Synthesis and characterisation of BODIPY radical anions

The redox processes associated with BODIPY analogues are studied by electrochemical and spectroscopic methods revealing a characteristic profile for the persistent BODIPY radical and quenching of fluorescence upon reduction.     

Rediscovering cobalt's surface chemistry

Cobalt is an active metal for a variety of commercially and environmentally significant heterogeneously catalysed processes. Despite its importance, Co's surface chemistry is less studied compared to other key industrial catalyst metals. This stems in part from the difficulties associated with single crystal preparation and stability. Recent advances in scanning probe microscopy have enabled the atomic scale study of the structural, electronic, and magnetic properties of well-defined Co nanoparticles on metal substrates. Such systems offer an excellent platform to investigate the adsorption, diffusion, dissociation, and reaction of catalytically relevant molecules. Here we discuss the current understanding of metal-supported Co nanoparticles, review the limited literature on molecular adsorption, and suggest ways that they can be used to explore Co's rich surface chemistry. Our discussion is accompanied by new high resolution scanning tunnelling microscopy data from our group, which illustrate some of the interesting properties of these complex systems.     

Photooxygenation of a microbial arene oxidation product and regioselective Kornblum-DeLaMare rearrangement: total synthesis of zeylenols and zeylenones

We report the enantioselective total syntheses of zeylenol (+)-1, as well as its congeners (-)-7 and 16, and of 3-O-debenzoylzeylenone 28. To this end, a new variant of the Kornblum-DeLaMare rearrangement, which utilises neighbouring-group participation to impart regioselectivity, has been developed. The approach employs photooxygenation of building blocks derived from a microbial arene oxidation product.     

Computer Simulation Studies of Anisotropic Systems,III. Two-Dimensional Nematic Liquid Crystals

We have studied a two-dimensional ensemble of cylindrically symmetric particles interacting via a weak anisotropic potential using the Monte Carlo technique of computer simulation. The calculation is simplified by confining the particles to the sites of a triangular lattice. The internal energy, specific heat, second rank orientational order parameter and second rank orientational pair correlation function were calculated at various temperatures. The variation of the order parameter and pair correlation function shows that the system exhibits a transition from an orientationally disordered to a partially ordered phase. The temperature dependence of the specific heat suggests that the transition is second order or higher.

The possibility of the existence of order-disorder transitions in two dimensions is discussed. The results of the simulation are then compared with the predictions of a molecular field theory of orientational phase transitions. As expected the theory is found to be in poor agreement with the calculations.     

Fiber optic data busses for aircraft

Abstract

A variety of fiber optic data busses is being developed for aircraft applications. This article addresses five different data busses under consideration for both military and commercial aircraft. The impact of data bus protocol on component design, the effect of data bus topology on power budget and installation issues, and overall data bus performance are discussed.     

Accurate depolarization ratio measurements for all diatomic hydrogen isotopologues

The Raman depolarization ratios for individual Q₁(J”) branch lines of all diatomic hydrogen isotopologues – H₂, HD, D₂, HT, DT, and T₂ – were measured, for all rotational levels with population larger than 1/100 relative to the Boltzmann maximum at room temperature. For these measurements, the experimental setup normally used for the monitoring of the tritiated hydrogen molecules at KArlsruhe TRItium Neutrino experiment was adapted to optimally control the excitation laser power and polarization, and to precisely define the Raman light collection geometry. The measured Raman depolarization values were compared to theoretical values, which are linked to polarizability tensor quantities. For this, the ‘raw data’ were corrected taking into account distinct aspects affecting Raman depolarization data, including (1) excitation polarization impurities; (2) extended Raman excitation volumes; and (3) Raman light collection over finite solid angles. Our corrected depolarization ratios of the hydrogen isotopologues agree with the theoretical values (based on ab initio quantum calculations by R.J. LeRoy, University of Waterloo, Canada) to better than 5% for nearly all of the measured Q₁(J”) lines, with 1σ confidence level. The results demonstrate that reliable, accurate Raman depolarization ratios can be extracted from experimental measurements, which may be substantially distorted by excitation polarization impurities and by geometrical effects. Copyright © 2013 John Wiley & Sons, Ltd.     

Evaluation method for Raman depolarization measurements including geometrical effects and polarization aberrations

In this article, we address the notoriously difficult problem to quantitatively link measured Raman depolarization values to theoretical polarizability tensor quantities, since quantum calculations do not incorporate experimental parameters. For this, we introduce a numerical model to calculate, for realistic experimental configurations, effective Raman line strength functions, Φ, which find their way into depolarization ratios, ρ. The model is based on interlinked integrations over the angles in the light collection path and a finite Raman source volume along the excitation laser beam. The model deals also with the conditional aperture parameters, associated with more than one optical component in the light collection path. Finally, we also can take into account polarization aberrations introduced by the sample cell windows. The procedure was fully tested for Raman depolarization spectra of selected hydrogen isotopologues. Distinct aspects affecting Raman depolarization data were validated, namely: (1) excitation polarization impurities; (2) extended Raman excitation volumes; (3) Raman light collection over finite solid angles; and (4) polarization aberrations introduced by optics in the light collection path. The correction of the experimental measurement data for the aforementioned effects resulted in depolarization ratios for the Q₁(J " ) Raman lines of H₂ and T₂, which mostly differed by less than 5% from those obtained by quantum‐calculations. Copyright © 2013 John Wiley & Sons, Ltd.     

Joule–Thomson Effects on the Flow of Liquid Water

We present a revised form of the energy balance for the coupled thermodynamics of liquid water flowing in porous media and give examples of situations where a commonly used formulation based on transport of enthalpy leads to erroneous results. Assuming negligible contribution from kinetic energy as well as sources and sinks such as energy from radioactive decay, total energy conservation is reduced to a balance between changes in internal energy, enthalpy, conductive heat flux, and gravitational potential energy. The Joule–Thomson coefficient is defined as the change in temperature with respect to an increase in pressure at constant enthalpy. Because liquid water has a negative Joule–Thomson coefficient at low temperatures, at a constant gravitational potential water cools as it compresses and heats as it expands. If one ignores the gravitational energy, transport of enthalpy alone leads to water heating by 2 \(^\circ \) C per kilometer as it is brought up from depth. The corrected energy balance transports methalpy, which is enthalpy plus gravitational potential energy. Although the simpler form leads to small changes in the temperature profile for typical simulations, there are several instances where this effect may prove to be important. The most important impact of the erroneous form is probably in the field of geothermal energy production, where the creation of a few degrees of heat in a simulation could lead to miscalculation of power plant efficiencies.