Experimental realization of an exact solution to the Vlasov equations for an expanding plasma

We study the expansion of ultracold neutral plasmas in the regime in which inelastic collisions are negligible. The plasma expands due to the thermal pressure of the electrons, and for an initial spherically symmetric Gaussian density profile, the expansion is self-similar. Measurements of the plasma size and ion kinetic energy using fluorescence imaging and spectroscopy show that the expansion follows an analytic solution of the Vlasov equations for an adiabatically expanding plasma.     

Kinetic energy oscillations in annular regions of ultracold neutral plasmas

A study of ion equilibration in annular regions of ultracold strontium plasmas is reported. Plasmas are formed by photoionizing laser-cooled atoms with a pulsed dye laser. The experimental probe is spatially-resolved absorption spectroscopy using the ²S_1/2-²P_1/2 transition of the Sr⁺ ion. The kinetic energy of the ions is calculated from the Doppler broadening of the spectrum, and it displays clear oscillations during the first microsecond after plasma formation. The oscillations, which are a characteristic of strong coulomb coupling, are fit with a simple phenomenological model incorporating damping and density variation in the plasma.     

Ruthenium-Decorated Lipid Vesicles: Light-Induced Release of [Ru(terpy)(bpy)(OH(2))](2+) and Thermal Back Coordination

Electrostatic forces play an important role in the interaction between large transition metal complexes and lipid bilayers. In this work, a thioether-cholestanol hybrid ligand (4) was synthesized, which coordinates to ruthenium(II) via its sulfur atom and intercalates into lipid bilayers via its apolar tail. By mixing its ruthenium complex [Ru(terpy)(bpy)(4)](2+) (terpy = 2,2';6',2'-terpyridine; bpy = 2,2'-bipyridine) with either the negatively charged lipid dimyristoylphosphatidylglycerol (DMPG) or with the zwitterionic lipid dimyristoylphosphatidylcholine (DMPC), large unilamellar vesicles decorated with ruthenium polypyridyl complexes are formed. Upon visible light irradiation the ruthenium-sulfur coordination bond is selectively broken, releasing the ruthenium fragment as the free aqua complex [Ru(terpy)(bpy)(OH(2))](2+). The photochemical quantum yield under blue light irradiation (452 nm) is 0.0074(8) for DMPG vesicles and 0.0073(8) for DMPC vesicles (at 25 °C), which is not significantly different from similar homogeneous systems. Dynamic light scattering and cryo-TEM pictures show that the size and shape of the vesicles are not perturbed by light irradiation. Depending on the charge of the lipids, the cationic aqua complex either strongly interacts with the membrane (DMPG) or diffuses away from it (DMPC). Back coordination of [Ru(terpy)(bpy)(OH(2))](2+) to the thioether-decorated vesicles takes place only at DMPG bilayers with high ligand concentrations (25 mol %) and elevated temperatures (70 °C). During this process, partial vesicle fusion was also observed. We discuss the potential of such ruthenium-decorated vesicles in the context of light-controlled molecular motion and light-triggered drug delivery.     

Electron-temperature evolution in expanding ultracold neutral plasmas

We have used the free expansion of ultracold neutral plasmas as a time-resolved probe of electron temperature. A combination of experimental measurements of the ion expansion velocity and numerical simulations characterize the crossover from an elastic-collision regime at low initial Gamma(e), which is dominated by adiabatic cooling of the electrons, to the regime of high Gamma(e) in which inelastic processes drastically heat the electrons. We identify the time scales and relative contributions of various processes, and we experimentally show the importance of radiative decay and disorder-induced electron heating for the first time in ultracold neutral plasmas.     

Mechanistic investigations of the ethylene tetramerisation reaction

The unprecedented selective tetramerisation of ethylene to 1-octene was recently reported. In the present study various mechanistic aspects of this novel transformation were investigated. The unusually high 1-octene selectivity in chromium-catalyzed ethylene tetramerisation reactions is caused by the unique extended metallacyclic mechanism in operation. Both 1-octene and higher 1-alkenes are formed by further ethylene insertion into a metallacycloheptane intermediate, whereas 1-hexene is formed by elimination from this species as in other reported trimerisation reactions. This is supported by deuterium labeling studies, analysis of the molar distribution of 1-alkene products, and identification of secondary co-oligomerization reaction products. In addition, the formation of two C6 cyclic products, methylenecyclopentane and methylcyclopentane, is discussed, and a bimetallic disproportionation mechanism to account for the available data is proposed.     

Bose–Einstein condensation in atomic hydrogen

The addition of atomic hydrogen to the set of gases in which Bose–Einstein condensation can be observed expands the range of parameters over which this remarkable phenomenon can be studied. Hydrogen, with the lowest atomic mass, has the highest transition temperature, 50 μK in our experiments. The very weak interaction between the atoms results in a high ratio of the condensate to normal gas densities, even at modest condensate fractions. Using cryogenic rather than laser precooling generates large condensates. Finally, two-photon spectroscopy is introduced as a versatile probe of the phase transition: condensation in real space is manifested by the appearance of a high-density component in the gas, condensation in momentum space is readily apparent in the momentum distribution, and the phase transition line can be delineated by following the evolution of the density of the normal component.     

One-Pot Regioselective γ-Trifluoromethylthiolation and γ-Methylthiolation of Enals

We describe herein the direct electrophilic γ-trifluoromethylthiolation and γ-methylthiolation of enals, via the in situ formation of the corresponding silyl dienol ether. This one-pot process is carried out under simple and mild reaction conditions and is compatible with a variety of functional groups.