Unexpectedly superior enantioselectivity for trans-stilbene cis-dihydroxylation over anchored triosmium carbonyl species in confined Al-MCM-41 channels

Superior enantioselectivity in the dihydroxylation of trans-stilbene catalysed by anchored triosmium carbonyl species without using a chiral modifier is observed inside sterically congested MCM-41 channels; this effect is more pronounced through the introduction of surface Al sites into the silicate.

Fractionated crystallization and fractionated melting of confined PEO microdomains in PB-b-PEO and PE-b-PEO diblock copolymers

The confined crystallization of poly(ethylene oxide) (PEO) in predominantly spherical microdomains formed by several diblock copolymers was studied and compared. Two polybutadiene-b-poly(ethylene oxide) diblock copolymers were prepared by sequential anionic polymerization (with approximately 90 and 80 wt % polybutadiene (PB)). These were compared to equivalent samples after catalytic hydrogenation that produced double crystalline polyethylene-b-poly(ethylene oxide) diblock copolymers. Both systems are segregated into microdomains as indicated by small-angle X-ray scattering (SAXS) experiments performed in the melt and at lower temperatures. However, the PB-b-PEO systems exhibited a higher degree of order in the melt. A predominantly spherical morphology of PEO in a PB or a PE matrix was observed by both SAXS and transmission electron microscopy, although a possibly mixed morphology (spheres and cylinders) was formed when the PEO composition was close to the cylinder-sphere domain transitional composition as indicated by SAXS. Differential scanning calorimetry experiments showed that a fractionated crystallization process for the PEO occurred in all samples, indicating that the PE cannot nucleate PEO in these diblock copolymers. A novel result was the observation of a subsequent fractionated melting that reflected the crystallization process. Sequential isothermal crystallization experiments allowed us to thermally separate at least three different crystallization and melting peaks for the PEO microdomains. The lowest melting point fraction was the most important in terms of quantity and corresponded to the crystallization of isolated PEO spheres (or cylinders) that were either superficially or homogeneously nucleated. This was confirmed by Avrami index values of approximately 1. The isothermal crystallization results indicate that the PE matrix restricts the crystallization of the covalently bonded PEO to a higher degree compared to PB.

Magnetically separable, carbon-supported nanocatalysts for the manufacture of fine chemicals

The best of both worlds: The synthesis of carbon-encapsulated iron-based magnetic nanoparticles is described. With such small catalysts that have macroscopic magnetic properties, the advantages of homogeneous or colloidal and heterogeneous catalysts can be combined.

A simple analysis of thermodynamic properties for classical plasmas: I. theory

By eliminating the short range negative divergence of the Debye–Hückel pair distribution function, but retaining the exponential charge screening known to operate at large interparticle separation, the thermodynamic properties of one-component plasmas of point ions or charged hard spheres can be well represented even in the strong coupling regime. Predicted electrostatic free energies agree within 5% of simulation data for typical Coulomb interactions up to a factor of 10 times the average kinetic energy. Here, this idea is extended to the general case of a uniform ionic mixture, comprising an arbitrary number of components, embedded in a rigid neutralizing background. The new theory is implemented in two ways: (i) by an unambiguous iterative algorithm that requires numerical methods and breaks the symmetry of cross correlation functions; and (ii) by invoking generalized matrix inverses that maintain symmetry and yield completely analytic solutions, but which are not uniquely determined. The extreme computational simplicity of the theory is attractive when considering applications to complex inhomogeneous fluids of charged particles.

Radar observations of non-thermal plasmas at different aspect angles

Data are presented from the EISCAT CP-3-E experiment which show the presence of non-thermal plasma over a range of latitudes. The O+ ion-velocity distribution function is almost toroidal when the electric field reaches values of 125 mV m−1. The ion temperature derived from such data assuming a Maxwellian distribution function will overestimate the true ion temperature when the observing angle is large with respect to the magnetic field, and underestimate the temperature when the aspect angle is small. When the expressions for the distribution function are extended to include mixed ion composition, an improvement is sometimes found in fitting the observed data, and estimates of the composition can be made. Such an analysis suggests that N2+ can occasionally form a significant part of the total ion density in a narrow height region centred at 275 km.

Observations of nonthermal plasmas at different aspect angles

Data are presented from the EISCAT (European Incoherent Scatter (Facility)) CP-3-E experiment which show large increases in the auroral zone convection velocities (>2 km s−1) over a wide range of latitudes. These are larger than the estimated neutral thermal speed and allow a study of the plasma in a nonthermal state over a range of observing angles. Spectra are presented which show a well-defined central peak, consistent with an ion velocity distribution function which significantly departs from a Maxwellian form. As the aspect angle decreases, the central peak becomes less obvious. Simulated spectra, derived using theoretical expressions for the O+ ion velocity distribution function based on the generalized relaxation collision model, are compared with the observations and show good first-order, qualitative agreement. It is shown that ion temperatures derived from the observations, with the assumption of a Maxwellian distribution function, are an overestimate of the true ion temperature at large aspect angles and an underestimate at low aspect angles. The theoretical distribution functions have been included in the “standard” incoherent scatter radar analysis procedure, and attempts have been made to derive realistic ionospheric parameters from nonthermal plasma observations. If the expressions for the distribution function are extended to include mixed ion composition, a significant improvement is found in fitting some of the observed spectra, and estimates of the ion composition can be made. The non-Maxwellian analysis of the data revealed that the spectral shape distortion parameter, D*, was significantly higher in this case for molecular ions than for atomic ions in a thin height slab roughly 40 km thick. This would seem unlikely if the main molecular ions present were NO+. We therefore suggest that N2+ formed a significant proportion of the molecular ions present during these observations.

Model predictions of the occurrence of non-Maxwellian plasmas, and analysis of their effects on EISCAT data

The recent identification of non-thermal plasmas using EISCAT data has been made possible by their occurrence during large, short-lived flow bursts. For steady, yet rapid, ion convection the only available signature is the shape of the spectrum, which is unreliable because it is open to distortion by noise and sampling uncertainty and can be mimicked by other phenomena. Nevertheless, spectral shape does give an indication of the presence of non-thermal plasma, and the characteristic shape has been observed for long periods (of the order of an hour or more) in some experiments. To evaluate this type of event properly one needs to compare it to what would be expected theoretically. Predictions have been made using the coupled thermosphere-ionosphere model developed at University College London and the University of Sheffield to show where and when non-Maxwellian plasmas would be expected in the auroral zone. Geometrical and other factors then govern whether these are detectable by radar. The results are applicable to any incoherent scatter radar in this area, but the work presented here concentrates on predictions with regard to experiments on the EISCAT facility.

Do the legs of magnetic clouds contain twisted flux-rope magnetic fields?

Magnetic clouds (MCs) are a subset of interplanetary coronal mass ejections (ICMEs) characterised primarily by a smooth rotation in the magnetic field direction indicative of the presence of a magnetic flux rope. Energetic particle signatures suggest MC flux ropes remain magnetically connected to the Sun at both ends, leading to widely used model of global MC structure as an extended flux rope, with a loop-like axis stretching out from the Sun into the heliosphere and back to the Sun. The time of flight of energetic particles, however, suggests shorter magnetic field line lengths than such a continuous twisted flux rope would produce. In this study, two simple models are compared with observed flux rope axis orientations of 196 MCs to show that the flux rope structure is confined to the MC leading edge. The magnetic cloud “legs,” which magnetically connect the flux rope to the Sun, are not recognisable as MCs and thus are unlikely to contain twisted flux rope fields. Spacecraft encounters with these non-flux rope legs may provide an explanation for the frequent observation of non-magnetic cloud ICMEs.