Bis(azidophenyl)phosphole building block for extended π-conjugated systems

Novel bis(azidophenyl)phosphole sulfide building block 8 has been developed to give access to a plethora of phosphole-containing π-conjugated systems in a simple synthetic step. This was explored for the reaction of the two azido moieties with phenyl-, pyridyl- and thienylacetylenes, to give bis(aryltriazolyl)-extended π-systems, having either the phosphole sulfide (9) or the phosphole (10) group as central ring. These conjugated frameworks exhibit intriguing photophysical and electrochemical properties that vary with the nature of the aromatic end-group. The λ3-phospholes 10 display blue fluorescence (λem = 460–469 nm) with high quan-tum yield (ΦF = 0.134–0.309). The radical anion of pyridylsubstituted phosphole sulfide 9b was observed with UV/Vis spectroscopy. TDDFT calculations on the extended π-systems showed some variation in the shape of the HOMOs, which was found to have an effect on the extent of charge transfer, depending on the aromatic end-group. Some fine-tuning of the emission maxima was observed, albeit subtle, showing a decrease in conjugation in the order thienyl � phenyl � pyridyl. These results show that variations in the distal ends of such π-systems have a subtle but significant effect on photophysical properties.

The impact of obesity-related single nucleotide polymorphisms on appetite and energy intake: a pilot study

An increasing number of studies have reported a heritable component for the regulation of energy intake and eating behaviour, although the individual polymorphisms and their ‘effect size’ are not fully elucidated. The aim of the present study was to examine the relationship between specific SNP and appetite responses and energy intake in overweight men. In a randomised cross-over trial, forty overweight men (age 32 (sd 09) years; BMI 27 (sd 2) kg/m2) attended four sessions 1 week apart and received three isoenergetic and isovolumetric servings of dairy snacks or water (control) in random order. Appetite ratings were determined using visual analogue scales and energy intake at an ad libitum lunch was assessed 90 min after the dairy snacks. Individuals were genotyped for SNP in the fat mass and obesity-associated (FTO), leptin (LEP), leptin receptor (LEPR) genes and a variant near the melanocortin-4 receptor (MC4R) locus. The postprandial fullness rating over the full experiment following intake of the different snacks was 17·2 % (P= 0·026) lower in A carriers compared with TT homozygotes for rs9939609 (FTO, dominant) and 18·6 % (P= 0·020) lower in G carriers compared with AA homozygotes for rs7799039 (LEP, dominant). These observations indicate that FTO and LEP polymorphisms are related to the variation in the feeling of fullness and may play a role in the regulation of food intake. Further studies are required to confirm these initial observations and investigate the ‘penetrance’ of these genotypes in additional population subgroups.

Predicting the risks from climate change to forage and crop production for animal feed

Climate change is expected to bring warmer temperatures, changes to rainfall patterns, and increased frequency of extreme weather. Projections of climate impacts on feed crops show that there will likely be opportunities for increased productivity as well as considerable threats to crop productivity in different parts of the world over the next 20 to 50 years. On balance, we anticipate substantial risks to the volume, volatility, and quality of animal feed supply chains from climate change. Adaptation strategies and investment informed by high quality research at the interface of crop and animal science will be needed, both to respond to climate change and to meet the increasing demand for animal products expected over the coming decades.

Implementing ‘Site BIM’: a case study of ICT innovation on a large hospital project

Numerous Building Information Modelling (BIM) tools are well established and potentially beneficial in certain uses. However, issues of adoption and implementation persist, particularly for on-site use of BIM tools in the construction phase. We describe an empirical case-study of the implementation of an innovative ‘Site BIM’ system on a major hospital construction project. The main contractor on the project developed BIM-enabled tools to allow site workers using mobile tablet personal computers to access design information and to capture work quality and progress data on-site. Accounts show that ‘Site BIM’, while judged to be successful and actively supporting users, was delivered through an exploratory and emergent development process of informal prototyping. Technical IT skills were adopted into the construction project through personal relationships and arrangements rather than formal processes. Implementation was driven by construction project employees rather than controlled centrally by the corporate IT function.

Promoting the use of BaP as a marker for PAH exposure in UK soils

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants that frequently accumulate in soils. There is therefore a requirement to determine their levels in contaminated environments for the purposes of determining impacts on human health. PAHs are a suite of individual chemicals, and there is an ongoing debate as to the most appropriate method for assessing the risk to humans from them. Two methods predominate: the surrogate marker approach and the toxic equivalency factor. The former assumes that all chemicals in a mixture have an equivalent toxicity. The toxic equivalency approach estimates the potency of individual chemicals relative to the usually most toxic Benzo(a)pyrene. The surrogate marker approach is believed to overestimate risk and the toxic equivalency factor to underestimate risk. When analysing the risks from soils, the surrogate marker approach is preferred due to its simplicity, but there are concerns because of the potential diversity of the PAH profile across the range of impacted soils. Using two independent data sets containing soils from 274 sites across a diverse range of locations, statistical analysis was undertaken to determine the differences in the composition of carcinogenic PAH between site locations, for example, rural versus industrial. Following principal components analysis, distinct population differences were not seen between site locations in spite of large differences in the total PAH burden between individual sites. Using all data, highly significant correlations were seen between BaP and other carcinogenic PAH with the majority of r2 values > 0.8. Correlations with the European Food Standards Agency (EFSA) summed groups, that is, EFSA2, EFSA4 and EFSA8 had even higher correlations (r2 > 0.95). We therefore conclude that BaP is a suitable surrogate marker to represent mixtures of PAH in soil during risk assessments.

In vitro assessment of the bioaccessibility of brominated flame retardants in indoor dust using a colon extended model of the human gastrointestinal tract

An in vitro colon extended physiologically based extraction test (CEPBET) which incorporates human gastrointestinal tract (GIT) parameters (including pH and chemistry, solid-to-fluid ratio, mixing and emptying rates) was applied for the first time to study the bioaccessibility of brominated flame retardants (BFRs) from the 3 main GIT compartments (stomach, small intestine and colon) following ingestion of indoor dust. Results revealed the bioaccessibility of γ-HBCD (72%) was less than that for α- and β-isomers (92% and 80% respectively) which may be attributed to the lower aqueous solubility of the γ-isomer (2 μg L−1) compared to the α- and β-isomers (45 and 15 μg L−1 respectively). No significant change in the enantiomeric fractions of HBCDs was observed in any of the studied samples. However, this does not completely exclude the possibility of in vivo enantioselective absorption of HBCDs, as the GIT cell lining and bacterial flora – which may act enantioselectively – are not included in the current CE-PBET model. While TBBP-A was almost completely (94%) bioaccessible, BDE-209 was the least (14%) bioaccessible of the studied BFRs. Bioaccessibility of tri-hepta BDEs ranged from 32–58%. No decrease in the bioaccessibility with increasing level of bromination was observed in the studied PBDEs.

The credit relationship between Henry III and merchants of Douai and Ypres, 1247-70

This article looks at an important but neglected aspect of medieval sovereign debt, namely ‘accounts payable’ owed by the Crown to merchants and employees. It focuses on the unusually well-documented relationship between Henry III, King of England between 1216 and 1272, and Flemish merchants from the towns of Douai and Ypres, who provided cloth on credit to the royal wardrobe. From the surviving royal documents, we reconstruct the credit advanced to the royal wardrobe by the merchants of Ypres and Douai for each year between 1247 and 1270, together with the king's repayment history. The interactions between the king and the merchants are then analysed. The insights from this analysis are applied to the historical data to explain the trading decisions made by the merchants during this period, as well as why the strategies of the Yprois sometimes differed from those of the Douaissiens.

A comparison of the anticancer properties of isoxanthohumol and 8-prenylnaringenin using in vitro models of colon cancer

The hops plant (Humulus lupulus L.) is an essential ingredient in beer and contains a number of potentially bioactive prenylflavonoids, the predominant being the weakly estrogenic isoxanthohumol (Ix), which can be converted to the more strongly estrogenic 8-PN by the colonic microbiota. The aim of this study was to investigate the biological activity of 8-PN and Ix using in vitro models representing key stages of colorectal carcinogenesis, namely cell growth and viability (MTT assay), cell-cycle progression (DNA content assay), DNA damage (Comet assay), and invasion (Matrigel assay). A significant decrease in Caco-2 cell viability was noted after both 8-PN and Ix treatments at the higher doses (40 and 50 μM, respectively) although the impact on cell cycle differed between the two compounds. The decreased cell viability observed after Ix treatment was associated with a concentration-dependent increase in G2/M and an increased sub-G1 cell-cycle fraction, whereas treatment with 8-PN was associated with an elevated G0/G1 and an increased sub-G1 cell-cycle fraction. Significant antigenotoxic activity was noted at all 8-PN concentrations tested (5-40 μM). Although significant antigenotoxic activity was also noted with Ix treatment at ≤25 μM, at a higher dose, Ix itself exerted genotoxic activity. In a dose-dependent manner, both compounds inhibited HT115 cell invasion with reductions up to 52 and 46% for Ix and 8-PN, respectively, in comparison to untreated cells. This study demonstrated that both Ix and its gut microbial metabolite 8-PN exert anticancer effects on models of key stages of colon tumourigenesis.

Radical Conservatism

In 1938, Yugoslav sculptor Oscar Nemon arrived in Britain, having fled the Nazi invasion of Brussels, where he was living with Magritte. He was part of the European avant-garde that came to the UK as a refugee. Shortly thereafter, Nemon proposed a bold architectural plan to construct a temple of universal ethics in London and was in correspondence over this with central figures in Britain. After the war, he became know for his portrayal of figures like Churchil, culminating in a bust of Margaret Thatcher that is currently at the Tory HQ. Shown at Castlefield Gallery in 2013-2014, Radical Conservatism was an exhibition that explored the space between these two moments and asked whether these two terms are really antithetical. In the British context in particular, where the European avant-garde never really took hold, a kind of reactionary modernism has always defined a culture wary of revolution. But today more than ever, with the left increasingly holding on to the past of the welfare state as an ideal, and the right quietly revolutionising our world through neoliberal reforms, the paradigms of radicalism and conservatism need to be redefined. Can conservatism be seen as a radical position in itself? If art is defined by a movement towards the new - could 'holding on to the past' stubbornly be seen as a critical position, now that neo-liberalism has forced a far more radical shift in politics than the left has managed in a long time? Curated by Pil and Galia Kollectiv, featuring work by Chris Evans, IRWIN, Pil and Galia Kollectiv, Joseph Lewis, Patrick Moran, Oscar Nemon and Public Movement and a symposium with contributions from Professor Alun Rowlands and Robert Garnett.

The performance of football club managers: skill or luck?

This paper evaluates the extent to which the performance of English Premier League football club managers can be attributed to skill or luck when measured separately from the characteristics of the team. We first use a specification that models managerial skill as a fixed effect and we examine the relationship between the number of points earned in league matches and the club’s wage bill, transfer spending, and the extent to which they were hit by absent players through injuries, suspensions or unavailability. We next implement a bootstrapping approach to generate a simulated distribution of average points that could have taken place after the impact of the manager has been removed. The findings suggest that there are a considerable number of highly skilled managers but also several who perform below expectations. The paper proceeds to illustrate how the approach adopted could be used to determine the optimal time for a club to part company with its manager. We are able to identify in advance several managers who the analysis suggests could have been fired earlier and others whose sackings were hard to justify based on their performances.