Electrochemical studies of bi- and polymetallic complexes featuring acetylide based bridging ligands

Acetylide-based bridging ligands have been widely used in the preparation of complexes that display a degree of electronic interaction between metal-based redox groups located at the ligand termini. The electrochemical response of these systems has been selectively reviewed, with a focus on the variation in properties that accompany changes in the structure of the bridging ligand and the nature of the metal groups.

Syntheses, x-ray structures, photochemistry, redox properties, and DFT calculations of interconvertible fac- and mer-[Mn(SPS)(CO)3] isomers containing a flexible SPS-based pincer ligand

The lithium salt of the anionic SPS pincer ligand composed of a central hypervalent lambda(4)-phosphinine ring bearing two ortho-positioned diphenylphosphine sulfide side arms reacts with [Mn(CO)(5)Br] to give fac-[Mn(SPS)(CO)(3)], This isomer can be converted photochemicaily to mer-[Mn(SPS)(CO)(3)], with a very high quantum yield (0.80 +/- 0.05). The thermal backreaction is slow (taking ca. 8 h at room temperature), in contrast to rapid electrodecatalyzed mer-to-fac isomerization triggered by electrochemical reduction of mer-[Mn(SPS)(CO)(3)]. Both geometric isomers of [Mn(SPS)(CO)(3)] have been characterized by X-ray crystallography. Both isomers show luminescence from a low-lying (IL)-I-3 (SPS-based) excited state. The light emission of fac-[Mn(SPS)(CO)(3)] is largely quenched by the efficient photoisomerization occurring probably from a low-lying Mn-CO dissociative excited state. Density functional theory (DFT) and time-dependent DFT calculations describe the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of fac- and mer-[Mn(CO)(3)(SPS)] as ligand-centered orbitals, largely localized on the phosphinine ring of the SPS pincer ligand. In line with the ligand nature of its frontier orbitals, fac-[Mn(SPS)(CO)(3)] is electrochemically reversibly oxidized and reduced to the corresponding radical cation and anion, respectively. The spectroscopic (electron paramagnetic resonance, IR, and UV-vis) characterization of the radical species provides other evidence for the localization of the redox steps on the SIPS ligand. The smaller HOMO-LUMO energy difference in the case of mer-[Mn(CO)(3)(SPS)], reflected in the electronic absorption and emission spectra, corresponds with its lower oxidation potential compared to that of the fac isomer. The thermodynamic instability of mer-[Mn(CO)(3)(SPS)], confirmed by the DFT calculations, increases upon one-electron reduction and oxidation of the complex.

Facebook faith - social networking in a faith based community

This paper views the increasing social networking as an efficient emerging ministry to the moveable generation. Through social network such as Facebook, ministry from a pastoral perspective can become more authentic and meaningful. Ministry is relational. Social Networking sites provide a strong platform to being part in other people’s life. Social networking and living online builds community beyond geographical boarders. Young adults and youths digital identity often reflects their faith, this is supported by research which suggests a practice of more openness to share and expose private issues online. Spiritual and religious views are freely shared, creating sacred spaces in the midst of life practising a holistic faith identity in a secular community. Providing a strong platform for information flow, Social Network is attractive in a postmodern society where inviting people to join in events are perceived as non threatening, making church community events transparent and available to people who do not attend church, inviting spiritual friendships and relationships. Social Networking strengthens relationship in a non hierarchical manner and invites the minister into lives where there previously would have been barriers, engaging in prayer and bible study as well as pastoral care through social networking, thus relationships deepens via social networking making people real. It has been observed that, although community building happens on the net, church affiliation loyalty remains to the local community. Therefore presence ministry though social networks emerges as a core form of ministry, where relations to youth who move from local church to university campuses are kept alive. The asynchronous nature of communication within social networking eases the minister in her work. The minister is able to engage with many individuals at the same time. Before the minister could visit one person at a time, now she visits 5-6 individuals at any given time. Therefore social networking not only increases the quality of the work, but also empowers the minister to be more efficient.

A novel shape feature for fast region-based pedestrian recognition

A new class of shape features for region classification and high-level recognition is introduced. The novel Randomised Region Ray (RRR) features can be used to train binary decision trees for object category classification using an abstract representation of the scene. In particular we address the problem of human detection using an over segmented input image. We therefore do not rely on pixel values for training, instead we design and train specialised classifiers on the sparse set of semantic regions which compose the image. Thanks to the abstract nature of the input, the trained classifier has the potential to be fast and applicable to extreme imagery conditions. We demonstrate and evaluate its performance in people detection using a pedestrian dataset.

Less-is-more effects in knowledge-based heuristic inference

Inference on the basis of recognition alone is assumed to occur prior to accessing further information (Pachur & Hertwig, 2006). A counterintuitive result of this is the “less-is-more” effect: a drop in the accuracy with which choices are made as to which of two or more items scores highest on a given criterion as more items are learned (Frosch, Beaman & McCloy, 2007; Goldstein & Gigerenzer, 2002). In this paper, we show that less-is-more effects are not unique to recognition-based inference but can also be observed with a knowledge-based strategy provided two assumptions, limited information and differential access, are met. The LINDA model which embodies these assumptions is presented. Analysis of the less-is-more effects predicted by LINDA and by recognition-driven inference shows that these occur for similar reasons and casts doubt upon the “special” nature of recognition-based inference. Suggestions are made for empirical tests to compare knowledge-based and recognition-based less-is-more effects

The nature of Arctic polar vortices in chemistry-climate models

The structure of the Arctic stratospheric polar vortex in three chemistry–climate models (CCMs) taken from the CCMVal-2 intercomparison is examined using zonal mean and geometric-based methods. The geometric methods are employed by taking 2D moments of potential vorticity fields that are representative of the polar vortices in each of the models. This allows the vortex area, centroid location and ellipticity to be determined, as well as a measure of vortex filamentation. The first part of the study uses these diagnostics to examine how well the mean state, variability and extreme variability of the polar vortices are represented in CCMs compared to ERA-40 reanalysis data, and in particular for the UMUKCA-METO, NIWA-SOCOL and CCSR/NIES models. The second part of the study assesses how the vortices are predicted to change in terms of the frequency of sudden stratospheric warmings and their general structure over the period 1960–2100. In general, it is found that the vortices are climatologically too far poleward in the CCMs and produce too few large-scale filamentation events. Only a small increase is observed in the frequency of sudden stratospheric warming events from the mean of the CCMVal-2 models, but the distribution of extreme variability throughout the winter period is shown to change towards the end of the twentyfirst century.

Do national cultural differences affect the nature and characteristics of HRM practices? Evidence from Australian and Hong Kong construction firms on remuneration and job autonomy

Human resource management (HRM) plays a pivotal role in attracting and retaining talents. However, there is growing recognition in international HRM literature that the adoption of the widely accepted US/Harvard-inspired HRM model ignores the influences of cultural contexts on HRM practices in different countries. This notion has not been empirically investigated in the construction industry. Based on survey responses from 604 construction professionals from Australia and Hong Kong, this study examines whether: (i) national cultural differences influence individuals’ preference for types of remuneration and job autonomy, (ii) actual organizational HRM practices reflect such preferences and (iii) gaps between individuals’ preferences and actual organizational HRM practices affect job satisfaction. Results showed significant difference in HRM preferences between Australian and Hong Kong respondents and these are reflected in the distinct types of HRM practices adopted by construction firms in the two countries. Findings further indicated that the gap between individuals’ preferences and actual organizational HRM practices is associated with job satisfaction. The results support existing mainstream research and highlight the deficiency of the acultural treatment of HRM that is still apparent in construction management literature. An uncritical literature in the area not only hinders theory development but also potentially undermines the ability of construction firms to attract, recruit, and retain scarce talents.

Fighting Al-Qaeda in Yemen? Rethinking the nature of the Islamist threat and the effectiveness of US counterterrorism strategy

This paper evaluates the US’ perception of and response to al-Qaeda in the Arabian Peninsula (AQAP) operating in Yemen. It evaluates the empirical evidence on which the present understanding of the group is based, the implications of the socio-political context in which it operates, and the uneasy position of the Yemeni government in the war against terror as it has been affected by US policy from the early 1990s to the present. In the contested Yemeni state, AQAP is competing for political legitimacy and is increasingly dependent on public support. The US’ kill-or-capture response, the “on-off” nature of its support that has made Yemen vulnerable to the influence of al-Qaeda in the past, and the actions of the Yemeni government itself, which depends on the continued existence of the threat to secure financial support vital for political survival, means that none of the measures being taken has the potential to defeat AQAP.

Transaction based indices for the UK commercial real estate market: an exploration using IPD transaction data

The nature of private commercial real estate markets presents difficulties for monitoring market performance. Assets are heterogeneous and spatially dispersed, trading is infrequent and there is no central marketplace in which prices and cash flows of properties can be easily observed. Appraisal based indices represent one response to these issues. However, these have been criticised on a number of grounds: that they may understate volatility, lag turning points and be affected by client influence issues. Thus, this paper reports econometrically derived transaction based indices of the UK commercial real estate market using Investment Property Databank (IPD) data, comparing them with published appraisal based indices. The method is similar to that presented by Fisher, Geltner, and Pollakowski (2007) and used by Massachusett, Institute of Technology (MIT) on National Council of Real Estate Investment Fiduciaries (NCREIF) data, although it employs value rather than equal weighting. The results show stronger growth from the transaction based indices in the run up to the peak in the UK market in 2007. They also show that returns from these series are more volatile and less autocorrelated than their appraisal based counterparts, but, surprisingly, differences in turning points were not found. The conclusion then debates the applications and limitations these series have as measures of market performance.

The monitoring of ecological quality and the classification of standing waters in temperate regions: a review and proposal based on a worked scheme for British waters

This paper reviews the ways that quality can be assessed in standing waters, a subject that has hitherto attracted little attention but which is now a legal requirement in Europe. It describes a scheme for the assessment and monitoring of water and ecological quality in standing waters greater than about I ha in area in England & Wales although it is generally relevant to North-west Europe. Thirteen hydrological, chemical and biological variables are used to characterise the standing water body in any current sampling. These are lake volume, maximum depth, onductivity, Secchi disc transparency, pH, total alkalinity, calcium ion concentration, total N concentration,winter total oxidised inorganic nitrogen (effectively nitrate) concentration, total P concentration, potential maximum chlorophyll a concentration, a score based on the nature of the submerged and emergent plant community, and the presence or absence of a fish community. Inter alia these variables are key indicators of the state of eutrophication, acidification, salinisation and infilling of a water body.

Representing the acquisition and use of energy by individuals in agent-based models of animal populations

Summary 1. Agent-based models (ABMs) are widely used to predict how populations respond to changing environments. As the availability of food varies in space and time, individuals should have their own energy budgets, but there is no consensus as to how these should be modelled. Here, we use knowledge of physiological ecology to identify major issues confronting the modeller and to make recommendations about how energy budgets for use in ABMs should be constructed. 2. Our proposal is that modelled animals forage as necessary to supply their energy needs for maintenance, growth and reproduction. If there is sufficient energy intake, an animal allocates the energy obtained in the order: maintenance, growth, reproduction, energy storage, until its energy stores reach an optimal level. If there is a shortfall, the priorities for maintenance and growth/reproduction remain the same until reserves fall to a critical threshold below which all are allocated to maintenance. Rates of ingestion and allocation depend on body mass and temperature. We make suggestions for how each of these processes should be modelled mathematically. 3. Mortality rates vary with body mass and temperature according to known relationships, and these can be used to obtain estimates of background mortality rate. 4. If parameter values cannot be obtained directly, then values may provisionally be obtained by parameter borrowing, pattern-oriented modelling, artificial evolution or from allometric equations. 5. The development of ABMs incorporating individual energy budgets is essential for realistic modelling of populations affected by food availability. Such ABMs are already being used to guide conservation planning of nature reserves and shell fisheries, to assess environmental impacts of building proposals including wind farms and highways and to assess the effects on nontarget organisms of chemicals for the control of agricultural pests. Keywords: bioenergetics; energy budget; individual-based models; population dynamics.

Identifying key knowledge needs for evidence-based conservation of wild insect pollinators: a collaborative cross-sectoral exercise

In response to evidence of insect pollinator declines, organisations in many sectors, including the food and farming industry, are investing in pollinator conservation. They are keen to ensure that their efforts use the best available science. We convened a group of 32 ‘conservation practitioners’ with an active interest in pollinators and 16 insect pollinator scientists. The conservation practitioners include representatives from UK industry (including retail), environmental non-government organisations and nature conservation agencies. We collaboratively developed a long list of 246 knowledge needs relating to conservation of wild insect pollinators in the UK. We refined and selected the most important knowledge needs, through a three-stage process of voting and scoring, including discussions of each need at a workshop. We present the top 35 knowledge needs as scored by conservation practitioners or scientists. We find general agreement in priorities identified by these two groups. The priority knowledge needs will structure ongoing work to make science accessible to practitioners, and help to guide future science policy and funding. Understanding the economic benefits of crop pollination, basic pollinator ecology and impacts of pesticides on wild pollinators emerge strongly as priorities, as well as a need to monitor floral resources in the landscape.

'Nature Conservation': a new dimension in Open Access publishing bridging science and application

This Editorial presents the focus, scope and policies of the inaugural issue of Nature Conservation, a new open access, peer-reviewed journal bridging natural sciences, social sciences and hands-on applications in conservation management. The journal covers all aspects of nature conservation and aims particularly at facilitating better interaction between scientists and practitioners. The journal will impose no restrictions on manuscript size or the use of colour. We will use an XML-based editorial workflow and several cutting-edge innovations in publishing and information dissemination. These include semantic mark-up of, and enhancements to published text, data, and extensive cross-linking within the journal and to external sources. We believe the journal will make an important contribution to better linking science and practice, offers rapid, peer-reviewed and flexible publication for authors and unrestricted access to content.

The prevalence and nature of prescribing and monitoring errors in English general practice – a retrospective case note review

Objective To determine the prevalence and nature of prescribing and monitoring errors in general practices in England. Design Retrospective case note review of unique medication items prescribed over a 12 month period to a 2% random sample of patients. Mixed effects logistic regression was used to analyse the data. Setting Fifteen general practices across three primary care trusts in England. Data sources Examination of 6048 unique prescription items prescribed over the previous 12 months for 1777 patients. Main outcome measures Prevalence of prescribing and monitoring errors, and severity of errors, using validated definitions. Results Prescribing and/or monitoring errors were detected in 4.9% (296/6048) of all prescription items (95% confidence interval 4.4 - 5.5%). The vast majority of errors were of mild to moderate severity, with 0.2% (11/6048) of items having a severe error. After adjusting for covariates, patient-related factors associated with an increased risk of prescribing and/or monitoring errors were: age less than 15 (Odds Ratio (OR) 1.87, 1.19 to 2.94, p=0.006) or greater than 64 years (OR 1.68, 1.04 to 2.73, p=0.035), and higher numbers of unique medication items prescribed (OR 1.16, 1.12 to 1.19, p<0.001). Conclusion Prescribing and monitoring errors are common in English general practice, although severe errors are unusual. Many factors increase the risk of error. Having identified the most common and important errors, and the factors associated with these, strategies to prevent future errors should be developed based on the study findings.