Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.

Pose and Structure Recovery using Active Models

A new formulation of a pose refinement technique using ``active'' models is described. An error term derived from the detection of image derivatives close to an initial object hypothesis is linearised and solved by least squares. The method is particularly well suited to problems involving external geometrical constraints (such as the ground-plane constraint). We show that the method is able to recover both the pose of a rigid model, and the structure of a deformable model. We report an initial assessment of the performance and cost of pose and structure recovery using the active model in comparison with our previously reported ``passive'' model-based techniques in the context of traffic surveillance. The new method is more stable, and requires fewer iterations, especially when the number of free parameters increases, but shows somewhat poorer convergence.

Private industrial project management: a systems-based case study

The technique of linear responsibility analysis is used for a retrospective case study of a private industrial development consisting of an extension to existing buildings to provide a warehouse, services block and packing line. The organizational structure adopted on the project is analysed using concepts from systems theory which are included in Walker's theoretical model of the structure of building project organizations (Walker, 1981). This model proposes that the process of building provision can be viewed as systems and subsystems which are differentiated from each other at decision points. Further to this, the subsystems can be viewed as the interaction of managing system and operating system. Using Walker's model, a systematic analysis of the relationships between the contributors gives a quantitative assessment of the efficacy of the organizational structure used. The causes of the client's dissatisfaction with the outcome of the project were lack of integration and complexity of the managing system. However, there was a high level of satisfaction with the completed project and this is reflected by the way in which the organization structure corresponded to the model's propositions.

The Universal Common Good: Faith-Based Partnerships and Sustainable Development

Partnership is increasingly espoused as the best relationship between members of the sustainable development aid chain, and implies a respect for the position of all and a desire to avoid a situation where one group dominates another. It also implies a form of relationship that is not just 'better' for the sake of it but that is more able to help achieve sustainable development. However, given the inevitable inequalities in power between donors that have the resources and field partners that do not it can be hard to put this ideal into practice. This paper explores the function of partnership within a group of closely related institutions that comprise the Catholic Church development chain. The research focussed on three Catholic Church based donors (one from the USA and two from Europe) and their partners in Abuja Ecclesiastical Province, Nigeria. Relationships between and within various strata of the Church in Nigeria were also examined. Relationships were 'patchy' at all levels. One of the donors had a significant operational presence in Nigeria and this was regarded by some respondents as a parallel structure that seriously undermined local bodies. However, while problems existed, there was a sense of inter-dependence arising from a shared sense of values and Catholic Social Teaching, which allowed partners to work through their stresses and conflicts. It is the innate sustainability of the aid chain itself founded upon a set of shared values that provided the space and time for problems to be addressed. Copyright (C) 2008 John Wiley & Sons, Ltd and ERP Environment.

Evidence for an apartheid-like social structure in early Anglo-Saxon England

The role of migration in the Anglo-Saxon transition in England remains controversial. Archaeological and historical evidence is inconclusive, but current estimates of the contribution of migrants to the English population range from less than 10 000 to as many as 200 000. In contrast, recent studies based on Y-chromosome variation posit a considerably higher contribution to the modern English gene pool (50-100%). Historical evidence suggests that following the Anglo-Saxon transition, people of indigenous ethnicity were at an economic and legal disadvantage compared to those having Anglo-Saxon ethnicity. It is likely that such a disadvantage would lead to differential reproductive success. We examine the effect of differential reproductive success, coupled with limited intermarriage between distinct ethnic groups, on the spread of genetic variants. Computer simulations indicate that a social structure limiting intermarriage between indigenous Britons and an initially small Anglo-Saxon immigrant population provide a plausible explanation of the high degree of Continental male-line ancestry in England.

Use of an artificial root to examine the influence of 8-hydroxyquinoline on soil microbial activity and bacterial community structure

Invasive plant species have been shown to alter the microbial community composition of the soils they invade and it is suggested that this below-ground perturbation of potential pathogens, decomposers or symbionts may feedback positively to allow invasive success. Whether these perturbations are mediated through specific components of root exudation are not understood. We focussed on 8-hydroxyquinoline, a putative allelochemical of Centaurea diffusa (diffuse knapweed) and used an artificial root system to differentiate the effects of 8-hydroxyquinoline against a background of total rhizodeposition as mimicked through supply of a synthetic exudate solution. In soil proximal (0-10 cm) to the artificial root, synthetic exudates had a highly significant (P < 0.001) influence on dehydrogenase, fluorescein diacetate hydrolysis and urease activity. in addition, 8-hydroxyquinoline was significant (p = 0.003) as a main effect on dehydrogenase activity and interacted with synthetic exudates to affect urease activity (p = 0.09). Hierarchical cluster analysis of 16S rDNA-based DGGE band patterns also identified a primary affect of synthetic exudates and a secondary affect of 8-hydroxyquinoline on bacterial community structure. Thus, we show that the artificial rhizosphere produced by the synthetic exudates was the predominant effect, but, that the influence of the 8-hydroxyquinoline signal on the activity and structure of soil microbial communities could also be detected. (C) 2009 Elsevier Ltd. All rights reserved.

A conventionally managed project: a systems based case study

The technique of linear responsibility analysis is used for a retrospective case study of a private development consisting of an extension to an existing building to provide a wholesale butchery facility. The project used a conventionally organized management process. The organization structure adopted on the project is analysed using concepts from the systems theory, which are included in Walkers theoretical model of the structure of building project organizations. This model proposes that the process of building provision can be viewed as systems and sub-systems that are differentiated from each other at decision points. Further to this, the sub-systems can be viewed as the interaction of managing system and operating system. Using Walkers model, a systematic analysis of the relationships between the contributors gives a quantitative assessment of the efficiency of the organizational structure used. The project's organization structure diverged from the models propositions resulting in delay to the project's completion and cost overrun but the client was satisfied with the project functionally.

A project managed by a multi disciplinary practice: a systems based case study.

The technique of linear responsibility analysis is used for a retrospective case study of a private industrial development consisting of an engineering factory and offices. A multi-disciplinary professional practice was used to manage and design the project. The organizational structure adopted on the project is analysed using concepts from systems theory which are included in Walker's theoretical model of the structure of building project organizations (Walker, 1981). This model proposes that the process of buildings provision can be viewed as systems and sub-systems which are differentiated form each other at decision points. Further to this, the sub-systematic analysis of the relationship between the contributors gives a quantitative assessment of the efficiency of the organizational structure used. There was a high level of satisfaction with the completed project and this is reflected by the way in which the organization structure corresponded to the model's proposition. However, the project was subject to string environmental forces which the project organization was not capable of entirely overcoming.

An analysis of the management of a public sector project: a systems-based case study

The management of a public sector project is analysed using a model developed from systems theory. Linear responsibility analysis is used to identify the primary and key decision structure of the project and to generate quantitative data regarding differentiation and integration of the operating system, the managing system and the client/project team. The environmental context of the project is identified. Conclusions are drawn regarding the project organization structure's ability to cope with the prevailing environmental conditions. It is found that the complexity of the managing system imposed on the project was unable to achieve this and created serious deficiencies in the outcome of the project.

Adjoint goal-based error norms for adaptive mesh ocean modelling

Flow in the world's oceans occurs at a wide range of spatial scales, from a fraction of a metre up to many thousands of kilometers. In particular, regions of intense flow are often highly localised, for example, western boundary currents, equatorial jets, overflows and convective plumes. Conventional numerical ocean models generally use static meshes. The use of dynamically-adaptive meshes has many potential advantages but needs to be guided by an error measure reflecting the underlying physics. A method of defining an error measure to guide an adaptive meshing algorithm for unstructured tetrahedral finite elements, utilizing an adjoint or goal-based method, is described here. This method is based upon a functional, encompassing important features of the flow structure. The sensitivity of this functional, with respect to the solution variables, is used as the basis from which an error measure is derived. This error measure acts to predict those areas of the domain where resolution should be changed. A barotropic wind driven gyre problem is used to demonstrate the capabilities of the method. The overall objective of this work is to develop robust error measures for use in an oceanographic context which will ensure areas of fine mesh resolution are used only where and when they are required. (c) 2006 Elsevier Ltd. All rights reserved.

Case-based analysis in user requirements modelling for knowledge construction

Context: Learning can be regarded as knowledge construction in which prior knowledge and experience serve as basis for the learners to expand their knowledge base. Such a process of knowledge construction has to take place continuously in order to enhance the learners’ competence in a competitive working environment. As the information consumers, the individual users demand personalised information provision which meets their own specific purposes, goals, and expectations. Objectives: The current methods in requirements engineering are capable of modelling the common user’s behaviour in the domain of knowledge construction. The users’ requirements can be represented as a case in the defined structure which can be reasoned to enable the requirements analysis. Such analysis needs to be enhanced so that personalised information provision can be tackled and modelled. However, there is a lack of suitable modelling methods to achieve this end. This paper presents a new ontological method for capturing individual user’s requirements and transforming the requirements onto personalised information provision specifications. Hence the right information can be provided to the right user for the right purpose. Method: An experiment was conducted based on the qualitative method. A medium size of group of users participated to validate the method and its techniques, i.e. articulates, maps, configures, and learning content. The results were used as the feedback for the improvement. Result: The research work has produced an ontology model with a set of techniques which support the functions for profiling user’s requirements, reasoning requirements patterns, generating workflow from norms, and formulating information provision specifications. Conclusion: The current requirements engineering approaches provide the methodical capability for developing solutions. Our research outcome, i.e. the ontology model with the techniques, can further enhance the RE approaches for modelling the individual user’s needs and discovering the user’s requirements.

Temperature-responsive properties and drug solubilization capacity of amphiphilic copolymers based on N-vinylpyrrolidone and vinyl propyl ether

A series of amphiphilic copolymers were synthesized by free-radical copolymerization of N-vinylpyrrolidone (NVP) with vinyl propyl ether (VPE), and the structure of the copolymers was characterized by elemental analysis and gel permeation chromatography. The reactivity of VPE in copolymerization was found to be significantly lower than the reactivity of NVP, which resulted in a decrease of copolymers’ yields and molecular weights with higher content of VPE in the feed mixture. An investigation of the behavior of the copolymers in aqueous solutions at different temperatures by dynamic light scattering revealed the presence of lower critical solution temperature, which depending on the content of VPE ranged within 23−38 °C. Aqueous solutions of these copolymers were studied by fluorescent spectroscopy with pyrene as a polarity probe to reveal the formation of hydrophobic domains. The copolymers were found to be useful for enhancing the solubility of riboflavin in water.

The Structure and implications of children's attitudes to school

The paper reports a study of children's attitudes to school based on a questionnaire survey of 845 pupils in their first year of secondary school in England, together with interviews with a sample of the children. A clearly structured set of attitudes emerged from a factor analysis which showed a distinction between instrumental and affective aspects of attitudes but also dimensions within these, including a sense of teacher commitment and school as a difficult environment. Virtually all children had a strong sense of the importance of doing well at school. However, a substantial minority were not sure that they would stay on after 16. There were few differences between boys and girls or between children from different socio-economic backgrounds but children planning to leave at 16 enjoyed school less and were less sure that it had anything to offer them. There was an almost universal commitment to the value of education but, for a minority, an ambivalence about the experience and relevance of schooling for them.

Excited vibrational state microwave spectra, structure, and force-field of trifluorosilane

The J = 2−1 microwave spectrum of six isotopic species of HSiF3 has been observed and assigned in excited states of five of the six fundamental vibrations. The assignment is based on relative intensities, double resonance experiments, and trial anharmonic force constant calculations. Analysis of the spectra leads to experimental values for five of the constants, all three l-doubling constants qt, one Fermi resonance constant φ233, and one zeta constant. The harmonic force field has been refined to all the available data on vibration wavenumbers, centrifugal distortion constants, and zeta constants. The cubic anharmonic force field has been refined to the data on and qt constants, using two models: a valence force model with two cubic force constants for SiH and SiF stretching, and a more sophisticated model. With the help of these calculations, the following equilibrium structure has been determined: re(SiH) = 1.4468(±5) Å, re(SiF) = 1.5624(±1) Å, HSiF = 110.64(±3)°,

Modelling the lava dome extruded at Soufrière Hills Volcano, Montserrat, August 2005–May 2006. Part I: Dome shape and internal structure

Lava domes comprise core, carapace, and clastic talus components. They can grow endogenously by inflation of a core and/or exogenously with the extrusion of shear bounded lobes and whaleback lobes at the surface. Internal structure is paramount in determining the extent to which lava dome growth evolves stably, or conversely the propensity for collapse. The more core lava that exists within a dome, in both relative and absolute terms, the more explosive energy is available, both for large pyroclastic flows following collapse and in particular for lateral blast events following very rapid removal of lateral support to the dome. Knowledge of the location of the core lava within the dome is also relevant for hazard assessment purposes. A spreading toe, or lobe of core lava, over a talus substrate may be both relatively unstable and likely to accelerate to more violent activity during the early phases of a retrogressive collapse. Soufrière Hills Volcano, Montserrat has been erupting since 1995 and has produced numerous lava domes that have undergone repeated collapse events. We consider one continuous dome growth period, from August 2005 to May 2006 that resulted in a dome collapse event on 20th May 2006. The collapse event lasted 3 h, removing the whole dome plus dome remnants from a previous growth period in an unusually violent and rapid collapse event. We use an axisymmetrical computational Finite Element Method model for the growth and evolution of a lava dome. Our model comprises evolving core, carapace and talus components based on axisymmetrical endogenous dome growth, which permits us to model the interface between talus and core. Despite explicitly only modelling axisymmetrical endogenous dome growth our core–talus model simulates many of the observed growth characteristics of the 2005–2006 SHV lava dome well. Further, it is possible for our simulations to replicate large-scale exogenous characteristics when a considerable volume of talus has accumulated around the lower flanks of the dome. Model results suggest that dome core can override talus within a growing dome, potentially generating a region of significant weakness and a potential locus for collapse initiation.