Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate

Pentacoordinate silicon derivatives with a chloromethyl ligand are versatile compounds that are usually obtained from the corresponding tetravalent trialkoxy- or trihalogeno(chloromethyl)silane. We describe herein the synthesis of a chloromethylsilicate bearing two Martin’s ligands readily obtained by addition of in situ generated chloromethyllithium to a spirosilane. The reactivity of this new species was evaluated and it has been established that the chloride is displaced by strong nucleophiles such as alkyllithiums and (hetero)aryllithiums. In Lewis acidic conditions, the pentacoordinate silicon species rearranges through a formal insertion of a methylene into one Si–C bond, to form a new tetravalent spirosilane with a six-membered ring. The same kind of rearrangement can be triggered also by addition of a Lewis base. The mechanism of the rearrangement in both conditions has been studied by means of DFT calculations.     

The Standard Model from LHC to future colliders

This review summarizes the results of the activities which have taken place in 2014 within the Standard Model Working Group of the “What Next” Workshop organized by INFN, Italy. We present a framework, general questions, and some indications of possible answers on the main issue for Standard Model physics in the LHC era and in view of possible future accelerators.     

Control of an axisymmetric subsonic air jet by plasma actuator

It is known that surface non-thermal plasma actuators have proved their efficiency for aerodynamics flow control. In this study, a dielectric barrier discharge (DBD) is mounted on the diffuser of an axisymmetric turbulent air jet in order to control the flow separation along a 12-degree diffuser bevel. The momentum created by the actuator is applied to separate an air flow naturally attached to the diffuser for air flow velocity up to 40 m s⁻¹. Laser sheet visualizations and LDV measurements are achieved to characterize the unforced and forced air jet. The flow separation, the induced velocity fluctuations, the jet mixing improvement and vectoring are investigated. The main results of this study demonstrate that DBD actuators are suitable to fully detach the air flow along the bevel for a velocity of 20 m s⁻¹ and that a jet vectoring between 13.5° and 5.5° could be achieved for velocity ranging between 20 and 40 m s⁻¹. Considerations about a potential improvement of the jet mixing are also introduced and the laser sheet visualization attests that induced flow perturbations are highly 3D.     

Optimization of a dielectric barrier discharge actuator by stationary and non-stationary measurements of the induced flow velocity: application to airflow control

Several studies have shown that a surface dielectric barrier discharge (DBD) may be used as an electrohydrodynamic (EHD) actuator in order to control airflows. In this paper, a parametric study has been performed in order to increase the velocity of the ionic wind induced by such actuators. The results show that an optimization of geometrical and electrical parameters allows us to obtain a time-averaged ionic wind velocity up to 8 m/s at 0.5 mm from the wall. Moreover, non-stationary measurements of the induced wind have been performed with synchronized records of current and voltage signals. These experiments show that the DBD actuator seems to generate a pulsed velocity at the same frequency than the applied high voltage.     

Phosphine-free perfluoro-tagged palladium nanoparticles supported on fluorous silica gel: application to the Heck reaction

The immobilization of phosphine-free perfluoro-tagged palladium nanoparticles Pd-1 on fluorous silica gel (FSG) and their utilization in the Heck reaction have been investigated. High yields of vinylic substitution products have been obtained. Recycling studies have shown that the solid-supported palladium catalyst can be readily recovered and reused several times without significant loss of activity. Reactions and recovery of the solid-supported palladium catalyst system can be carried out in the presence of air, without any particular precaution.     

Vine copula modeling dependence among cyber risks: A dangerous regulatory paradox

Dependence among different cyber risk classes is a fundamentally underexplored topic in the literature. However, disregarding the dependence structure in cyber risk management leads to inconsistent estimates of potential unintended losses. To bridge this gap, this article adopts a regulatory perspective to develop vine copulas to capture dependence. In quantifying the solvency capital requirement gradient for cyber risk measurement according to Solvency II, a dangerous paradox emerges: an insurance company does not tend to provide cyber risk hedging products as they are excessively expensive and would require huge premiums that it would not be possible to find policyholders.     

A Newly Designed Water Soluble Uranyl-Salophen Complex for Anion Recognition

A novel water-soluble uranyl-salophen (salophen=N,N‘-disalicylidene-o-phenylenediaminate) complex was obtained. Solubility was achieved in aqueous methyl-β-cyclodextrin solutions, taking advantage of the host-guest interactions established with the adamantyl moieties present on the ligand skeleton. Such an approach facilitates the synthesis of the receptor and the purification processes and, in perspective, can be definitely applicable to other molecular scaffolds. UV/Vis titration experiments demonstrate that the capacity of the uranyl-salophen core to behave as a receptor for anions is retained in water and appears comparable with that previously reported for other water-soluble uranyl-salophen systems. Hence the presence of cyclodextrins does not interfere with molecular recognition processes.