Concerted and stepwise proton-coupled electron transfers in aquo/hydroxo complex couples in water: oxidative electrochemistry of [Os(II)(bpy)(2)(py)(OH(2))](2+)

Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.     

Towards improving the utilization of university teaching space

There is a perception that teaching space in universities is a rather scarce resource. However, some studies have revealed that in many institutions it is actually chronically under-used. Often, rooms are occupied only half the time, and even when in use they are often only half full. This is usually measured by the ‘utilization’ which is defined as the percentage of available ‘seat-hours’ that are employed. Within real institutions, studies have shown that this utilization can often take values as low as 20–40%. One consequence of such a low level of utilization is that space managers are under pressure to make more efficient use of the available teaching space. However, better management is hampered because there does not appear to be a good understanding within space management (near-term planning) of why this happens. This is accompanied, within space planning (long-term planning) by a lack of experise on how best to accommodate the expected low utilizations. This motivates our two main goals: (i) To understand the factors that drive down utilizations, (ii) To set up methods to provide better space planning. Here, we provide quantitative evidence that constraints arising from timetabling and location requirements easily have the potential to explain the low utilizations seen in reality. Furthermore, on considering the decision question ‘Can this given set of courses all be allocated in the available teaching space?’ we find that the answer depends on the associated utilization in a way that exhibits threshold behaviour: There is a sharp division between regions in which the answer is ‘almost always yes’ and those of ‘almost always no’. Through analysis and understanding of the space of potential solutions, our work suggests that better use of space within universities will come about through an understanding of the effects of timetabling constraints and when it is statistically likely that it will be possible for a set of courses to be allocated to a particular space. The results presented here provide a firm foundation for university managers to take decisions on how space should be managed and planned for more effectively. Our multi-criteria approach and new methodology together provide new insight into the interaction between the course timetabling problem and the crucial issue of space planning.     

Status of electroweak phase transition and baryogenesis

I review recent progress on the electroweak phase transition and baryogenesis, focusing on the minimal supersymmetric Standard Model as the source of new physics.     

A new model for automated examination timetabling

Automated examination timetabling has been addressed by a wide variety of methodologies and techniques over the last ten years or so. Many of the methods in this broad range of approaches have been evaluated on a collection of benchmark instances provided at the University of Toronto in 1996. Whilst the existence of these datasets has provided an invaluable resource for research into examination timetabling, the instances have significant limitations in terms of their relevance to real-world examination timetabling in modern universities. This paper presents a detailed model which draws upon experiences of implementing examination timetabling systems in universities in Europe, Australasia and America.