Rigid ferrocenophane and its metal complexes with transition and alkaline-earth metal ions

The rigid [6]ferrocenophane, L-1, was synthesised by condensation of 1,1'-ferrocene dicarbaldehyde with trans-1,2-diaminocyclohexane in high dilution at r.t. followed by reduction. When other experimental conditions were employed, the [6,6,6]ferrocenephane (L-2) was also obtained. Both compounds were characterised by single crystal X-ray crystallography. The protonation of L-1 and its metal complexation were evaluated by the effect on the electron-transfer process of the ferrocene (fc) unit of L-1 using cyclic voltammetry (CV) and square wave voltammetry (SWV) in anhydrous CH3CN solution and in 0.1 M (Bu4NPF6)-Bu-n as the supporting electrolyte. The electrochemical process of L-1 between 300 and 900 mV is complicated by amine oxidation. On the other hand, an anodic shift from the fc/fc(+) wave of L-1 of 249, 225, 81 and 61 mV was observed by formation of Zn2+, Ni2+, Pd2+ and Cu2+ complexes, respectively. Whereas Mg2+ and Ca2+ only have with L-1 weak interactions and they promote the acid-base equilibrium of L-1. This reveals that L-1 is an interesting molecular redox sensor for detection of Zn2+ and Ni2+, although the kinetics of the Zn2+ complex formation is much faster than that of the Ni2+ one. The X-ray crystal structure of [(PdLCl2)-Cl-1] was determined and showed a square-planar environment with Pd(II) and Fe(II) centres separated by 3.781(1) angstrom. The experimental anodic shifts were elucidated by DFT calculations on the [(MLCl2)-Cl-1] series and they are related to the nature of the HOMO of these complexes and a four-electron, two-orbital interaction.

Organocatalytic enantioselective construction of nitrocyclohexanes containing multiple chiral centres via a cascade reaction

The stereoselective construction of complex molecules with multiple stereogenicity in a single step represents an extremely useful, but challenging approach to complexity in chemical synthesis. The development of organocatalytic cascade processes has proven useful in these studies, but reports where four or more stereocentres are created in a single step from just two achiral reagents are rare. Herein we report the development of a novel asymmetric domino Michael-Michael reaction between nitrohex-4-enoates and nitro-olefins to generate cyclohexanes of high complexity, including one with a quaternary centre, and one with five contiguous stereocentres. This methodology provides access to a range of useful nitrocyclohexane derivatives, including a novel class of a-lycorane-like structures.

Sustainability in the built environment

This introductory chapter sets the scene for the book, providing an overview of sustainability in the built environment. With a bias towards buildings and the urban environment, it illustrates the range of issues that impinge upon global carbon reduction and the mechanisms available to help bring about change. Climate change, and its impact on built environment, is briefly introduced and sustainability in the built environment and associated factors are described. The specific topics relating to sustainable design and management of the built environment, including policy and assessment, planning, energy, water and waste, technology, supply and demand, occupants’ behaviour and management have been highlighted. This chapter emphasises the importance of a systemic approach in delivering a sustainable built environment.

Overexpression of marA, soxS and acrB in veterinary isolates of Salmonella enterica rarely correlates with cyclohexane tolerance

Objectives: To determine the contribution of the AcrAB efflux system to cyclohexane tolerance in Salmonella enterica. Methods: The expression of the efflux pump gene, acrB, and regulators marA and soxS from 46 isolates of S. enterica of 14 different serovars was determined by comparative RT-PCR and denaturing HPLC analysis. Results: Twenty-one of the 46 isolates were cyclohexane tolerant, a phenotype associated with multiple antibiotic resistance (MAR) and overexpression of efflux pumps. Of the cyclohexane-tolerant isolates 81% were MAR, whereas only 44% of the cyclohexane-susceptible isolates were MAR, confirming the association between cyclohexane tolerance and MAR. However, there was no correlation between cyclohexane tolerance or MAR and overexpression of acrB, soxS or marA. Conclusions: These data suggest that cyclohexane tolerance in S. enterica can be mediated by an acrB-independent mechanism.

Mapping the trickle out benefits of social and environmental enterprises: a pilot study of an East African eco business

• Objectives The objective of this paper is to propose a framework for mapping the sustainable development and poverty alleviation impacts of social and environmental enterprises in Africa. This framework is then piloted with reference to an East African Ecobusiness. • Prior Work This paper is based on data collected as part of a wider research project examining social and environmental enterprises across the 19 countries of Southern and Eastern Africa. In total, the sustainable development and poverty alleviation impacts of 20 in-depth case studies in 4 countries are being examined. • Approach Data was collected using in-depth interviews with multiple stakeholders associated with the case study business. Secondary materials were also analysed and a quantitative survey of customers undertaken. • Results In addition to their impacts on the environment, African eco businesses can also have substantial social, economic and wider poverty alleviation impacts. This paper maps the impacts of a case study East African ecobusiness, as part of developing a social and environmental enterprise impact framework for Africa and the wider developing world. In our case study, positive and negative impacts are identified, while questions are raised in relation to tradeoffs between social and environmental objectives and temporal dimensions of impact. The usefulness of existing frameworks for understanding the social, environmental and development impacts of these kinds of organisations are also considered. • Implications This paper outlines the necessity of building an African-centric impact map to capture the multi-level poverty alleviation and sustainable development impacts of social and environmental enterprise activity in developing world environments. The framework proposed also offers guidance to businesses operating in Africa about the factors that might be considered as part of their wider social and environmental responsibilities. • Value Assessing the impact of social and environmental enterprises, especially as a route to development within low income countries, is receiving increasing attention in academia and beyond. This paper presents a useful contribution to the scarce literature on social and environmental enterprises in Africa.

Planning autonomous vehicles in the absence of speed lanes using an elastic strip

Planning of autonomous vehicles in the absence of speed lanes is a less-researched problem. However, it is an important step toward extending the possibility of autonomous vehicles to countries where speed lanes are not followed. The advantages of having nonlane-oriented traffic include larger traffic bandwidth and more overtaking, which are features that are highlighted when vehicles vary in terms of speed and size. In the most general case, the road would be filled with a complex grid of static obstacles and vehicles of varying speeds. The optimal travel plan consists of a set of maneuvers that enables a vehicle to avoid obstacles and to overtake vehicles in an optimal manner and, in turn, enable other vehicles to overtake. The desired characteristics of this planning scenario include near completeness and near optimality in real time with an unstructured environment, with vehicles essentially displaying a high degree of cooperation and enabling every possible(safe) overtaking procedure to be completed as soon as possible. Challenges addressed in this paper include a (fast) method for initial path generation using an elastic strip, (re-)defining the notion of completeness specific to the problem, and inducing the notion of cooperation in the elastic strip. Using this approach, vehicular behaviors of overtaking, cooperation, vehicle following,obstacle avoidance, etc., are demonstrated.

Large-scale dynamics associated with clustering of extratropical cyclones affecting Western Europe

Some recent winters in Western Europe have been characterized by the occurrence of multiple extratropical cyclones following a similar path. The occurrence of such cyclone clusters leads to large socio-economic impacts due to damaging winds, storm surges, and floods. Recent studies have statistically characterized the clustering of extratropical cyclones over the North Atlantic and Europe and hypothesized potential physical mechanisms responsible for their formation. Here we analyze 4 months characterized by multiple cyclones over Western Europe (February 1990, January 1993, December 1999, and January 2007). The evolution of the eddy driven jet stream, Rossby wave-breaking, and upstream/downstream cyclone development are investigated to infer the role of the large-scale flow and to determine if clustered cyclones are related to each other. Results suggest that optimal conditions for the occurrence of cyclone clusters are provided by a recurrent extension of an intensified eddy driven jet toward Western Europe lasting at least 1 week. Multiple Rossby wave-breaking occurrences on both the poleward and equatorward flanks of the jet contribute to the development of these anomalous large-scale conditions. The analysis of the daily weather charts reveals that upstream cyclone development (secondary cyclogenesis, where new cyclones are generated on the trailing fronts of mature cyclones) is strongly related to cyclone clustering, with multiple cyclones developing on a single jet streak. The present analysis permits a deeper understanding of the physical reasons leading to the occurrence of cyclone families over the North Atlantic, enabling a better estimation of the associated cumulative risk over Europe.

Environmental agreements as a Hawk-Dove game with confirmed proposals

This paper aims at two different contributions to the literature on international environmental agreements. First, we model environmental agreements as a generic situation, characterized as a Hawk-Dove game with multiple asymmetric equilibria. Second, the article applies the theory on non-cooperative games with confirmed proposals, based on an alternating proposals bargaining protocol, as a way of overcoming the usual problems of coordination and bargaining failures in environmental agreement games, due to payoff asymmetry and equilibrium multiplicity.