Kinetic and structure–activity studies of the triazolium ion-catalysed benzoin condensation

Steady-state kinetic and structure–activity studies of a series of six triazolium-ion pre-catalysts 2a–2f were investigated for the benzoin condensation. These data provide quantitative insight into the role of triazolium N-aryl substitution under synthetically relevant catalytic conditions in a polar solvent environment. Kinetic behaviour was significantly different to that previously reported for a related thiazolium-ion pre-catalyst 1, with the observed levelling of initial rate constants to νmax at high aldehyde concentrations for all triazolium catalysts. Values for νmax for 2a–2f increase with electron withdrawing N-aryl substituents, in agreement with reported optimal synthetic outcomes under catalytic conditions, and vary by 75-fold across the series. The levelling of rate constants supports a change in rate-limiting step and evidence supports the assignment of the Breslow-intermediate forming step to the plateau region. Correlation of νmax reaction data yielded a positive Hammett ρ-value (ρ = +1.66) supporting the build up of electron density adjacent to the triazolium N-Ar in the rate-limiting step favoured by electron withdrawing N-aryl substituents. At lower concentrations of aldehyde, both Breslow-intermediate and benzoin formation are partially rate-limiting

Scale in education research: towards a multi-scale methodology

This article explores some theoretical and methodological problems concerned with scale in education research through a critique of a recent mixed-method project. The project was framed by scale metaphors drawn from the physical and earth sciences and I consider how recent thinking around scale, for example in ecosystems and human geography might offer helpful points and angles of view on the challenges of thinking spatially in education research. Working between the spatial metaphors of ecology scholars and the critiques of the human geographers, for example the hypercomplex social space in Lefebvre’s political-economic thinking and the fluid, simultaneous, multiple spatialities of Massey’s post-structuralism, I problematize space and scale in education research. Interweaving these geographical ideas with Giddens’ structuration and Bourdieu’s theory of practice, both of which employed what might be termed scale-bridging to challenge social science’s entrenched paradigms, leads me to reconsider what is possible and desirable in the study of education systems. Following the spatial turn in the social sciences generally, there is an outstanding need to theorise multi-scale methodology for education research

The Association of Coloproctology of Great Britain and Ireland consensus guidelines in emergency colorectal surgery

ACKNOWLEDGEMENTS Review and editing: S.R. Brown, Professor of Surgery, Sheffield Teaching Hospitals NHS Foundation Trust, Sheffield, UK. Email [email protected]. Patient summary: R.G. Arnott, Retired Professor, Patient Liaison Group, Association of Coloproctology of Great Britain and Ireland, Royal College of Surgeons of England, London, UK. Email [email protected]. Delphi review: C.P. Macklin. BMedSci BM BS FRCS DM, Consultant Colorectal Surgeon, Mid Yorkshire Hospitals, UK. Email [email protected] reviewedPublisher PD

Dialectics and difference: against Harvey's dialectical post-Marxism

David Harvey`s recent book, Justice, nature and the geography of difference (JNGD), engages with a central philosophical debate that continues to dominate human geography: the tension between the radical Marxist project of recent decades and the apparently disempowering relativism and `play of difference' of postmodern thought. In this book, Harvey continues to argue for a revised `post-Marxist' approach in human geography which remains based on Hegelian-Marxian principles of dialectical thought. This article develops a critique of that stance, drawing on the work of Jacques Derrida, Gilles Deleuze and Felix Guattari. I argue that dialectical thinking, as well as Harvey's version of `post-Marxism', has been undermined by the wide-ranging `post-' critique. I suggest that Harvey has failed to appreciate the full force of this critique and the implications it has for `post-Marxist' ontology and epistemology. I argue that `post-Marxism', along with much contemporary human geography, is constrained by an inflexible ontology which excessively prioritizes space in the theory produced, and which implements inflexible concepts. Instead, using the insights of several `post-' writers, I contend there is a need to develop an ontology of `context' leading to the production of `contextual theories'. Such theories utilize flexible concepts in a multilayered understanding of ontology and epistemology. I compare how an approach which produces a `contextual theory' might lead to more politically empowering theory than `post-Marxism' with reference to one of Harvey's case studies in JNGD

Into the divide: community identities and the visualisation of place

This article discusses the experience of place in a profoundly divided urban area of Sheffield. At a time when the gap between affluence and poverty has reached its widest point since the 1960s, this paper explores the relationship between individuals and their sense of place and of the trenchant divisions separating communities. The study employs various methods but centres upon the use of hand drawn maps; creating a dialogue between the interviewers and a number of local residents. These maps and the accompanying commentaries demonstrate the diverse individual sense of a particular place and a dialectical sense of space. The resulting picture is one of both the persistence of historical divisions, suggesting regulation and control through planning and policing, but also of complex entanglements of social identities, habitus and place which defy easy categorisiation

The behaviour of dark matter associated with four bright cluster galaxies in the 10kpc core of Abell 3827

Galaxy cluster Abell 3827 hosts the stellar remnants of four almost equally bright elliptical galaxies within a core of radius 10kpc. Such corrugation of the stellar distribution is very rare, and suggests recent formation by several simultaneous mergers. We map the distribution of associated dark matter, using new Hubble Space Telescope imaging andVery Large Telescope/Multi-Unit Spectroscopic Explorer integral field spectroscopy of a gravitationally lensed system threaded through the cluster core. We find that each of the central galaxies retains a dark matter halo, but that (at least) one of these is spatially offset from its stars. The best-constrained offset is $1.62^{+0.47}_{-0.49}$kpc, where the 68 per cent confidence limit includes both statistical error and systematic biases in mass modelling. Such offsets are not seen in field galaxies, but are predicted during the long infall to a cluster, if dark matter self-interactions generate an extra drag force. With such a small physical separation, it is difficult to definitively rule out astrophysical effects operating exclusively in dense cluster core environments - but if interpreted solely as evidence for self-interacting dark matter, this offset implies a cross-section σDM/m∼(1.7±0.7)×10−4cm2g−1×(tinfall/109 yr)−2, where tinfall is the infall duratio

Climate change adaptation and cross-sectoral policy coherence in southern Africa

To be effective, climate change adaptation needs to be mainstreamed across multiple sectors and greater policy coherence is essential. Using the cases of Malawi, Tanzania and Zambia, this paper investigates the extent of coherence in national policies across the water and agriculture sectors and to climate change adaptation goals outlined in national development plans. A two-pronged qualitative approach is applied using Qualitative Document Analysis of relevant policies and plans, combined with expert interviews from non-government actors in each country. Findings show that sector policies have differing degrees of coherence on climate change adaptation, currently being strongest in Zambia and weakest in Tanzania. We also identify that sectoral policies remain more coherent in addressing immediate-term disaster management issues of floods and droughts rather than longer-term strategies for climate adaptation. Coherence between sector and climate policies and strategies is strongest when the latter has been more recently developed. However to date, this has largely been achieved by repackaging of existing sectoral policy statements into climate policies drafted by external consultants to meet international reporting needs and not by the establishment of new connections between national sectoral planning processes. For more effective mainstreaming of climate change adaptation, governments need to actively embrace longer-term cross-sectoral planning through cross-Ministerial structures, such as initiated through Zambia’s Interim Climate Change Secretariat, to foster greater policy coherence and integrated adaptation planning