Enhanced production of runaway electrons during a disruptive termination of discharges heated with lower hybrid power in the Frascati Tokamak Upgrade

We report on the observation of a large production of runaway electrons during a disruptive termination of discharges heated with lower-hybrid waves at the Frascati Tokamak Upgrade. The runaway current plateaus, which can carry up to 80% of the predisruptive current, are observed more often than in normal Ohmic disruptions. The largest runaway currents correspond to the slowest plasma current decay rates. This trend is opposite to what is observed in most tokamaks. We attribute this anomalous behavior to the acceleration of the preexistent wave-resonant suprathermal electrons during the disruption decay phase. These results could be relevant for the operation of the ITER tokamak whenever a sizeable amount of lower-hybrid power is made available.     

Homogenization of a conductive suspension in a Stokes–Boussinesq flow

Radiant spherical suspensions have an ε-periodic distribution in a tridimensional incompressible viscous fluid governed by the Stokes–Boussinesq system. We perform the homogenization procedure when the radius of the solid spheres is of order ε³ (the critical size of perforations for the Navier-Stokes system) and when the ratio of the fluid/solid conductivities is of order ε⁶, the order of the total volume of suspensions. Adapting the methods used in the study of small inclusions, we prove that the macroscopic behavior is described by a Brinkman–Boussinesq type law and two coupled heat equations, where certain capacities of the suspensions and of the radiant sources appear.     

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

Switchable polymerization provides the opportunity to regulate polymer sequence and structure in a one‐pot process from mixtures of monomers. Herein we report the use of O₂ as an external stimulus to switch the polymerization mechanism from the radical polymerization of vinyl monomers mediated by (Salen)Co^III?R [Salen=N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine; R=alkyl] to the ring‐opening copolymerization (ROCOP) of CO₂/epoxides. Critical to this process is unprecedented monooxygen insertion into the Co?C bond, as rationalized by DFT calculations, leading to the formation of (Salen)Co^III?O?R as an active species to initiate ROCOP. Diblock poly(vinyl acetate)‐b‐polycarbonate could be obtained by ROCOP of CO₂/epoxides with preactivation of (Salen)Co end‐capped poly(vinyl acetate). Furthermore, a poly(vinyl acetate)‐b‐poly(methyl acrylate)‐b‐polycarbonate triblock copolymer was successfully synthesized by a (Salen)cobalt‐mediated sequential polymerization with an O₂‐triggered switch in a one‐pot process.     

Optical lattice induced light shifts in an yb atomic clock

We present an experimental study of the lattice-induced light shifts on the (1)S(0) --> (3)P(0) optical clock transition (nu(clock) approximately 518 THz) in neutral ytterbium. The "magic" frequency nu(magic) for the 174Yb isotope was determined to be 394 799 475(35) MHz, which leads to a first order light shift uncertainty of 0.38 Hz. We also investigated the hyperpolarizability shifts due to the nearby 6s6p(3)P(0) --> 6s8p(3)P(0), 6s8p(3)P(2), and 6s5f(3)F(2) two-photon resonances at 759.708, 754.23, and 764.95 nm, respectively. By measuring the corresponding clock transition shifts near these two-photon resonances, the hyperpolarizability shift was estimated to be 170(33) mHz for a linear polarized, 50 microK deep, lattice at the magic wavelength. These results indicate that the differential polarizability and hyperpolarizability frequency shift uncertainties in a Yb lattice clock could be held to well below 10(-17).     

Allylic alkylation and ring-closing metathesis in sequence: a successful cohabitation of Pd and Ru

An allylic alkylation/ring-closing metathesis domino catalytic process, wherein a palladium and a ruthenium catalyst are concomitantly present in the reaction mixture from the outset of the reaction, is developed. Evidence for Grubbs' catalysts activity in allylic alkylation is also reported.     

New picropodophyllin analogs via palladium-catalyzed allylic alkylation-Hiyama cross-coupling sequences

Unsaturated malonyl esters underwent Pd-catalyzed intramolecular allylic alkylation to give 4-vinyl-substituted gamma-lactones. In contrast to the formerly studied cyclization of malonamides, this reaction could be achieved only with a substrate incorporating a suitably positioned silicon moiety, which directs the ionization toward the desired eta(3)-allylpalladium complex. The resulting 4-[dimethyl-(2-thienyl)silylvinyl]lactone could be subsequently engaged into Hiyama couplings with various iodoarenes, to give the corresponding 4-(alpha-styryl)-gamma-lactones. The use of a specifically substituted iodoarene generated an advanced tetracyclic lactone intermediate incorporating rings A-D of lignans belonging to the podophyllotoxin family. Subsequent electrophilic aromatic substitution with a variety of electron-rich arenes afforded the target picropodophyllin analogs.     

Effect of the nature of the metal atom on hydrogen bonding and proton transfer to [Cp*MH3(dppe)]: tungsten versus molybdenum

The hydrogen-bonding and proton-transfer pathway to complex [Cp*W(dppe)H(3)] (Cp*=eta(5)-C(5)Me(5); dppe=Ph(2)PCH(2)CH(2)PPh(2)) was investigated experimentally by IR, NMR, UV/Vis spectroscopy in the presence of fluorinated alcohols, p-nitrophenol, and HBF(4), and by using DFT calculations for the [CpW(dhpe)H(3)] model (Cp=eta(5)-C(5)H(5); dhpe=H(2)PCH(2)CH(2)PH(2)) and for the real system. A study of the interaction with weak acids (CH(2)FCH(2)OH, CF(3)CH(2)OH, (CF(3))(2)CHOH) allowed the determination of the basicity factor, E(j)=1.73+/-0.01, making this compound the most basic hydride complex reported to date. A computational investigation revealed several minima for the [CpW(dhpe)H(3)] adducts with CF(3)CH(2)OH, (CF(3))(2)CHOH, and 2(CF(3))(2)CHOH and confirms that these interactions are stronger than those established by the Mo analogue. Their geometries and relative energies are closely related to those of the homologous Mo systems, with the most stable adducts corresponding to H bonding with M-H sites, however, the geometric and electronic parameters reveal that the metal center plays a greater role in the tungsten systems. Proton-transfer equilibria are observed with the weaker proton donors, the proton-transfer step for the system [Cp*W(dppe)H(3)]/HOCH(CF(3))(2) in toluene having DeltaH=(-3.9+/-0.3) kcal mol(-1) and DeltaS=(-17+/-2) cal mol(-1) K(-1). The thermodynamic stability of the proton-transfer product is greater for W than for Mo. Contrary to the Mo system, the protonation of the [Cp*W(dppe)H(3)] appears to involve a direct proton transfer to the metal center without a nonclassical intermediate, although assistance is provided by a hydride ligand in the transition state.