Following the creation of active gold nanocatalysts from phosphine-stabilized molecular clusters

The phosphine-stabilised gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in-situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic re-arrangements in the topology of the cluster core.

Comparing the fit between BREEAM assessment and design processes

This paper explores the mapping of the environmental assessment process onto design and construction processes. A comparative case study method is used to identify and account for variations in the ‘fit’ between these two processes. The analysis compares eight BREEAM projects (although relevant to LEED, GreenStar, etc.) and distinguishes project-level characteristics and dynamics. Drawing on insights from literature on sustainable construction and assessment methods, an analytic framework is developed to examine the effect of clusters of project and assessment level elements on different types of fit (tight, punctual and bolt-on). Key elements distinguishing between types include: prior working experience with project team members, individual commitment to sustainable construction, experience with sustainable construction, project continuity, project-level ownership of the assessment process, and the nature and continuity of assessor involvement. Professionals with ‘sustainable’ experience used BREEAM judiciously to support their designs (along with other frameworks), but less committed professionals tended to treat it purely as an assessment method. More attention needs to be paid to individual levels of engagement with, and understanding of, sustainability in general (rather than knowledge of technical solutions to individual credits), to ownership of the assessment process and to the potential effect of discontinuities at the project level on sustainable design.

Individual assets, market structure and the drivers of return

Much UK research and market practice on portfolio strategy and performance benchmarking relies on a sector‐geography subdivision of properties. Prior tests of the appropriateness of such divisions have generally relied on aggregated or hypothetical return data. However, the results found in aggregate may not hold when individual buildings are considered. This paper makes use of a dataset of individual UK property returns. A series of multivariate exploratory statistical techniques are utilised to test whether the return behaviour of individual properties conforms to their a priori grouping. The results suggest strongly that neither standard sector nor regional classifications provide a clear demarcation of individual building performance. This has important implications for both portfolio strategy and performance measurement and benchmarking. However, there do appear to be size and yield effects that help explain return behaviour at the property level.

How do multilateral institutions influence individual perceptions of international affairs? Evidence from Europe and Asia

To date there has been no systematic study of the relationship between individuals’ opinions of different institutions and their perceptions of world affairs. This article tries to fill this gap by using a large cross-country data set comprising nine EU members and seven Asian nations and instrumental variable bivariate probit regression analysis. Controlling for a host of factors, the article shows that individuals’ confidence in multilateral institutions affects their perceptions of whether or not their country is being treated fairly in international affairs. This finding expands upon both theoretical work on multilateral institutions that has focused on state actors’ rationale for engaging in multilateral cooperation and empirical work that has treated confidence in multilateral institutions as a dependent variable. The article also shows that individuals’ confidence in different international organizations has undifferentiated effects on their perceptions of whether or not their country is being treated fairly in international affairs, though individuals more knowledgeable about international affairs exhibit slightly different attitudes. Finally, the article demonstrates significant differences in opinion across Europe and Asia.

A method to assess individual research outputs

We present here a straightforward method which can be used to obtain a quantitative indication of an individual research output for an academic. Different versions, selections and options are presented to enable a user to easily calculate values both for stand-alone papers and overall for the collection of outputs for a person. The procedure is particularly useful as a metric to give a quantitative indication of the research output of a person over a time window. Examples are included to show how the method works in practice and how it compares to alternative techniques.

Using an individual-based model to select among alternative foraging strategies of woodpigeons: data support a memory-based model with a flocking mechanism

Population modelling is increasingly recognised as a useful tool for pesticide risk assessment. For vertebrates that may ingest pesticides with their food, such as woodpigeon (Columba palumbus), population models that simulate foraging behaviour explicitly can help predicting both exposure and population-level impact. Optimal foraging theory is often assumed to explain the individual-level decisions driving distributions of individuals in the field, but it may not adequately predict spatial and temporal characteristics of woodpigeon foraging because of the woodpigeons’ excellent memory, ability to fly long distances, and distinctive flocking behaviour. Here we present an individual-based model (IBM) of the woodpigeon. We used the model to predict distributions of foraging woodpigeons that use one of six alternative foraging strategies: optimal foraging, memory-based foraging and random foraging, each with or without flocking mechanisms. We used pattern-oriented modelling to determine which of the foraging strategies is best able to reproduce observed data patterns. Data used for model evaluation were gathered during a long-term woodpigeon study conducted between 1961 and 2004 and a radiotracking study conducted in 2003 and 2004, both in the UK, and are summarised here as three complex patterns: the distributions of foraging birds between vegetation types during the year, the number of fields visited daily by individuals, and the proportion of fields revisited by them on subsequent days. The model with a memory-based foraging strategy and a flocking mechanism was the only one to reproduce these three data patterns, and the optimal foraging model produced poor matches to all of them. The random foraging strategy reproduced two of the three patterns but was not able to guarantee population persistence. We conclude that with the memory-based foraging strategy including a flocking mechanism our model is realistic enough to estimate the potential exposure of woodpigeons to pesticides. We discuss how exposure can be linked to our model, and how the model could be used for risk assessment of pesticides, for example predicting exposure and effects in heterogeneous landscapes planted seasonally with a variety of crops, while accounting for differences in land use between landscapes.

Incorporating toxicokinetics into an individual-based model for more realistic pesticide exposure estimates: A case study of the wood mouse

The potential risk of agricultural pesticides to mammals typically depends on internal concentrations within individuals, and these are determined by the amount ingested and by absorption, distribution, metabolism, and excretion (ADME). Pesticide residues ingested depend, amongst other things, on individual spatial choices which determine how much and when feeding sites and areas of pesticide application overlap, and can be calculated using individual-based models (IBMs). Internal concentrations can be calculated using toxicokinetic (TK) models, which are quantitative representations of ADME processes. Here we provide a population model for the wood mouse (Apodemus sylvaticus) in which TK submodels were incorporated into an IBM representation of individuals making choices about where to feed. This allows us to estimate the contribution of individual spatial choice and TK processes to risk. We compared the risk predicted by four IBMs: (i) “AllExposed-NonTK”: assuming no spatial choice so all mice have 100% exposure, no TK, (ii) “AllExposed-TK”: identical to (i) except that the TK processes are included where individuals vary because they have different temporal patterns of ingestion in the IBM, (iii) “Spatial-NonTK”: individual spatial choice, no TK, and (iv) “Spatial-TK”: individual spatial choice and with TK. The TK parameters for hypothetical pesticides used in this study were selected such that a conventional risk assessment would fail. Exposures were standardised using risk quotients (RQ; exposure divided by LD50 or LC50). We found that for the exposed sub-population including either spatial choice or TK reduced the RQ by 37–85%, and for the total population the reduction was 37–94%. However spatial choice and TK together had little further effect in reducing RQ. The reasons for this are that when the proportion of time spent in treated crop (PT) approaches 1, TK processes dominate and spatial choice has very little effect, and conversely if PT is small spatial choice dominates and TK makes little contribution to exposure reduction. The latter situation means that a short time spent in the pesticide-treated field mimics exposure from a small gavage dose, but TK only makes a substantial difference when the dose was consumed over a longer period. We concluded that a combined TK-IBM is most likely to bring added value to the risk assessment process when the temporal pattern of feeding, time spent in exposed area and TK parameters are at an intermediate level; for instance wood mice in foliar spray scenarios spending more time in crop fields because of better plant cover.

Neuroanatomy of individual differences in language in adult males with autism

One potential source of heterogeneity within autism spectrum conditions (ASC) is language development and ability. In 80 high-functioning male adults with ASC, we tested if variations in developmental and current structural language are associated with current neuroanatomy. Groups with and without language delay differed behaviorally in early social reciprocity, current language, but not current autistic features. Language delay was associated with larger total gray matter (GM) volume, smaller relative volume at bilateral insula, ventral basal ganglia, and right superior, middle, and polar temporal structures, and larger relative volume at pons and medulla oblongata in adulthood. Despite this heterogeneity, those with and without language delay showed significant commonality in morphometric features when contrasted with matched neurotypical individuals (n = 57). In ASC, better current language was associated with increased GM volume in bilateral temporal pole, superior temporal regions, dorsolateral fronto-parietal and cerebellar structures, and increased white matter volume in distributed frontal and insular regions. Furthermore, current language–neuroanatomy correlation patterns were similar across subgroups with or without language delay. High-functioning adult males with ASC show neuroanatomical variations associated with both developmental and current language characteristics. This underscores the importance of including both developmental and current language as specifiers for ASC, to help clarify heterogeneity.

Pit clusters and the temporality of occupation: an earlier Neolithic site at Kilverstone, Thetford, Norfolk

This paper discusses 226 earlier Neolithic pits found at Kilverstone in Norfolk. In particular, it focuses on the dynamics involved in the site's creation, investigating what had happened to the material found in the pits prior to deposition, and exploring the material connections (refitting sherds and flints) across the site. As a result of these material insights, it proved possible to shed important light on the character of that place in particular, and on the temporality of Neolithic deposition and occupation in general.

Phosphorescence quantum yield enhanced by intermolecular hydrogen bonds in Cu4I4 clusters in the solid state

Organo-copper(I) halide complexes with a Cu4I4 cubane core and cyclic amines as ligands have been synthesized and their crystal structures have been defined. Their solid state photophysical properties have been measured and correlated with the crystal structure and packing. A unique and remarkably high luminescence quantum yield (76%) has been measured for one of the complexes having the cubane clusters arranged in a columnar structure and held together by N–HI hydrogen bonds. This high luminescence quantum yield is correlated with a slow radiationless deactivation rate of the excited state and suggests a rather strong enhancement of the cubane core rigidity bestowed by the hydrogen bond pattern. Some preliminary thin film deposition experiments show that these compounds could be considered to be good candidates for applications in electroluminescent devices because of their bright luminescence, low cost and relatively easy synthesis processes

A novel combined biomarker including plasma carotenoids, vitamin C, and ferric reducing antioxidant power is more strongly associated with fruit and vegetable intake than the individual components

BACKGROUND: Monitoring of fruit and vegetable (F&V) intake is fraught with difficulties. Available dietary assessment methods are associated with considerable error, and the use of biomarkers offers an attractive alternative. Few studies to date have examined the use of plasma biomarkers to monitor or predict the F&V intake of volunteers consuming a wide range of intakes from both habitual F&V and manipulated diets. OBJECTIVE: This study tested the hypothesis that an integrated biomarker calculated from a combination of plasma vitamin C, cholesterol-adjusted carotenoid concentration and Ferric Reducing Antioxidant Power (FRAP) had more power to predict F&V intake than each individual biomarker. METHODS: Data from a randomized controlled dietary intervention study [FLAVURS (Flavonoids University of Reading Study); n = 154] in which the test groups observed sequential increases of 2.3, 3.2, and 4.2 portions of F&Vs every 6 wk across an 18-wk period were used in this study. RESULTS: An integrated plasma biomarker was devised that included plasma vitamin C, total cholesterol-adjusted carotenoids, and FRAP values, which better correlated with F&V intake (r = 0.47, P < 0.001) than the individual biomarkers (r = 0.33, P < 0.01; r = 0.37, P < 0.001; and r = 0.14, respectively; P = 0.099). Inclusion of urinary potassium concentration did not significantly improve the correlation. The integrated plasma biomarker predicted F&V intake more accurately than did plasma total cholesterol-adjusted carotenoid concentration, with the difference being significant at visit 2 (P < 0.001) and with a tendency to be significant at visit 1 (P = 0.07). CONCLUSION: Either plasma total cholesterol-adjusted carotenoid concentration or the integrated biomarker could be used to distinguish between high- and moderate-F&V consumers. This trial was registered at www.controlled-trials.com as ISRCTN47748735.

Long term individual load forecast under different electrical vehicles uptake scenarios

More and more households are purchasing electric vehicles (EVs), and this will continue as we move towards a low carbon future. There are various projections as to the rate of EV uptake, but all predict an increase over the next ten years. Charging these EVs will produce one of the biggest loads on the low voltage network. To manage the network, we must not only take into account the number of EVs taken up, but where on the network they are charging, and at what time. To simulate the impact on the network from high, medium and low EV uptake (as outlined by the UK government), we present an agent-based model. We initialise the model to assign an EV to a household based on either random distribution or social influences - that is, a neighbour of an EV owner is more likely to also purchase an EV. Additionally, we examine the effect of peak behaviour on the network when charging is at day-time, night-time, or a mix of both. The model is implemented on a neighbourhood in south-east England using smart meter data (half hourly electricity readings) and real life charging patterns from an EV trial. Our results indicate that social influence can increase the peak demand on a local level (street or feeder), meaning that medium EV uptake can create higher peak demand than currently expected.

Corruption and individual ethics: insights from a public procurement auction

This article proposes an auction model where two firms compete for obtaining the license for a public project and an auctioneer acting as a public official representing the political power, decides the winner of the contest. Players as firms face a social dilemma in the sense that the higher is the bribe offered, the higher would be the willingness of a pure monetary maximizer public official to give her the license. However, it implies inducing a cost of reducing all players’ payoffs as far as our model includes an endogenous externality, which depends on bribe. All players’ payoffs decrease with the bribe (and increase with higher quality). We find that the presence of bribe aversion in either the officials’ or the firms’ utility function shifts equilibrium towards more pro-social behavior. When the quality and bribe-bid strategy space is discrete, multiple equilibria emerge including more pro-social bids than would be predicted under a continuous strategy space.

Hybrid materials through linkage of chalcogenide tetrahedral clusters

Tetrahedral chalcogenide clusters, with their well-defined molecular structures and interesting properties, are attractive building blocks for hybrid materials, in which porosity may be integrated with electronic or optical properties. Linkage of tetrahedral clusters often occurs through bridging chalcogenolate ligands, and results in extended structures of inorganic connectivity. However, linkage of tetrahedral clusters via organic ligands is also possible and a number of coordination polymers have already been reported. Recent advances on the synthesis and crystal structures of extended hybrid structures based on tetrahedral clusters are described here.