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.

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.

Adaptation-induced collective dynamics of a single-cell protozoan

We investigate the behavior of a single-cell protozoan in a narrow tubular ring. This environment forces them to swim under a one-dimensional periodic boundary condition. Above a critical density, single-cell protozoa aggregate spontaneously without external stimulation. The high-density zone of swimming cells exhibits a characteristic collective dynamics including translation and boundary fluctuation. We analyzed the velocity distribution and turn rate of swimming cells and found that the regulation of the turing rate leads to a stable aggregation and that acceleration of velocity triggers instability of aggregation. These two opposing effects may help to explain the spontaneous dynamics of collective behavior. We also propose a stochastic model for the mechanism underlying the collective behavior of swimming cells.

Can valuation factors be prescribed? The case of collective enfranchisement and leasehold extension of flats in England and Wales

Recent concerns over the valuation process in collective leasehold enfranchisement and lease extension cases have culminated in new legislation. To underpin this, the Government (Department of Environment Transport and the Regions (DETR)) commissioned new research, which examined whether the valuation of the freehold in such cases could be simplified through the prescription of either yield or marriage value/relativity. This paper, which is based on that research, examines whether it is possible or desirable to prescribe such factors in the valuation process. Market, settlement and Local Valuation Tribunal (LVT) decisions are analysed, and the basis of 'relativity charts' used in practice is critically examined. Ultimately the imperfect nature of the market in freehold investment sales and leasehold vacant possession sales means that recommendations must rest on an analysis of LVT data. New relativity curves are developed from this data and used in conjunction with an alternative approach to valuation yields (based on other investment assets). However, the paper concludes that although the prescription of yields and relativity is possible, it is not fully defensible because of problems in determining risk premia; that the evidential basis for relativity consists of LVT decisions; and that a formula approach would tend to 'lead' the market as a whole.

From short-range barotropic modelling to extended-range global weather prediction: a 40-year perspective

At the end of the 20th century, we can look back on a spectacular development of numerical weather prediction, which has, practically uninterrupted, been going on since the middle of the century. High-resolution predictions for more than a week ahead for any part of the globe are now routinely produced and anyone with an Internet connection can access many of these forecasts for anywhere in the world. Extended predictions for several seasons ahead are also being done — the latest El Niño event in 1997/1998 is an example of such a successful prediction. The great achievement is due to a number of factors including the progress in computational technology and the establishment of global observing systems, combined with a systematic research program with an overall strategy towards building comprehensive prediction systems for climate and weather. In this article, I will discuss the different evolutionary steps in this development and the way new scientific ideas have contributed to efficiently explore the computing power and in using observations from new types of observing systems. Weather prediction is not an exact science due to unavoidable errors in initial data and in the models. To quantify the reliability of a forecast is therefore essential and probably more so the longer the forecasts are. Ensemble prediction is thus a new and important concept in weather and climate prediction, which I believe will become a routine aspect of weather prediction in the future. The limit between weather and climate prediction is becoming more and more diffuse and in the final part of this article I will outline the way I think development may proceed in the future.

Large-scale dynamics of the mesosphere and lower thermosphere: an analysis using the extended Canadian Middle Atmosphere Model

The extended Canadian Middle Atmosphere Model is used to investigate the large-scale dynamics of the mesosphere and lower thermosphere (MLT). It is shown that the 4-day wave is substantially amplified in southern polar winter in the presence of instabilities arising from strong vertical shears in the MLT zonal mean zonal winds brought about by parameterized nonorographic gravity wave drag. A weaker 4-day wave in northern polar winter is attributed to the weaker wind shears that result from weaker parameterized wave drag. The 2-day wave also exhibits a strong dependence on zonal wind shears, in agreement with previous modeling studies. In the equatorial upper mesosphere, the migrating diurnal tide provides most of the resolved westward wave forcing, which varies semiannually in conjunction with the tide itself; resolved forcing by eastward traveling disturbances is dominated by smaller scales. Nonmigrating tides and other planetary-scale waves play only a minor role in the zonal mean zonal momentum budget in the tropics at these heights. Resolved waves are shown to play a significant role in the zonal mean meridional momentum budget in the MLT, impacting significantly on gradient wind balance. Balance fails at low latitudes as a result of a strong Reynolds stress associated with the migrating diurnal tide, an effect which is most pronounced at equinox when the tide is strongest. Resolved and parameterized waves account for most of the imbalance at higher latitudes in summer. This results in the gradient wind underestimating the actual eastward wind reversal by up to 40%.

Zonal-mean dynamics of extended recoveries from stratospheric sudden warmings

The recovery of the Arctic polar vortex following stratospheric sudden warmings is found to take upward of 3 months in a particular subset of cases, termed here polar-night jet oscillation (PJO) events. The anomalous zonal-mean circulation above the pole during this recovery is characterized by a persistently warm lower stratosphere, and above this a cold midstratosphere and anomalously high stratopause, which descends as the event unfolds. Composites of these events in the Canadian Middle Atmosphere Model show the persistence of the lower-stratospheric anomaly is a result of strongly suppressed wave driving and weak radiative cooling at these heights. The upper-stratospheric and lower-mesospheric anomalies are driven immediately following the warming by anomalous planetary-scale eddies, following which, anomalous parameterized nonorographic and orographic gravity waves play an important role. These details are found to be robust for PJO events (as opposed to sudden warmings in general) in that many details of individual PJO events match the composite mean. Azonal-mean quasigeostrophic model on the sphere is shown to reproduce the response to the thermal and mechanical forcings produced during a PJO event. The former is well approximated by Newtonian cooling. The response can thus be considered as a transient approach to the steady-state, downward control limit. In this context, the time scale of the lower-stratospheric anomaly is determined by the transient, radiative response to the extended absence of wave driving. The extent to which the dynamics of the wave-driven descent of the stratopause can be considered analogous to the descending phases of the quasi-biennial oscillation (QBO) is also discussed.

Extended Canadian middle atmosphere model: zonal-mean climatology and physical parameterizations

This paper describes the energetics and zonal-mean state of the upward extension of the Canadian Middle Atmosphere Model, which extends from the ground to ~210 km. The model includes realistic parameterizations of the major physical processes from the ground up to the lower thermosphere and exhibits a broad spectrum of geophysical variability. The rationale for the extended model is to examine the nature of the physical and dynamical processes in the mesosphere/lower thermosphere (MLT) region without the artificial effects of an imposed sponge layer which can modify the circulation in an unrealistic manner. The zonal-mean distributions of temperature and zonal wind are found to be in reasonable agreement with observations in most parts of the model domain below ~150 km. Analysis of the global-average energy and momentum budgets reveals a balance between solar extreme ultraviolet heating and molecular diffusion and a thermally direct viscous meridional circulation above 130 km, with the viscosity coming from molecular diffusion and ion drag. Below 70 km, radiative equilibrium prevails in the global mean. In the MLT region between ~70 and 120 km, many processes contribute to the global energy budget. At solstice, there is a thermally indirect meridional circulation driven mainly by parameterized nonorographic gravity-wave drag. This circulation provides a net global cooling of up to 25 K d^-1.

Dynamical control of the mesosphere by orographic and non-orographic gravity wave drag during the extended northern winters of 2006 and 2009

A version of the Canadian Middle Atmosphere Model (CMAM) that is nudged toward reanalysis data up to 1 hPa is used to examine the impacts of parameterized orographic and non-orographic gravity wave drag (OGWD and NGWD) on the zonal-mean circulation of the mesosphere during the extended northern winters of 2006 and 2009 when there were two large stratospheric sudden warmings. The simulations are compared to Aura Microwave Limb Sounder (MLS) observations of mesospheric temperature, carbon monoxide (CO) and derived zonal winds. The control simulation, which uses both OGWD and NGWD, is shown to be in good agreement with MLS. The impacts of OGWD and NGWD are assessed using simulations in which those sources of wave drag are removed. In the absence of OGWD the mesospheric zonal winds in the months preceding the warmings are too strong, causing increased mesospheric NGWD, which drives excessive downwelling, resulting in overly large lower mesospheric values of CO prior to the warming. NGWD is found to be most important following the warmings when the underlying westerlies are too weak to allow much vertical propagation of the orographic gravity waves to the mesosphere. NGWD is primarily responsible for driving the circulation that results in the descent of CO from the thermosphere following the warmings. Zonal mean mesospheric winds and temperatures in all simulations are shown to be strongly constrained by (i.e. slaved to) the stratosphere. Finally, it is demonstrated that the responses to OGWD and NGWD are non-additive due to their dependence and influence on the background winds and temperatures.

On collective intentions: collective action in economics and philosophy

Philosophers and economists write about collective action from distinct but related points of view. This paper aims to bridge these perspectives. Economists have been concerned with rationality in a strategic context. There, problems posed by “coordination games” seem to point to a form of rational action, “team thinking,” which is not individualistic. Philosophers’ analyses of collective intention, however, sometimes reduce collective action to a set of individually instrumental actions. They do not, therefore, capture the first person plural perspective characteristic of team thinking. Other analyses, problematically, depict intentions ranging over others’ actions. I offer an analysis of collective intention which avoids these problems. A collective intention aims only at causing an individual action, but its propositional content stipulates its mirroring in other minds.

Extended optimal estimation techniques for sea surface temperature from the Spinning Enhanced Visible and Infra-Red Imager (SEVIRI)

Sea surface temperature (SST) can be estimated from day and night observations of the Spinning Enhanced Visible and Infra-Red Imager (SEVIRI) by optimal estimation (OE). We show that exploiting the 8.7 μm channel, in addition to the “traditional” wavelengths of 10.8 and 12.0 μm, improves OE SST retrieval statistics in validation. However, the main benefit is an improvement in the sensitivity of the SST estimate to variability in true SST. In a fair, single-pixel comparison, the 3-channel OE gives better results than the SST estimation technique presently operational within the Ocean and Sea Ice Satellite Application Facility. This operational technique is to use SST retrieval coefficients, followed by a bias-correction step informed by radiative transfer simulation. However, the operational technique has an additional “atmospheric correction smoothing”, which improves its noise performance, and hitherto had no analogue within the OE framework. Here, we propose an analogue to atmospheric correction smoothing, based on the expectation that atmospheric total column water vapour has a longer spatial correlation length scale than SST features. The approach extends the observations input to the OE to include the averaged brightness temperatures (BTs) of nearby clear-sky pixels, in addition to the BTs of the pixel for which SST is being retrieved. The retrieved quantities are then the single-pixel SST and the clear-sky total column water vapour averaged over the vicinity of the pixel. This reduces the noise in the retrieved SST significantly. The robust standard deviation of the new OE SST compared to matched drifting buoys becomes 0.39 K for all data. The smoothed OE gives SST sensitivity of 98% on average. This means that diurnal temperature variability and ocean frontal gradients are more faithfully estimated, and that the influence of the prior SST used is minimal (2%). This benefit is not available using traditional atmospheric correction smoothing.

Literal and extended use of kinship terms in documentary papryi

Kinship terms in papyrus letters do not always refer to actual relatives and so pose many problems for modern readers. But by examining all the kinship terms in six centuries of letters it is possible to discover some rules governing the use of kinship terms: in some situations they appear to be always literal, and in others they appear to be almost always extended, though a third group of contexts remains ambiguous. The rules are complex and depend on the particular kinship term involved, the date of writing, the use of names, the position of the kinship term in the letter, and the person to whom it connects the referent.

Dynamic group communication for large-scale parallel data mining

Exascale systems are the next frontier in high-performance computing and are expected to deliver a performance of the order of 10^18 operations per second using massive multicore processors. Very large- and extreme-scale parallel systems pose critical algorithmic challenges, especially related to concurrency, locality and the need to avoid global communication patterns. This work investigates a novel protocol for dynamic group communication that can be used to remove the global communication requirement and to reduce the communication cost in parallel formulations of iterative data mining algorithms. The protocol is used to provide a communication-efficient parallel formulation of the k-means algorithm for cluster analysis. The approach is based on a collective communication operation for dynamic groups of processes and exploits non-uniform data distributions. Non-uniform data distributions can be either found in real-world distributed applications or induced by means of multidimensional binary search trees. The analysis of the proposed dynamic group communication protocol has shown that it does not introduce significant communication overhead. The parallel clustering algorithm has also been extended to accommodate an approximation error, which allows a further reduction of the communication costs. The effectiveness of the exact and approximate methods has been tested in a parallel computing system with 64 processors and in simulations with 1024 processing elements.

Service oriented approach to facility management using extended building information modelling

Facility management (FM), from a service oriented approach, addresses the functions and requirements of different services such as energy management, space planning and security service. Different service requires different information to meet the needs arising from the service. Object-based Building Information Modelling (BIM) is limited to support FM services; though this technology is able to generate 3D models that semantically represent facility’s information dynamically over the lifecycle of a building. This paper presents a semiotics-inspired framework to extend BIM from a service-oriented perspective. The extended BIM, which specifies FM services and required information, will be able to express building service information in the right format for the right purposes. The service oriented approach concerns pragmatic aspect of building’s information beyond semantic level. The pragmatics defines and provides context for utilisation of building’s information. Semiotics theory adopted in this paper is to address pragmatic issues of utilisation of BIM for FM services.