Fully fluorinated imidodiphosphinate shells for visible- and NIR-Emitting lanthanides: Hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C-F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di-(pentafluorophinoyl)}-P,P-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X-H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F(20)tpip)(3)], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF(20)tpip and [Gd(F(20)tpip)(3)] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F(20)tpip)(3)] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.

Hylambatin and (Thr)11-hylambatin from the skin secretion of the African hyperoliid frog, Kassina maculata: Structural characterisation, precursor cDNA cloning and preliminary pharmacological testing

The tachykinins hylambatin and (Thr)11-hylambatin have been isolated from the defensive skin secretion of the African hyperoliid frog, Kassina maculata,. Hylambatin (DPPDPNRFYGMMamide) is revised in structure from the original sequence by a single site substitution (Asn/Asp at position 6), and (Thr)11-hylambatin, a novel tachykinin, differs in structure from hylambatin by a single Thr/Met substitution. (Thr)11-hylambatin is five- to ten-fold more abundant than hylambatin in secretions. Synthetic replicates of both peptides were active in smooth muscle preparations including the rat tail artery, rat ileum and bovine trachea. While hylambatin displayed activity consistent with an NK1-receptor ligand, (Thr)11-hylambatin was more active than either substance P or neurokinin A in both NK1- and NK-2 receptor rich preparations. Incorporation of a threoninyl residue rather than the canonical leucyl residue at the penultimate position in both substance P and neurokinin A, generated active ligands in both arterial and intestinal smooth muscle preparations. Hylambatin precursor cDNAs, designated HYBN-1 and HYBN-2, respectively, were cloned from a skin library by 3'- and 5'-RACE reactions. Both were highly-homologous containing open-reading frames of 66 amino acids encoding single copies of either hylambatin or (Thr)11-hylambatin. These data reveal a hitherto unrecognized structure/activity attribute of mammalian tachykinin receptors revealed though discovery of a novel amphibian skin-derived, site-substituted peptide ligand.

Millimeter-wave stealth radio for special operations forces

For Special Operations Forces, an important attribute of any future radio will be the ability to conceal transmissions from the enemy while transmitting large amounts of data for situational awareness and communications. These requirements will mean that military wireless systems designers will need to consider operating frequencies in the mm-wave bands: The high data rates that are achievable at these frequencies and the propagation characteristics at this wavelength will provide many benefits for the implementation of 'stealth radio'. This article discusses some of the recent advances in RF front-end technology, alongside physical layer transmission schemes that could be employed for millimeter-wave soldier-mounted radio. The operation of a hypothetical millimeter-wave soldier-to-soldier communications system that makes use of smart antenna technology is also described.

SuperWASP observations of long timescale photometric variations in cataclysmic variables

Aims: We investigated whether the predictions and results of Stanishev et al. (2002, A&A, 394, 625) concerning a possible relationship between eclipse depths in PX And and its retrograde disc precession phase, could be confirmed in long term observations made by SuperWASP. In addition, two further CVs (DQ Her and V795 Her) in the same SuperWASP data set were investigated to see whether evidence of superhump periods and disc precession periods were present and what other, if any, long term periods could be detected. Methods: Long term photometry of PX And, V795 Her and DQ Her was carried out and Lomb-Scargle periodogram analysis undertaken on the resulting light curves. For the two eclipsing CVs, PX And and DQ Her, we analysed the potential variations in the depth of the eclipse with cycle number. Results: The results of our period and eclipse analysis on PX And confirm that the negative superhump period is 0.1417 ± 0.0001d. We find no evidence of positive superhumps in our data suggesting that PX And may have been in a low state during our observations. We improve on existing estimates of the disc precession period and find it to be 4.43 ± 0.05d. Our results confirm the predictions of Stanishev et al. (2002). We find that DQ Her does not appear to show a similar variation for we find no evidence of negative superhumps or of a retrograde disc precession. We also find no evidence of positive superhumps or of a prograde disc precession and we attribute the lack of positive superhumps in DQ Her to be due to the high mass ratio of this CV. We do however find evidence for a modulation of the eclipse depth over a period of 100 days which may be linked with solar-type magnetic cycles which give rise to long term photometric variations. The periodogram analysis for V795 Her detected the likely positive superhump period 0.1165d, however, neither the 0.10826d orbital period nor the prograde 1.53d disc precession period were seen. Here though we have found a variation in the periodogram power function at the positive superhump period, over a period of at least 120 days.

Extensive optical and near-infrared observations of the nearby, narrow-lined type Ic SN 2007gr: days 5 to 415

We present photometric and spectroscopic observations at optical and near-infrared wavelengths of the nearby type Ic supernova 2007gr. These represent the most extensive data-set to date of any supernova of this sub-type, with frequent coverage from shortly after discovery to more than one year post-explosion. We deduce a rise time to B-band maximum of 11.5 +/- 2.7 d. We find a peak B-band magnitude of M-B = -16.8, and light curves which are remarkably similar to the so-called "hypernova" SN 2002ap. In contrast, the spectra of SNe 2007gr and 2002ap show marked differences, not least in their respective expansion velocities. We attribute these differences primarily to the density profiles of their progenitor stars at the time of explosion i.e. a more compact star for SN 2007gr compared to SN 2002ap. From the quasi-bolometric light curve of SN 2007gr, we estimate that 0.076 +/- 0.010 M-circle dot of Ni-56 was produced in the explosion. Our near-infrared (IR) spectra clearly show the onset and disappearance of the first overtone of carbon monoxide (CO) between similar to 70 to 175 d relative to B-band maximum. The detection of the CO molecule implies that ionised He was not microscopically mixed within the carbon/oxygen layers. From the optical spectra, near-IR light curves, and colour evolution, we find no evidence for dust condensation in the ejecta out to about +400 d. Given the combination of unprecedented temporal coverage, and high signal-to-noise data, we suggest that SN 2007gr could be used as a template object for supernovae of this sub-class.

A Scalable and Programmable Modular Traffic Manager Architecture

A key issue in the design of next generation Internet routers and switches will be provision of traffic manager (TM) functionality in the datapaths of their high speed switching fabrics. A new architecture that allows dynamic deployment of different TM functions is presented. By considering the processing requirements of operations such as policing and congestion, queuing, shaping and scheduling, a solution has been derived that is scalable with a consistent programmable interface. Programmability is achieved using a function computation unit which determines the action (e.g. drop, queue, remark, forward) based on the packet attribute information and a memory storage part. Results of a Xilinx Virtex-5 FPGA reference design are presented.

The development of national in-group bias: English children's attributions of characteristics to English, American and German people

This study investigated the development of national in-group bias in 5-11-year-old children. Three hundred and seven English children were asked to attribute characteristics to their own national group either on its own or in conjunction with attributing characteristics to one of two national out-groups, either Americans or Germans. The importance which the children ascribed to their own national identity in relationship to their other social identities was also assessed. It was found that, with increasing age, there was an increase in the number of negative characteristics attributed to the national in-group, and an increase in the number of positive characteristics attributed to the two out-groups, the net result being an overall reduction in in-group bias across this age range. However, in-group favouritism was still exhibited at all ages. Greater importance was attributed to national identity with increasing age. However, the characteristics attributed to the English in-group did not vary as a function of the comparative out-group which was present while the attributions were being made. The presence of a comparative out-group also did not affect the importance that was ascribed to the national identity. These findings suggest that children are relatively insensitive to the prevailing comparative context when making judgments about national groups.

Testing the stability of the benefit transfer function for discrete choice contingent valuation data

This paper examines the stability of the benefit transfer function across 42 recreational forests in the British Isles. A working definition of reliable function transfer is Put forward, and a suitable statistical test is provided. A novel split sample method is used to test the sensitivity of the models' log-likelihood values to the removal of contingent valuation (CV) responses collected at individual forest sites, We find that a stable function improves Our measure of transfer reliability, but not by much. We conclude that, in empirical Studies on transferability, considerations of function stability are secondary to the availability and quality of site attribute data. Modellers' can study the advantages of transfer function stability vis-a-vis the value of additional information on recreation site attributes. (c) 2008 Elsevier GmbH. All rights reserved.

Children’s attributions of belief to humans and God: cross-cultural evidence

The capacity to attribute beliefs to others in order to understand action is one of the mainstays of human cognition. Yet it is debatable whether children attribute beliefs in the same way to all agents. In this paper, we present the results of a false-belief task concerning humans and God run with a sample of Maya children aged 4–7, and place them in the context of several psychological theories of cognitive development. Children were found to attribute beliefs in different ways to humans and God. The evidence also speaks to the debate concerning the universality and uniformity of the development of folk-psychological reasoning.

Chernobyl: Living with Risk and Uncertainty

The nuclear accident in Chernobyl in 1986 is a dramatic example of the type of incidents that are characteristic of a risk society. The consequences of the incident are indeterminate, the causes complex and future developments unpredictable. Nothing can compensate for its effects and it affects a broad population indiscriminately. This paper examines the lived experience of those who experienced biographical disruption as residents of the region on the basis of qualitative case studies carried out in 2003 in the Chernobyl regions of Russia, Ukraine and Belarus. Our analysis indicates that informants tend to view their future as highly uncertain and unpredictable; they experience uncertainty about whether they are already contaminated, and they have to take hazardous decisions about where to go and what to eat. Fear, rumours and experts compete in supplying information to residents about the actual and potential consequences of the disaster, but there is little trust in, and only limited awareness of, the information that is provided. Most informants continue with their lives and do what they must or even what they like, even where the risks are known. They often describe their behaviour as being due to economic circumstances; where there is extreme poverty, even hazardous food sources are better than none. Unlike previous studies, we identify a pronounced tendency among informants not to separate the problems associated with the disaster from the hardships that have resulted from the break-up of the USSR, with both events creating a deep-seated sense of resignation and fatalism. Although most informants hold their governments to blame for lack of information, support and preventive measures, there is little or no collective action to have these put in place. This contrasts with previous research which has suggested that populations affected by disasters attribute crucial significance to that incident and, as a consequence, become increasingly politicized with regard to related policy agendas.

Predator diversity enhances secondary production and decreases the likelihood of trophic cascades

We manipulated the diversity of top predators in a three trophic level marine food web. The food web included four top benthic marine fish predators (black goby, rock goby, sea scorpion and shore rockling), an intermediate trophic level of small fish, and a lower trophic level of benthic invertebrates. We kept predator density constant and monitored the response of the lower trophic levels. As top predator diversity increased, secondary production increased. We also observed that in the presence of the manipulated fish predators, the density of small gobiid fish (intermediate consumers) was suppressed, releasing certain groups of benthic invertebrates (caprellid amphipods, copepods, nematodes and spirorbid worms) from heavy intermediate predation pressure. We attribute the mechanism responsible for this trophic cascade to a trait-mediated indirect interaction, with the small gobiid fish changing their use of space in response to altered predator diversity. In the absence of top fish predators, a full-blown trophic cascade occurs. Therefore the diversity of predators reduces the likelihood of trophic cascades occurring and hence provides insurance against the loss of an important ecosystem function (i.e. secondary production).

Towards an understanding of the causes and effects of software requirements change: two case studies

Changes to software requirements not only pose a risk to the successful delivery of software applications but also provide opportunity for improved usability and value. Increased understanding of the causes and consequences of change can support requirements management and also make progress towards the goal of change anticipation. This paper presents the results of two case studies that address objectives arising from that ultimate goal. The first case study evaluated the potential of a change source taxonomy containing the elements ‘market’, ‘organisation’, ‘vision’, ‘specification’, and ‘solution’ to provide a meaningful basis for change classification and measurement. The second case study investigated whether the requirements attributes of novelty, complexity, and dependency correlated with requirements volatility. While insufficiency of data in the first case study precluded an investigation of changes arising due to the change source of ‘market’, for the remainder of the change sources, results indicate a significant difference in cost, value to the customer and management considerations. Findings show that higher cost and value changes arose more often from ‘organisation’ and ‘vision’ sources; these changes also generally involved the co-operation of more stakeholder groups and were considered to be less controllable than changes arising from the ‘specification’ or ‘solution’ sources. Results from the second case study indicate that only ‘requirements dependency’ is consistently correlated with volatility and that changes coming from each change source affect different groups of requirements. We conclude that the taxonomy can provide a meaningful means of change classification, but that a single requirement attribute is insufficient for change prediction. A theoretical causal account of requirements change is drawn from the implications of the combined results of the two case studies.

The Ontology of Thisness

The paper seeks to give an account of what it is for an individual to instantiate thisness, and how an individual and its thisness are related (where the thisness of an individual x is the property of being identical to x). Such an account is completely lacking in the literature, even among those who defend and make use of thisness. My approach is to seek out a model for the instantiation of thisness by canvassing realist accounts of the substance/attribute relation , and then make appropriate modifications to the most likely candidate in order to accommodate an individual's instantiation of thisness (the accounts cannot be strictly identical for reasons that I explain). I go on to suggest that the model can be appropriately applied in the case of other individuals which might instantiate thisness: for example, persons and events (where these are conceived as fundamental categories of ontology distinct from material substances).

The 'Europeanization' of Reference Groups

In this paper we address the question of the relative importance of within and between country differences in income and material deprivation in the European Union in the context of recent suggestions that insufficient attention has been paid to the latter. In particular, we respond to the argument that the 'state bounded' relative income approach obscures the significance of EU-wide reference groups. Making use of EU-SILC 2004, we have sought to quantify the magnitude of relevant within and between country differences and their relative impact. Overall, our analysis supports the view that the predominant frame of reference is a national one. The limited impact of European reference groups observed in our analysis does not require explanation in terms of the emergence of a European social stratification system. Furthermore, the significance of such comparisons depends not only on the expectations of those affected by European inequalities but on the degree of legitimacy afforded to ensuing demands. While an EU-wide income-threshold can provide information regarding progress of the Union towards greater social cohesion, its usage for this purpose does not require a strong sense of European identity. Given the current status of the European Social Model, it would seem unwise to attribute an undue degree of policy relevance to the relatively modest impact of EU-wide reference groups revealed in our analysis.

Self-disclosure decision making based on intimacy and privacy

Autonomous agents may encapsulate their principals' personal data attributes. These attributes may be disclosed to other agents during agent interactions, producing a loss of privacy. Thus, agents need self-disclosure decision-making mechanisms to autonomously decide whether disclosing personal data attributes to other agents is acceptable or not. Current self-disclosure decision-making mechanisms consider the direct benefit and the privacy loss of disclosing an attribute. However, there are many situations in which the direct benefit of disclosing an attribute is a priori unknown. This is the case in human relationships, where the disclosure of personal data attributes plays a crucial role in their development. In this paper, we present self-disclosure decision-making mechanisms based on psychological findings regarding how humans disclose personal information in the building of their relationships. We experimentally demonstrate that, in most situations, agents following these decision-making mechanisms lose less privacy than agents that do not use them. (C) 2012 Elsevier Inc. All rights reserved.