Reactions of the iso-butyl radical during 1,1′-azoisobutane pyrolysis

Quantitative analysis of the products formed in 1,1′-azoisobutane pyrolyses in the temperature range of 553°–602°K has shown that the major reactions of the iso-butyl radical are Analysis of initial rate data gave log₁₀k₄/(k_c)^1/2(cm^?3/2.mol ^1/2.sec^?1/2) = 7.54±0.44 ? (136.5 + 4.8) kJ/mol/2.303RT, the Arrhenius parameters obtained being in good agreement with thermodynamic data for reaction (4). Measured values of k_a/(k_c)^1/2 where k_a is the rate constant of the reaction iC₄H₉ + AIB → iC₄H₁₀ +. AIB were consistent with published parameters determined by photolysis of 1,1′-azoisobutane. Combination of photolysis and pyrolysis data gave log₁₀ k_a/(k_c)^1/2(cm^3/2.mol^?1/22.sec^?1/2) = 3.68 ± 0.15 ? (27.2 ± 1.2) kJ/mol/2.303RT. The crosscombination ratio for methyl and iso-butyl radicals has been found to be 0.25, indicating that the geometric mean rule does not hold for methyl and iso-butyl radicals.     

Interaction of cobalt(II) and nickel(II) with a gamma-linked, bis-beta-diketone ligand to yield an unusual coordination motif

Discrete cobalt(II) and nickel(II) complexes of type ML (where L is a bis(2,4-pentanedionate) derivative incorporating a -SCH2CH2S- bridge between the gamma-carbons of respective beta-diketone units) have been synthesised and represent the first examples in which a gamma-substituted, thioether-containing beta-diketone ligand coordinates via a sulfur and oxygen donor in preference to the classical coordination mode involving both beta-diketonate oxygens.     

Single-mode plane-polarized ytterbium-doped large-core fiber laser with 633-W continuous-wave output power

We demonstrate a cladding-pumped single-mode plane-polarized ytterbium-doped fiber laser generating 633 W of continuous-wave output power at 1.1 microm with 67% slope efficiency and a polarization extinction ratio better than 16 dB. The laser is end pumped through both fiber ends and shows no evidence of roll-over, even at the highest output power, which is limited only by the available pump power.     

Single-frequency, single-mode, plane-polarized ytterbium-doped fiber master oscillator power amplifier source with 264 W of output power

We present a single-frequency, single-mode, plane-polarized ytterbium-doped all-fiber master oscillator power amplifier source at 1060 nm generating 264 W of continuous-wave output power. The final-stage amplifier operated with a high gain of 19 dB and a high conversion efficiency of 68%. There was no evidence of rollover from stimulated Brillouin scattering even at the highest output power, and the maximum output was limited only by the available pump power.     

Radiation-driven hydrodynamics of high- hohlraums on the national ignition facility

The first hohlraum experiments on the National Ignition Facility (NIF) using the initial four laser beams tested radiation temperature limits imposed by plasma filling. For a variety of hohlraum sizes and pulse lengths, the measured x-ray flux shows signatures of filling that coincide with hard x-ray emission from plasma streaming out of the hohlraum. These observations agree with hydrodynamic simulations and with an analytical model that includes hydrodynamic and coronal radiative losses. The modeling predicts radiation temperature limits with full NIF (1.8 MJ), greater, and of longer duration than required for ignition hohlraums.     

Nonequilibrium raftlike membrane domains under continuous recycling

We present a model for the kinetics of spontaneous membrane domain (raft) assembly that includes the effect of membrane recycling ubiquitous in living cells. We show that domains can have a broad power-law distribution with an average radius that scales with the 1/4 power of the domain lifetime when the line tension at the domain edges is large. For biologically reasonable recycling and diffusion rates, the average domain radius is in the tens of nm range, consistent with observations. This represents one possible link between signaling (involving rafts) and traffic (recycling) in cells. Finally, we present evidence that suggests that the average raft size may be the same for all scale-free recycling schemes.     

Productive chloroarene C-cl bond activation: palladium/phosphine-catalyzed methods for oxidation of alcohols and hydrodechlorination of chloroarenes

The palladium/phosphine-catalyzed productive chloroarene C-Cl bond activation provides general, efficient, and functional group friendly methods for the selective oxidation of alcohols and the hydrodechlorination of chloroarenes.     

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