The photochemistry of dioxorhenium(V)

The excited-state properties of trans-ReO₂(py)₄⁺ (ReO₂⁺) in acetonitrile solution have been investigated. The excited-state absorption spectrum of ReO₂⁺ is dominated by bleaching of the ground state MLCT and d-d systems. The reduction potential of ReO₂^2+/+* is estimated from emission and electrochemical data to be -0.7 V (SSCE). The ReO₂⁺ excited state efficiently reduces methylviologen and other pyridinium and olefin acceptors. The resulting Re(VI) species oxidizes secondary alcohols and silanes. Acetophenone is the product of sec-phenethyl alcohol oxidation.

The emission properties of ReO₂⁺ in aqueous solutions of anionic and nonionic surfactants have been investigated. The emission and absorption maxima of ReO₂⁺ are dependent on the water content of its environment. Emission lifetimes vary over four orders of magnitude upon shifting from aqueous to nonaqueous environments. The emission lifetime has a large (8.6) isotope effect (k(H₂O)/k(D₂O)) that reflects its sensitivity towards the environment. These properties have been used to develop a model for the interactions of ReO₂⁺ with sodium dodecyl sulfate (SDS). A hydrophobic ReO₂⁺ derivative, ReO₂(3-Ph-py)₄⁺, has been used to probe micelles of nonionic surfactants, and these results are consistent with those obtained with SDS.

The emission properties of ReO₂⁺ in Nafion perfluorosulfonated membranes have been investigated. Absorption and emission spectroscopy indicate that the interior of the membrane is quite polar, similar to ethylene glycol. Two well-resolved emission components show different lifetimes and different isotope effects, indicative of varying degrees of solvent accessibility. These components are taken as evidence for chemically distinct regions in the polymer film, assigned as the interfacial region and the ion cluster region.

The unsubstituted pyridine complex shows monophasic, τ = 1.7 µs, emission decay when bound to calf thymus DNA. Switching to the 3-Ph-py complex yields a biphasic emission decay (τ₁ = 2.4 µs, τ₂ = 10 µs) indicative of an additional, solvent-inaccessible binding mode. Photoinduced electron transfer to methylviologen leads to oxidative cleavage of the DNA as detected by gel electrophoresis. Electrochemical and spectrophotometric techniques used with organic substrates also can be used to monitor the oxidation of DNA. Abstraction of the ribose 4' hydrogen by ReO₂²⁺ is a possible mechanism.

Extension theorems for functions of vanishing mean oscillation

A locally integrable function is said to be of vanishing mean oscillation (VMO) if its mean oscillation over cubes in R^d converges to zero with the volume of the cubes. We establish necessary and sufficient conditions for a locally integrable function defined on a bounded measurable set of positive measure to be the restriction to that set of a VMO function.

We consider the similar extension problem pertaining to BMO(ρ) functions; that is, those VMO functions whose mean oscillation over any cube is O(ρ(l(Q))) where l(Q) is the length of Q and ρ is a positive, non-decreasing function with ρ(0⁺) = 0.

We apply these results to obtain sufficient conditions for a Blaschke sequence to be the zeros of an analytic BMO(ρ) function on the unit disc.

Vortex generators near shock/ boundary layer interactions

Experiments have been performed in a blowdown supersonic wind tunnel to investigate the effect of arrays of sub-boundary layer vortex generators placed upstream of a normal shock/ boundary layer interaction. The investigation makes use of a recovery shock wave and the naturally grown turbulent boundary layer on the wind tunnel floor. Experiments were performed at Mach numbers of 1.5 and 1.3 and a freestream Reynolds number of 28 × 106. Two types of vortex generators were investigated - wedge-shaped and arrays of counter-rotating vanes. It was found that at Mach 1.5 the vane-type VGs eliminated and the wedge-type VGs greatly reduced the separation bubble under the shock. When placed in the supersonic part of the flow both VGs caused a wave pattern consisting of a shock, re-expansion and shock. The re-expansion and double shocks are undesirable features since they equate to increased total pressure losses and hence increased -wave drag. Furthermore there are indications that the vortex intensity is reduced by the normal shock/ boundary layer interaction. When the shock was located directly over the VGs there was no re-expansion present, but the 'damping' effect of the shock on the vortex persisted. It appears that the vortices produced by the wedge-shaped VGs lift off the surface more rapidly. Similar results were observed at Mach 1.3, where the flow was unseparated.

Active control of normal shock wave/turbulent boundary layer interaction using "Smart" piezoelectric flap actuators

This paper looks at active control of the normal shock wave/turbulent boundary layer interaction (SBLI) using smart flap actuators. The actuators are manufactured by bonding piezoelectric material to an inert substrate to control the bleed/suction rate through a plenum chamber. The cavity provides communication of signals across the shock, allowing rapid thickening of the boundary layer approaching the shock, which splits into a series of weaker shocks forming a lambda shock foot, reducing wave drag. Active control allows optimum control of the interaction, as it would be capable of positioning the control region around the original shock position and control the rate of mass transfer. © 2004 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.

Optical constants of cubic GaN/GaAs(001): Experiment and modeling

The optical constants epsilon(E)=epsilon(1)(E)+iepsilon(2)(E) of unintentionally doped cubic GaN grown on GaAs(001) have been measured at 300 K using spectral ellipsometry in the range of 1.5-5.0 eV. The epsilon(E) spectra display a structure, associated with the critical point at E-0 (direct gap) and some contribution mainly coming from the E-1 critical point. The experimental data over the entire measured spectral range (after oxide removal) has been fit using the Holden-Munoz model dielectric function [M. Munoz et al., J. Appl. Phys. 92, 5878 (2002)]. This model is based on the electronic energy-band structure near critical points plus excitonic and band-to-band Coulomb-enhancement effects at E-0, E-0 + Delta(0) and the E-1, E-1 + Delta(1), doublet. In addition to evaluating the energy of the E-0 critical point, the binding energy (R-1) of the two-dimensional exciton related to the E-1 critical point was estimated using the effective mass/k.p theory. The line, shape of the imaginary part of the cubic-GaN dielectric function shows excitonic effects at room temperature not withstanding that the exciton was not resolved. (C) 2003 American Institute of Physics.

CO2Y the intelligent green solution: minimising carbon emissions by maximising shared travel opportunity.

It is in the interests of everybody that the environment is protected. In view of the recent leaps in environmental awareness it would seem timely and sensible, therefore, for people to pool vehicle resources to minimise the damaging impact of emissions. However, this is often contrary to how complex social systems behave – local decisions made by self-interested individuals often have emergent effects that are in the interests of nobody. For software engineers a major challenge is to help facilitate individual decision-making such that individual preferences can be met, which, when accumulated, minimise adverse effects at the level of the transport system. We introduce this general problem through a concrete example based on vehicle-sharing. Firstly, we outline the kind of complex transportation problem that is directly addressed by our technology (CO2y™ - pronounced “cosy”), and also show how this differs from other more basic software solutions. The CO2y™ architecture is then briefly introduced. We outline the practical advantages of the advanced, intelligent software technology that is designed to satisfy a number of individual preference criteria and thereby find appropriate matches within a population of vehicle-share users. An example scenario of use is put forward, i.e., minimisation of grey-fleets within a medium-sized company. Here we comment on some of the underlying assumptions of the scenario, and how in a detailed real-world situation such assumptions might differ between different companies, and individual users. Finally, we summarise the paper, and conclude by outlining how the problem of pooled transportation is likely to benefit from the further application of emergent, nature-inspired computing technologies. These technologies allow systems-level behaviour to be optimised with explicit representation of individual actors. With these techniques we hope to make real progress in facing the complexity challenges that transportation problems produce.

John Wesley, the man and his mission

http://www.archive.org/details/johnwesleytheman00pikeuoft