Diorganoruthenium complexes incorporating noninnocent [C6H2(CH2ER2)2-3,5]22-(E = N, P) Bis-Pincer bridging ligands: synthesis, spectroelectrochemistry, and DFT studies

The dinuclear complex [(tpy)Ru-II(PCP-PCP)Ru-II(tPY)]Cl-2 (bridging PCP-PCP = 3,3',5,5'-tetrakis(diphenylphosphinomethyl)biphenyl, [C6H2(CH2PPh2)(2)-3,5](2)(2-)) was prepared via a transcyclometalation reaction of the bis-pincer ligand [PC(H)P-PC(H)P] and the Ru(II) precursor [Ru(NCN)(tpy)]Cl (NCN = [C6H3(CH2NMe2)(2)-2,6](-)) followed by a reaction with 2,2':6',2 ''-terpyridine (tpy). Electrochemical and spectroscopic properties of [(tpy)Ru-II(PCP-PCP)Ru-II(tPY)]Cl-2 are compared with those of the closely related [(tpy)Ru-II(NCN-NCN)Ru-II(tpy)](PF6)(2) (NCN-NCN = [C6H2(CH2- NMe2)(2)-3,5](2)(2-)) obtained by two-electron reduction of [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](PF6)(4). The molecular structure of the latter complex has been determined by single-crystal X-ray structure determination. One-electron reduction of [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](PF6)(4) and one-electron oxidation of [(tpy)Ru-II(PCP-PCP)RUII(tpy)]Cl-2 yielded the mixed-valence species [(tpy)Ru-III(NCN-NCN)RUII(tpy)](3+) and [(tpy)Ru-III(PCP-PCP)RUII(tpy)](3+), respectively. The comproportionation equilibrium constants K-c (900 and 748 for [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](4+) and [(tpy)Ru-II(PCP-PCP)RUII(tpy)](2+), respectively) determined from cyclic voltammetric data reveal comparable stability of the [Ru-III-Ru-II] state of both complexes. Spectroelectrochemical measurements and near-infrared (NIR) spectroscopy were employed to further characterize the different redox states with special focus on the mixed-valence species and their NIR bands. Analysis of these bands in the framework of Hush theory indicates that the mixed-valence complexes [(tpy)Ru-III(PCP-PCP)RUII(tpy)](3+) and [(tpy)Ru-III(NCN-NCN)RUII(tpy)](3+) belong to strongly coupled borderline Class II/Class III and intrinsically coupled Class III systems, respectively. Preliminary DFT calculations suggest that extensive delocalization of the spin density over the metal centers and the bridging ligand exists. TD-DFT calculations then suggested a substantial MLCT character of the NIR electronic transitions. The results obtained in this study point to a decreased metal-metal electronic interaction accommodated by the double-cyclometalated bis-pincer bridge when strong sigma-donor NMe2 groups are replaced by weak sigma-donor, pi-acceptor PPh2 groups

Towards a holistic modelling framework for embodied carbon and waste in the building lifecycle

As the building industry proceeds in the direction of low impact buildings, research attention is being drawn towards the reduction of carbon dioxide emission and waste. Starting from design and construction to operation and demolition, various building materials are used throughout the whole building lifecycle involving significant energy consumption and waste generation. Building Information Modelling (BIM) is emerging as a tool that can support holistic design-decision making for reducing embodied carbon and waste production in the building lifecycle. This study aims to establish a framework for assessing embodied carbon and waste underpinned by BIM technology. On the basis of current research review, the framework is considered to include functional modules for embodied carbon computation. There are a module for waste estimation, a knowledge-base of construction and demolition methods, a repository of building components information, and an inventory of construction materials’ energy and carbon. Through both static 3D model visualisation and dynamic modelling supported by the framework, embodied energy (carbon), waste and associated costs can be analysed in the boundary of cradle-to-gate, construction, operation, and demolition. The proposed holistic modelling framework provides a possibility to analyse embodied carbon and waste from different building lifecycle perspectives including associated costs. It brings together existing segmented embodied carbon and waste estimation into a unified model, so that interactions between various parameters through the different building lifecycle phases can be better understood. Thus, it can improve design-decision support for optimal low impact building development. The applicability of this framework is anticipated being developed and tested on industrial projects in the near future.

Defining a framework for the evaluation of information

In any enterprise, decisions need be made during the life cycle of information about its management. This requires information evaluation to take place; a little-understood process. For evaluation support to be both effective and resource efficient, some sort of automatic or semi-automatic evaluation method would be invaluable. Such a method would require an understanding of the diversity of the contexts in which evaluation takes place so that evaluation support can have the necessary context-sensitivity. This paper identifies the dimensions influencing the information evaluation process and defines the elements that characterise them, thus providing the foundations for a context-sensitive evaluation framework.

Stepwise construction of [Os6(CO)18(μ6-P)]-, a hexanuclear osmium cluster monoanion with trigonal-prismatic co-ordination for phosphorus: X-ray crystal structures of [Os6(μ-H)2(CO)20(MeCN)(μ3-PH)] and [PPh3Me][Os6(CO)18(μ6-P)]

Treatment of the labile cluster [Os3(CO)11(MeCN)] with PH3 affords the substituted product [Os3(CO)11(PH3)](1) in high yield. Subsequent reaction of (1) with Na2CO3 in MeOH, followed by acidification, gives the hydrido phosphido cluster [Os3(µ-H)(CO)10(µ-PH2)](2). When (2) is heated to 45–60 °C in the presence of [Os3(CO)11(MeCN)] a hexanuclear complex with the formulation [Os6(µ-H)2(CO)21(µ3-PH)](3) is obtained. If this reaction is repeated using [Os3(CO)10(MeCN)2] instead of [Os3(CO)11(MeCN)], an acetonitrile-containing product, [Os6(µ-H)2(CO)20(MeCN)(µ3-PH)](4), is obtained. An X-ray analysis of (4) shows that two Os3 triangular units are linked by a µ3-phosphinidene ligand, which symmetrically bridges an Os–Os edge of one triangle and is terminally co-ordinated to one Os atom of the second triangle. When (3) is treated with a weak base, such as [N(PPh3)2]Cl or [PPh3Me] Br, deprotonation to the corresponding cluster monoanion [Os6(µ-H)(CO)21(µ3-PH)]–(5) occurs. Treatment of (5) with a weak acid regenerates (3) in quantitative yield. Thermolysis of (3) leads to a closing up of the metal framework, affording the cluster [Os6(µ-H)(CO)18(µ6-P)], which readily deprotonates to give the anion [Os6(CO)18(µ6-P)]–(7) in the presence of [N(PPh3)2] Cl or [PPh3Me]Br. The same anion (7) may also be obtained by direct thermolysis of (5). An X-ray analysis of the [PPh3Me]+ salt of (7) confirms that the phosphorus occupies an interstitial site in a trigonal-prismatic hexaosmium framework, and co-ordinates to all six metal atoms with an average Os–P distance of 2.31 (1)Å. Proton and 31P n.m.r. data on all the new clusters are presented, and the position of the phosphorus resonance in the 31P n.m.r. spectrum is related to the changes in the environment of the phosphorus atom.

Panzootics and the poor: devising a global livestock disease prioritisation framework for poverty alleviation

Panzootics such as highly pathogenic avian influenza and Rift Valley fever have originated from the South, largely among poor communities. On a global level, approximately two-thirds of those individuals living on less than US$2 per day keep livestock. Consequently, there is a need to better target animal health interventions for poverty reduction using an evidence-based approach. Therefore, the paper offers a three-step prioritisation framework using calculations derived from standard poverty measures: the poverty gap and the head count ratio. Data from 265 poor livestock-keeping households in Kenya informed the study. The results demonstrate that, across a spectrum of producers, the dependence upon particular species varies. Furthermore, the same livestock disease has differing impacts on the depth and severity of poverty. Consequently, animal health interventions need to

Characterization of a highly biodiverse floodplain meadow using hyperspectral remote sensing within a plant functional trait framework

We assessed the potential for using optical functional types as effective markers to monitor changes in vegetation in floodplain meadows associated with changes in their local environment. Floodplain meadows are challenging ecosystems for monitoring and conservation because of their highly biodiverse nature. Our aim was to understand and explain spectral differences among key members of floodplain meadows and also characterize differences with respect to functional traits. The study was conducted on a typical floodplain meadow in UK (MG4-type, mesotrophic grassland type 4, according to British National Vegetation Classification). We compared two approaches to characterize floodplain communities using field spectroscopy. The first approach was sub-community based, in which we collected spectral signatures for species groupings indicating two distinct eco-hydrological conditions (dry and wet soil indicator species). The other approach was “species-specific”, in which we focused on the spectral reflectance of three key species found on the meadow. One herb species is a typical member of the MG4 floodplain meadow community, while the other two species, sedge and rush, represent wetland vegetation. We also monitored vegetation biophysical and functional properties as well as soil nutrients and ground water levels. We found that the vegetation classes representing meadow sub-communities could not be spectrally distinguished from each other, whereas the individual herb species was found to have a distinctly different spectral signature from the sedge and rush species. The spectral differences between these three species could be explained by their observed differences in plant biophysical parameters, as corroborated through radiative transfer model simulations. These parameters, such as leaf area index, leaf dry matter content, leaf water content, and specific leaf area, along with other functional parameters, such as maximum carboxylation capacity and leaf nitrogen content, also helped explain the species’ differences in functional dynamics. Groundwater level and soil nitrogen availability, which are important factors governing plant nutrient status, were also found to be significantly different for the herb/wetland species’ locations. The study concludes that spectrally distinguishable species, typical for a highly biodiverse site such as a floodplain meadow, could potentially be used as target species to monitor vegetation dynamics under changing environmental conditions.

A verification framework for interannual-to-decadal predictions experiments

Decadal predictions have a high profile in the climate science community and beyond, yet very little is known about their skill. Nor is there any agreed protocol for estimating their skill. This paper proposes a sound and coordinated framework for verification of decadal hindcast experiments. The framework is illustrated for decadal hindcasts tailored to meet the requirements and specifications of CMIP5 (Coupled Model Intercomparison Project phase 5). The chosen metrics address key questions about the information content in initialized decadal hindcasts. These questions are: (1) Do the initial conditions in the hindcasts lead to more accurate predictions of the climate, compared to un-initialized climate change projections? and (2) Is the prediction model’s ensemble spread an appropriate representation of forecast uncertainty on average? The first question is addressed through deterministic metrics that compare the initialized and uninitialized hindcasts. The second question is addressed through a probabilistic metric applied to the initialized hindcasts and comparing different ways to ascribe forecast uncertainty. Verification is advocated at smoothed regional scales that can illuminate broad areas of predictability, as well as at the grid scale, since many users of the decadal prediction experiments who feed the climate data into applications or decision models will use the data at grid scale, or downscale it to even higher resolution. An overall statement on skill of CMIP5 decadal hindcasts is not the aim of this paper. The results presented are only illustrative of the framework, which would enable such studies. However, broad conclusions that are beginning to emerge from the CMIP5 results include (1) Most predictability at the interannual-to-decadal scale, relative to climatological averages, comes from external forcing, particularly for temperature; (2) though moderate, additional skill is added by the initial conditions over what is imparted by external forcing alone; however, the impact of initialization may result in overall worse predictions in some regions than provided by uninitialized climate change projections; (3) limited hindcast records and the dearth of climate-quality observational data impede our ability to quantify expected skill as well as model biases; and (4) as is common to seasonal-to-interannual model predictions, the spread of the ensemble members is not necessarily a good representation of forecast uncertainty. The authors recommend that this framework be adopted to serve as a starting point to compare prediction quality across prediction systems. The framework can provide a baseline against which future improvements can be quantified. The framework also provides guidance on the use of these model predictions, which differ in fundamental ways from the climate change projections that much of the community has become familiar with, including adjustment of mean and conditional biases, and consideration of how to best approach forecast uncertainty.

A unifying framework for metrics for aggregating the climate effect of different emissions

Multi-gas approaches to climate change policies require a metric establishing ‘equivalences’ among emissions of various species. Climate scientists and economists have proposed four kinds of such metrics and debated their relative merits. We present a unifying framework that clarifies the relationships among them. We show, as have previous authors, that the global warming potential (GWP), used in international law to compare emissions of greenhouse gases, is a special case of the global damage potential (GDP), assuming (1) a finite time horizon, (2) a zero discount rate, (3) constant atmospheric concentrations, and (4) impacts that are proportional to radiative forcing. Both the GWP and GDP follow naturally from a cost–benefit framing of the climate change issue. We show that the global temperature change potential (GTP) is a special case of the global cost potential (GCP), assuming a (slight) fall in the global temperature after the target is reached. We show how the four metrics should be generalized if there are intertemporal spillovers in abatement costs, distinguishing between private (e.g., capital stock turnover) and public (e.g., induced technological change) spillovers. Both the GTP and GCP follow naturally from a cost-effectiveness framing of the climate change issue. We also argue that if (1) damages are zero below a threshold and (2) infinitely large above a threshold, then cost-effectiveness analysis and cost–benefit analysis lead to identical results. Therefore, the GCP is a special case of the GDP. The UN Framework Convention on Climate Change uses the GWP, a simplified cost–benefit concept. The UNFCCC is framed around the ultimate goal of stabilizing greenhouse gas concentrations. Once a stabilization target has been agreed under the convention, implementation is clearly a cost-effectiveness problem. It would therefore be more consistent to use the GCP or its simplification, the GTP.

A new framework for understanding inequalities between expatriates and host country nationals

An interdisciplinary theoretical framework is proposed for analysing justice in global working conditions. In addition to gender and race as popular criteria to identify disadvantaged groups in organizations, in multinational corporations (MNCs) local employees (i.e. host country nationals (HCNs) working in foreign subsidiaries) deserve special attention. Their working conditions are often substantially worse than those of expatriates (i.e. parent country nationals temporarily assigned to a foreign subsidiary). Although a number of reasons have been put forward to justify such inequalities—usually with efficiency goals in mind—recent studies have used equity theory to question the extent to which they are perceived as fair by HCNs. However, since perceptual equity theory has limitations, this study develops an alternative and non-perceptual framework for analysing such inequalities. Employment discrimination theory and elements of Rawls’s ‘Theory of Justice’ are the theoretical pillars of this framework. This article discusses the advantages of this approach for MNCs and identifies some expatriation practices that are fair according to our non-perceptual justice standards, whilst also reasonably (if not highly) efficient.

A very rare self-assembled ribbon of fused cyclic water pentamers encapsulated in a Cu-II based metal-organic framework

A metal organic framework of Cu-II, tartarate (tar) and 2,2'-bipyridyl (2,2'-bipy)], {[Cu(tar)(2,2'-bipy)]center dot 5H(2)O}(n)} (1) has been synthesized at the mild ambient condition and characterized by single crystal X-ray crystallography. In the compound, the Cu(2,2'-bipy) entities are bridged by tartarate ions which are coordinated to Cu-II by both hydroxyl and monodentate carboxylate oxygen to form a one-dimensional chain. The non-coordinated water molecules form ID water chains by edge-sharing cyclic water pentamers along with dangling water dimers. It shows reversible water expulsion upon heating. The water chains join the ID coordination polymeric chains to a 31) network through hydrogen-bond interactions.

A framework for assessing continuing professional development activities for satisfying pharmacy revalidation requirements

The United Kingdom’s pharmacy regulator contemplated using continuing professional development (CPD) in pharmacy revalidation in 2009, simultaneously asking pharmacy professionals to demonstrate the value of their CPD by showing its relevance and impact. The idea of linking new CPD requirements with revalidation was yet to be explored. Our aim was to develop and validate a framework to guide pharmacy professionals to select CPD activities that are relevant to their work and to produce a score sheet that would make it possible to quantify the impact and relevance of CPD. METHODS: We adapted an existing risk matrix, producing a CPD framework consisting of relevance and impact matrices. Concepts underpinning the framework were refined through feedback from five pharmacist teacher-practitioners. We then asked seven pharmacists to rate the relevance of the framework’s individual elements on a 4-point scale to determine content validity. We explored views about the framework through focus groups with six and interviews with 17 participants who had used it formally in a study. RESULTS: The framework’s content validity index was 0.91. Feedback about the framework related to three themes of penetrability of the framework, usefulness to completion of CPD, and advancement of CPD records for the purpose of revalidation. DISCUSSION: The framework can help professionals better select CPD activities prospectively, and makes assessment of CPD more objective by allowing quantification, which could be helpful for revalidation. We believe the framework could potentially help other health professionals with better management of their CPD irrespective of their field of practice.

Online data processing consent under EU law: a theoretical framework and empirical evidence from the UK

This article analyses the results of an empirical study on the 200 most popular UK-based websites in various sectors of e-commerce services. The study provides empirical evidence on unlawful processing of personal data. It comprises a survey on the methods used to seek and obtain consent to process personal data for direct marketing and advertisement, and a test on the frequency of unsolicited commercial emails (UCE) received by customers as a consequence of their registration and submission of personal information to a website. Part One of the article presents a conceptual and normative account of data protection, with a discussion of the ethical values on which EU data protection law is grounded and an outline of the elements that must be in place to seek and obtain valid consent to process personal data. Part Two discusses the outcomes of the empirical study, which unveils a significant departure between EU legal theory and practice in data protection. Although a wide majority of the websites in the sample (69%) has in place a system to ask separate consent for engaging in marketing activities, it is only 16.2% of them that obtain a consent which is valid under the standards set by EU law. The test with UCE shows that only one out of three websites (30.5%) respects the will of the data subject not to receive commercial communications. It also shows that, when submitting personal data in online transactions, there is a high probability (50%) of incurring in a website that will ignore the refusal of consent and will send UCE. The article concludes that there is severe lack of compliance of UK online service providers with essential requirements of data protection law. In this respect, it suggests that there is inappropriate standard of implementation, information and supervision by the UK authorities, especially in light of the clarifications provided at EU level.