Stereoisomerism in pentaerythritol-bridged cyclotriphosphazene tri-spiranes: spiro and ansa 1,3-propanediyldioxy disubstituted derivatives

Four isomeric products were isolated and purified from the reaction of 1,3-propanediol with the tetra-spirane cyclophosphazene-organophosphate compound (1): viz. the di-monospiro (2a), di-monoansa (2b) and two monospiro-monoansa derivatives (2c) and (2d). It is shown by 31P NMR spectroscopy on addition of a chiral solvating agent (CSA) that both the di-monospiro (2a) and di-monoansa (2b) derivatives are racemates, as expected, whereas no splitting of NMR signals occurred on addition of CSA to solutions of (2c) and (2d). It is found by X-ray crystallography that the two monospiro-monoansa spirane derivatives, (2c) and (2d), are meso diastereoisomers, which represent a new case of the stereochemistry of bis di-substituted cyclophosphazene derivatives of (1). It is also observed from the 31P NMR spectrum of the reaction mixture, supported by the yields of pure compounds, that formation of a spiro group is about 4.5 times more likely than that of an ansa moiety under the conditions of the reaction

Structural investigations of phosphorus-nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6-n)(NHBut)(n) derivatives

A series of compounds of the N3P3Cl(6-n)(NHBut)n family (where n = 0, 1, 2, 4 and 6) are presented and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBut) and N3P3Cl2(NHBut)4 have been determined at 120K and those of N3P3Cl6 and N3P3Cl4(NHBut)2 have been re-determined at 120K. These are compared with the known structure of N3P3(NHBut)6 studied at 150K. Trends in molecular parameters (phosphazene ring, P-Cl & P-N(HBut) distances, PCl2 angles and endo- and exo-cyclic phosphazene ring parameters) across the series are observed. Hydrogen-bonding motifs are identified, characterised and compared. Both the molecular and hydrogen bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBut) moiety

Virtue and austerity

Virtue ethics is often proposed as a third way in health-care ethics, that while consequentialism and deontology focus on action guidelines, virtue focuses on character; all three aim to help agents discern morally right action although virtue seems to have least to contribute to political issues, such as austerity. I claim: (1) This is a bad way to characterize virtue ethics. The 20th century renaissance of virtue ethics was first proposed as a response to the difficulty of making sense of ‘moral rightness’ outside a religious context. For Aristotle the right action is that which is practically best; that means best for the agent in order to live a flourishing life.There are no moral considerations besides this. (2) Properly characterized, virtue ethics can contribute to discussion of austerity. A criticism of virtue ethics is that fixed characteristics seem a bad idea in ever-changing environments; perhaps we should be generous in prosperity, selfish in austerity. Furthermore, empirical evidence suggests that people indeed do change with their environment. However, I argue that virtues concern fixed values not fixed behaviour; the values underlying virtue allow for different behaviour in different circumstances: in austerity, virtues still give the agent the best chance of flourishing. Two questions arise. (a) In austere environments might not injustice help an individual flourish by, say, obtaining material goods? No, because unjust acts undermine the type of society the agent needs for flourishing. (b) What good is virtue to those lacking the other means to flourish? The notion of degrees of flourishing shows that most people would benefit somewhat from virtue. However, in extreme circumstances virtue might harm rather than benefit the agent: such circumstances are to be avoided; virtue ethics thus has a political agenda to enable flourishing. This requires justice, a fortiori when in austerity

eBank UK: linking research data, scholarly communication and learning

This paper includes an overview of the changing landscape of scholarly communication and describes outcomes from the innovative eBank UK project, which seeks to build links from e-research through to e-learning. As introduction, the scholarly knowledge cycle is described and the role of digital repositories and aggregator services in linking data-sets from Grid-enabled projects to e-prints through to peer-reviewed articles as resources in portals and Learning Management Systems, are assessed. The development outcomes from the eBank UK project are presented including the distributed information architecture, requirements for common ontologies, data models, metadata schema, open linking technologies, provenance and workflows. Some emerging challenges for the future are presented in conclusion

Solution phase, solid state, and theoretical investigations on the MacMillan imidazolidinone

A combination of soln. phase NMR, X-ray crystallog. studies, and DFT calcns. provide a consistent structural conformation for iminium ions derived from the MacMillan imidazolidinone

Perspectives on environment and human health: an editorial

Human health and wellbeing are intimately linked to the state of the environment [...]This editorial work received from the European Union through the European Regional Development Fund based on COMPETE 2020 (Programa Operacional da Competitividade e Internacionalização) and projects ICT UIDB/04683/2020 and UIDP/04683/2020