravimetric analysis. A methodology for the reversible solubilization of other fullerene derivatives based on this work is also presented.     

One-Pot Synthesis of Phosphinylphosphonate Derivatives and Their Anti-Tumor Evaluations

This paper reports on the synthesis of new hydroxymethylene-(phosphinyl)phosphonates (HMPPs). A methodology has been developed to propose an optimized one-pot procedure without any intermediate purifications. Various aliphatic and (hetero)aromatic HMPPs were synthesized in good to excellent yields (53–98%) and the influence of electron withdrawing/donating group substitution on aromatic substrates was studied. In addition, the one-pot synthesis of HMPP was monitored by ³¹P NMR spectroscopy, allowing effective control of the end of the reaction and identification of all phosphorylated intermediate species, which enabled us to propose a reaction mechanism. Optimized experimental conditions were applied to the preparation of biological relevant aminoalkyl-HMPPs. A preliminary study of the complexation to hydroxyapatite (bone matrix) was carried out in order to verify its lower affinity towards bone compared to bisphosphonate molecules. Moreover, in vitro anti-tumor activity study revealed encouraging antiproliferative activities on three human cancer cell lines (breast, pancreas and lung).