Stereodivergent approach to the asymmetric synthesis of bacillariolides: A formal synthesis of ent-bacillariolide II

Asymmetric synthesis of densely functionalized bicyclic frameworks for entry into bacillariolides I/III and ent-bacillariolide II is reported. The key features are ring-closing metathesis of a pair of diastereomerically related dienes obtained through a stereodivergent route from a R-(+)-glyceraldehyde derivative, transformation of a nonstereoselective cyclopentene ester enolate alkylation process to a completely stereoselective one through alkylation of a bulky ester enolate with a bulky electrophile, and a remote silyloxymethyl group directed epoxidation.

Tin–osmium cluster formation with a monomeric tin(II) alkyl: the formation, crystal structure and reactivity of [Os3(µ-H)SnR(CO)10], a formal stannyne complex of the osmium triangle {R = C(SiMe3)2C5H4N-2}

The monomeric tin(II) species SnR2{R = C(SiMe3)2C5H4N-2} reacts with [Os3(H)2(CO)10] in hexane to give [Os3(µ-H)SnR(CO)10]1 quantitatively; 1 is the first formal stannyne complex of the triosmium nucleus, in which the picoline nitrogen is coordinated to the tin atom, and which is itself also reactive, being a potential precursor to high nuclearity SnOs clusters.

μ-Peroxo-μ-oxo-bis[bis(trimethylsilylmethyl)tin]: the first structurally characterised main-group metal η2-peroxide, a formal tin analogue of an ozonide

The title compound is the first µ-η2-peroxodimetallic species to be characterised for a main group metal, possessing a long peroxo O–O bond, and large C–Sn–C angles, and is an unexpected product from the oxidation of [SnR2][R = CH(SiMe3)2], with a structure analogous to an organic ozonide.

Citation and peer review of data: moving towards formal data publication

This paper discusses many of the issues associated with formally publishing data in academia, focusing primarily on the structures that need to be put in place for peer review and formal citation of datasets. Data publication is becoming increasingly important to the scientific community, as it will provide a mechanism for those who create data to receive academic credit for their work and will allow the conclusions arising from an analysis to be more readily verifiable, thus promoting transparency in the scientific process. Peer review of data will also provide a mechanism for ensuring the quality of datasets, and we provide suggestions on the types of activities one expects to see in the peer review of data. A simple taxonomy of data publication methodologies is presented and evaluated, and the paper concludes with a discussion of dataset granularity, transience and semantics, along with a recommended human-readable citation syntax.

Multiple-project discount rates for cost-benefit analysis in construction projects: A formal risk model for microgeneration renewable energy technologies

The traditional economic approach for appraising the costs and benefits of construction project Net Present Values involves the calculation of net returns for each investment option under different discount rates. An alternative approach consists of multiple-project discount rates based on risk modelling. The example of a portfolio of microgeneration renewable energy technology (MRET) is presented to demonstrate that risks and future available budget for re-investment can be taken into account when setting discount rates for construction project specifications in presence of uncertainty. A formal demonstration is carried out through a reversed intertemporal approach of applied general equilibrium. It is demonstrated that risk and the estimated available budget for future re-investment can be included in the simultaneous assessment of the costs and benefits of multiple projects.

Formal theory building for the avalanche game: explaining counter-intuitive behaviour of a complex system using geometrical and human behavioural/physiological effects

In 'Avalanche', an object is lowered, players staying in contact throughout. Normally the task is easily accomplished. However, with larger groups counter-intuitive behaviours appear. The paper proposes a formal theory for the underlying causal mechanisms. The aim is to not only provide an explicit, testable hypothesis for the source of the observed modes of behaviour-but also to exemplify the contribution that formal theory building can make to understanding complex social phenomena. Mapping reveals the importance of geometry to the Avalanche game; each player has a pair of balancing loops, one involved in lowering the object, the other ensuring contact. For more players, sets of balancing loops interact and these can allow dominance by reinforcing loops, causing the system to chase upwards towards an ever-increasing goal. However, a series of other effects concerning human physiology and behaviour (HPB) is posited as playing a role. The hypothesis is therefore rigorously tested using simulation. For simplicity a 'One Degree of Freedom' case is examined, allowing all of the effects to be included whilst rendering the analysis more transparent. Formulation and experimentation with the model gives insight into the behaviours. Multi-dimensional rate/level analysis indicates that there is only a narrow region in which the system is able to move downwards. Model runs reproduce the single 'desired' mode of behaviour and all three of the observed 'problematic' ones. Sensitivity analysis gives further insight into the system's modes and their causes. Behaviour is seen to arise only when the geometric effects apply (number of players greater than degrees of freedom of object) in combination with a range of HPB effects. An analogy exists between the co-operative behaviour required here and various examples: conflicting strategic objectives in organizations; Prisoners' Dilemma and integrated bargaining situations. Additionally, the game may be relatable in more direct algebraic terms to situations involving companies in which the resulting behaviours are mediated by market regulations. Finally, comment is offered on the inadequacy of some forms of theory building and the case is made for formal theory building involving the use of models, analysis and plausible explanations to create deep understanding of social phenomena.