Metal-organic frameworks (MOFs) are a relatively new class of porous materials, assembled from inorganic metal nodes and organic ligands. MOFs have garnered significant attention in the porous materials and adsorption fields in recent years due to their various attractive features such as high surface areas and pore volumes, tunable and uniform pore sizes, chemically functionalized adsorption sites, and potential for post-synthetic modification. These features give MOFs enormous potential for use in applications such as air purification, methane and hydrogen storage, separations, catalysis, sensing, and drug delivery. Therefore, synthesis and adsorption studies of MOFs have increased tremendously in recent years. Among the aforesaid applications, air purification and air quality control are important topics because existing porous media are ineffective at the adsorptive removal of toxic industrial chemicals (TICs) and chemical warfare agents. Thus, there is a critical need for radical improvements in these purification systems. MOFs have shown great potential to become next-generation filter media as they outperform the traditional porous materials such as activated carbons and zeolites in the air purification of TICs such as ammonia and sulfur dioxide. In spite of the numerous desirable attributes of MOFs, the practical use of these new materials in most applications hinges on their stability in humid or aqueous environments. The sensitivity of certain MOFs under humid conditions is well known, but systematic studies of the water stability properties of MOFs are lacking. This information is critical for identifying structural factors that are important for development of next-generation, water stable MOFs. In addition to the water stability issue, difficulty in the scale up of MOF synthesis has also plagued MOFs. Hence, the goal of this Ph.D. dissertation research is to design ammonia-selective, water stable MOFs that can be synthesized on a large scale. This work will have a direct impact on moving the MOF field forward to the commercial level. To achieve the aforementioned goal, this Ph.D. dissertation research has been divided into following three objectives: (1) Advance our understanding of the water stability of MOFs and develop design criteria for the construction of water stable MOFs. (2) Design water stable, ammonia-selective MOFs for next-generation chemical, biological, radiological, and nuclear (CBRN) filter media. (3) Investigate the scale-up of the UiO-66 MOF scaffold. Through the research efforts over the past four years, it is discovered that it is possible to adjust the water stability of pillared MOFs in both positive and negative directions by proper shielding of the ligand via functional groups. This study is the first of its kind and is of high value for the MOF community. This shielding concept is further extended by synthesizing 4 novel isostructural MOFs with methyl functional groups at different positions on the ligand. For the first time, light is shed on the important distinction between kinetic and thermodynamic water stability and experimental evidence for a kinetically governed water stability mechanism in these MOFs is provided. It is also demonstrated that, using catenation in combination with a pillaring strategy, it is possible to obtain water stable MOFs even when the pillar ligand has lower basicity (pKa value). Ammonia breakthrough measurements have shown that a hydroxyl functionalized Zr-based UiO-66 material is promising as it could offer a method for targeting the removal of specific chemical threats in a chemically stable framework that does not degrade in the presence of water. Large scale synthesis of a water stable MOF, UiO-66, is studied using glass vials and Teflon lined autoclaves. UiO-66 synthesis methods have been refined such that it is now possible to produce more than 70 times the yield obtained from the original synthesis report using the same reaction volume. This would result in a significant reduction of the MOF production cost at the industrial scale. Methane and hydrogen are ‘clean fuels’ (less CO2 emissions than petroleum) and MOFs are being tested for their on-board storage in cars due to the extremely high storage capacities of MOFs being promising enough to meet the requirements. Hence, more broadly, this Ph.D. dissertation work will lead to commercial applications of MOFs, which can revolutionize a variety of gas separation and storage problems such as CO2 capture, natural gas upgrading, and methane and hydrogen storage for clean fuel technologies. This would greatly reduce the environmental concerns faced by our society today.

Stetig steigende Ansprüche an ästhetisch ansprechenden festsitzenden Zahnersatz, haben zu einer enormen Entwicklung im Bereich der enossalen Implantologie geführt. Ebenso führte die Weiterentwicklung im Bereich dentaler Keramiken zu einer immer häufigeren Anwendung vollkeramischer Systeme. In der vorliegenden in-vitro-Studie wurde der Einfluss verschiedener Reinigungsmethoden auf die Haftkraft rezementierter implantatgetragener Zirkoniumdioxid-Kronengerüste untersucht. Die untersuchten Parameter waren: manuelle Entfernung der Zementreste mit Hilfe eines Heidemann Spatels, Säuberung durch Ausstrahlung der Suprakonstruktion mit Aluminiumdioxid (Korngröße: 110 μm, 2 bar, 15s Dauer), kombinierte manuelle Säuberung und Ultraschallreinigung (Isopropanolbad 99%ig). Für den Versuch wurden insgesamt 52 Probekörper mit den drei genannten Parametern, sowie eine Kontrollgruppe mit unbehandelten Zirkoniumdioxid-Käppchen je 13 Mal einem Abzugsversuch unterzogen. Zur Herstellung der Kronengerüste wurden die Titan-Abutments mit dem Cercon® eye Scanner (DeguDent, Hanau) eingescannt und die Zirkoniumdioxid-Käppchen daraufhin digital mit der CAD-Software Cercon® art modelliert und im Labor der Firma DeguDent, Hanau, gefräst. Anschließend wurden die Kronengerüste auf den Abutments mit TempBond® NE der Firma Kerr (Ratstatt, Deutschland) zementiert und in der Universalprüfmaschine Zwick Z007 (Zwick, Ulm) den Abzugsversuchen bis zur Dezementierung unterzogen. Die Auswertung der Abzüge erfolgte mit der Software „testXpert“. Die Ergebnisse zeigten, dass die Kombination aus manueller Reinigung und Ultraschallbad verglichen mit den anderen Methoden zu statistisch signifikant höheren Retentionswerten führte. Zwischen der reinen manuellen Säuberung und der Reinigung durch Ausstrahlen des Kronengerüstes zeigte sich kein klinisch relevanter und signifikanter Unterschied.

Les Metal-Organic Frameworks résultent de l'organisation de clusters métalliques et demolécules organiques chélatantes qui forment un réseau cristallin poreux. Leur découverte apermis des avancées majeures dans le domaine du stockage et de la séparation des gaz.Malheureusement la faible stabilité et l'acidité modérée de ces matériaux ne les rendent quepeu compétitifs par rapport aux zéolites dans le domaine du raffinage ou de la dépollution. Ils'agit d'explorer, avec ces matériaux, de nouvelles applications catalytiques en tirant partie deleur principale qualité : leur modularité. En effet le large choix de métaux, de ligands, ainsique la post fonctionnalisation de ces derniers permet la synthèse contrôlée de matériauxpossédant des propriétés de flexibilité, de confinement ainsi qu'un environnement chimiquesimilaire à celui des sites actifs des enzymes. Ce travail s'inspire du procédé catalytique desenzymes pour obtenir des MOFs hautement sélectifs en conditions douces. Nous décrivons ledéveloppement de méthodes pour encapsuler des catalyseurs organométalliques dans despores calibrés afin de modifier la sélectivité d'une réaction d'oxydation et stabiliser lecatalyseur. Quatre MOFs supportant des groupes amino ont été synthétisés afin de permettreleur post fonctionnalisation. Les propriétés de flexibilité ainsi que la distribution des sitespotentiellement actifs du MOF MIL-53 ont également été contrôlés grâce à lafonctionnalisation partielle de la structure. Enfin ces amino MOFs furent post fonctionnalisésen isocyanate en deux étapes afin d'améliorer la réactivité de la structure et de permettre legreffage de diverses amines. Ces outils pourraient permettre à court terme la conception deMOFs dont les pores ont un environnement semblable aux metalloenzymes.

Abstract dialectical frameworks (ADFs) have recently been proposed as a versatile generalization of Dung's abstract argumentation frameworks (AFs). In this paper, we present a comprehensive analysis of the computational complexity of ADFs. Our results show that while ADFs are one level up in the polynomial hierarchy compared to AFs, there is a useful subclass of ADFs which is as complex as AFs while arguably offering more modeling capacities. As a technical vehicle, we employ the approximation fixpoint theory of Denecker, Marek and Truszczyński, thus showing that it is also a useful tool for complexity analysis of operator-based semantics.

There is no single resource so essential to sustaining life and livelihoods than water (UNDP, 2005). Water is furthermore a strategic resource that not only gives life, but is also a catalyst for development; therefore water has to and must be at the centre of all development plans (Buyelwa, 2009). Water can be the limiting factor for economic growth, upliftment and social development due to its scarcity and uneven distribution. Strategic spatial interface and relationship with water resource planning and management is fundamental to development and realisation of spatial potential. Strategic spatial planning has many components of which the Spatial Development Framework forms the key regulation to guide development and inform investment opportunities. The goal of this study is to determine the degree to which water resource management and planning is incorporated in Spatial Development Frameworks in context of strategic spatial planning. Concurrently international strategic spatial planning procedures and water resource management principles are investigated to correlate the local situation with international trends. A Goal Achievement Matrix (GAM) with ten assessment principles is developed as a tool for evaluation of strategic spatial planning and water resource management documents in terms of the local municipal level. This GAM may be used and implemented as a comparative evaluation tool to compare the degree of integration and implementation of water resource management and strategic spatial planning of local municipal authorities internationally. The percentage score as achieved in evaluation of the GAM indicates the degree of integration of water resource management and planning with strategic spatial planning. The cumulative result of the GAM scored 68% which can be used as a degree of comparison in future studies with other local municipalities, even on an international level. Measured in terms of the different authority levels the local level performed the worst with a 50% GAM score whilst the national level has a high GAM score of 86%. The low local level score indicates that exceptional legislation and policies on national level are not sufficient to eradicate poverty, provide water for all and provide for long-term sustainability if the implementation at local level falters. The low local level score may also be attributed to a lack of institutional capacity and lack of appropriate skills. It is concluded that Spatial Development Frameworks (as a component of strategic spatial planning) and water resource management and planning on a local level are not effectively integrated and it is recommended that water resources and planned future development must be effectively managed and integrated in order to ensure sustainable communities at local level. As a planning recommendation, the Guidelines for the Development of Spatial Development Frameworks developed by the Department of Rural Development and Land Reform must be extended to incorporate the integrative approach between strategic spatial planning and water resource management as a fundamental aspect. The effective integration of water resource management and planning in strategic spatial planning is key to sustainable, equitable and viable communities. / Thesis (MArt et Scien (Urban and Regional Planning))--North-West University, Potchefstroom Campus, 2013.

There is no single resource so essential to sustaining life and livelihoods than water (UNDP, 2005). Water is furthermore a strategic resource that not only gives life, but is also a catalyst for development; therefore water has to and must be at the centre of all development plans (Buyelwa, 2009). Water can be the limiting factor for economic growth, upliftment and social development due to its scarcity and uneven distribution. Strategic spatial interface and relationship with water resource planning and management is fundamental to development and realisation of spatial potential. Strategic spatial planning has many components of which the Spatial Development Framework forms the key regulation to guide development and inform investment opportunities. The goal of this study is to determine the degree to which water resource management and planning is incorporated in Spatial Development Frameworks in context of strategic spatial planning. Concurrently international strategic spatial planning procedures and water resource management principles are investigated to correlate the local situation with international trends. A Goal Achievement Matrix (GAM) with ten assessment principles is developed as a tool for evaluation of strategic spatial planning and water resource management documents in terms of the local municipal level. This GAM may be used and implemented as a comparative evaluation tool to compare the degree of integration and implementation of water resource management and strategic spatial planning of local municipal authorities internationally. The percentage score as achieved in evaluation of the GAM indicates the degree of integration of water resource management and planning with strategic spatial planning. The cumulative result of the GAM scored 68% which can be used as a degree of comparison in future studies with other local municipalities, even on an international level. Measured in terms of the different authority levels the local level performed the worst with a 50% GAM score whilst the national level has a high GAM score of 86%. The low local level score indicates that exceptional legislation and policies on national level are not sufficient to eradicate poverty, provide water for all and provide for long-term sustainability if the implementation at local level falters. The low local level score may also be attributed to a lack of institutional capacity and lack of appropriate skills. It is concluded that Spatial Development Frameworks (as a component of strategic spatial planning) and water resource management and planning on a local level are not effectively integrated and it is recommended that water resources and planned future development must be effectively managed and integrated in order to ensure sustainable communities at local level. As a planning recommendation, the Guidelines for the Development of Spatial Development Frameworks developed by the Department of Rural Development and Land Reform must be extended to incorporate the integrative approach between strategic spatial planning and water resource management as a fundamental aspect. The effective integration of water resource management and planning in strategic spatial planning is key to sustainable, equitable and viable communities. / Thesis (MArt et Scien (Urban and Regional Planning))--North-West University, Potchefstroom Campus, 2013.

JavaScript is used on the web together with HTML and CSS, in many cases using frameworks for JavaScript such as jQuery and Backbone.js. This project is comparing the speed and memory allocation of the programming language JavaScript and its two most used frameworks as well as the language on its own. Since JavaScript is not very fast and it has some missing features or features that differ from browser to browser and frameworks solve this problem but at the cost of speed and memory allocation, the aim is to find out how well JavaScript and the two frameworks jQuery and Backbone.js are doing this on Google Chrome Canary. The results varied (mostly) between the implementations and show that the to-do application is a good enough example to use when comparing the results of heap allocation and CPU time of methods. The results where compared with their mean values and using ANOVA. JavaScript was the fastest, but it might not be enough for a developer to completely stop using frameworks. With JavaScript a developer can choose to create a custom framework, or use an existing one based on the results of this project.

Synthesis of polycrystalline, vs. single-crystalline porous materials, such as metal-organic frameworks (MOFs), is usually beneficial due to shorter synthetic time and higher yields. However, the structural characterization of these materials by X-ray powder diffraction can be complicated. Even more difficult, is to track structural changes of MOFs by in situ experiments. Hence, we designed several successful techniques for the structural investigation of porous MOFs. These methods utilize the Structure Envelope (SE) density maps. SEs are surfaces which describing the pore system with the framework. It was shown that these maps can be easily generated from the structure factors of a few (1 to 10) of the most intense low index reflections. Application of SE in Charge Flipping calculations shortens and simplifies structure determination of MOF materials. This method provides excellent MOF models which can be used as a good starting point for their refinement. However, the most interesting results have been found by using Difference Envelope Density (DED) analysis. DED plots are made by taking the difference between observed and calculated SE densities. This allows us to study guest related issues of MOFs such as, location of guest molecules in the pores, tracking activation of MOFs and gas loading, etc. We also have shown that, DED created from routine powder diffraction patterns might provide very important information about MOF structure itself. In fact DED can be used for study of interpenetration, substituents locations and effects conformational changes in the MOF ligands. Generation and analysis of SEs and DEDs are easy and straightforward. It provides the information needed to explain major deviations in structure-property relationship in MOFs. In our opinion, this method might become one of the important and routine techniques for MOFs structural analysis.

Ideas about water use and ethics have been linked for many thousands of years. In this millennium, water resources remain a primary area of concern throughout the world, including such issues as shortages, supply, flooding, quality, restoration, allocation and regulation. Today, electronic environmental news and specialty websites contain a breadth of information on current water resources conflicts and issues throughout the world. In many parts of the world, water quantity is decreasing and water quality is worsening, lack of access to improved water supplies is decreasing, as is access to basic sanitation. Water challenges relating to water quantity and water quality are increasingly common in Canada and the United States due to water resources being under increasing pressure from population growth, economic activity and intensifying competition for the water among users. Faced with these challenges, humans are confronted with momentous decisions. Before making more decisions that will have an influence over water resources, and in response to repeated calls for a water ethic, this research takes the perspective that it is necessary to explore the ethical intentions of decision-makers with respect to water resources legislation and policy in Canada. The ultimate goal is to define a set of principles for a proposed water ethic that could and should be implemented at the municipal level of government in Canada. A review of academic and professional literature and a mixed methods research approach comparing two case study areas was used to gain a baseline understanding of the potential influences of underlying ethical frameworks on policy makers in Calgary, Alberta and Guelph, Ontario. A proposed water ethic, containing a set of principles compiled from ethical considerations for water use in academic and professional literature, was also developed and presented to case study participants. Participants provided feedback on their strength of agreement with each principle, thoughts on modifications, improvements and/or deletions of any principle, and implementation considerations of the proposed water ethic at the municipal level of government. The results indicate that case study participants in both areas apply a variety of ethical frameworks when making professional decisions about water resources management, and when preparing water legislation and policy. A review of relevant legislation, policies, documents and strategies in the case study areas supports this conclusion. In particular, components of the Consequentialist ethical framework (a perspective that can be associated with sustainable development and sustainability) are most often acknowledged in the statements of intent of the participants and water resource legislation and policies. Respondents also indicated that value positions associated with the Intrinsic Value ethical framework influenced policy preparation and decision-making; however, the ethical considerations associated with this framework are not as obvious in the language and intent of relevant legislation, plans, documents, and strategies. The case study participants in both areas supported all six proposed principles of the proposed water ethic and offered only minor modifications to the presented wording and intent. The endorsed principles of the proposed water ethic are: (1) allocate sufficient water to maintain and enhance ecosystem integrity; (2) establish conservation and efficiency measures as a priority over new supply initiatives in water resources planning; (3) meet basic human needs and enhance equity; (4)establish open and participative decision-making processes; (5) identify and seek to obtain multiple sustainability benefits from water-centered initiatives; and, (6) explicitly acknowledge system complexity and emphasize precaution. The feedback from the participants about the proposed water ethic, in association with the results of the ethical frameworks, informed the eight implementation recommendations, including: (1) entrench a water ethic vision in Provincial and municipal legislation; (2) work from within existing governance structures and institutional arrangements; (3) use an incremental model of decision-making; (4) provide specific policy examples for each principle within a water ethic; (5) include realistic and measurable targets within the policies; (6) accept that all six water ethic principles are unlikely to be accepted at once; (7) ensure the overall vision of the water ethic, principles, associated examples, and measureable targets, are defensible; and, (8)acknowledge the importance of strategy. The recommendations acknowledge that while the proposed water ethic is presented as a package and each principle is valuable, conflict and trade-offs may occur during the implementation process. The recommendations are therefore pragmatic and take into account the current governance structures and institutional arrangements. There is a growing recognition that understanding the underlying ethical perspectives that influence decision-makers may contribute to more effective water resources management legislation and policy. This research adds to this body of knowledge by showing that it is possible to identify ethical frameworks, extract the defining characteristics associated with each framework, and use case studies to suggest which ethical frameworks assert varying degrees of influence. This link between theory and practice may help organizations recognize what ethical considerations influence decision-making and identify the strengths and limitations of these ethical approaches to managing water resources. In addition, prior to this study, research had only been conducted into the identification of principles for the ethical use of water and not into the potential for implementation of a realistic and desirable water ethic that reflects sustainability and lasting well-being at the municipal level of government in Canada. Several opportunities exist to build on this research. They include (1) investigate if the ethical intent of legislation and policy related to water resources management is put into practice, (2) identify other ethical frameworks that may apply to decision-making, (3) focus on political decision-makers and their claims and intentions about water use, (4) test the implementation of the water ethic proposed in this study, and (5) investigate how to integrate ethical considerations about water into checklists and protocols related to land use development, professional codes of conduct and standards, institutional and organizational training programs, performance measures for official plans, and as standard components for municipal council reports and ministerial presentations. This exploratory research concludes that policy makers are willing to become more aware of their underlying ethical underpinnings and to learn how ethical considerations embedded in legislation and policy have the potential to exert significant influence over the behaviour of current and future water users.

The music press and music journalism are rarely subjected to substantial academic investigation. Analysis of journalism often focuses on the production of news across various platforms to understand the nature of politics and public debate in the contemporary era. But it is not possible, nor is it necessary, to analyse all emerging forms of journalism in the same way for they usually serve quite different purposes. Music journalism, for example, offers consumer guidance based on the creation and maintenance of a relationship between reader and writer. By focusing on the changing aspects of this relationship, an analysis of music journalism gives us an understanding of the changing nature of media production, media texts and media readerships. Music journalism is dialogue. It is a dialogue produced within particular critical frameworks that speak to different readers of the music press in different ways. These frameworks are continually evolving and reflect the broader social trajectory in which music journalism operates. Importantly, the evolving nature of music journalism reveals much about the changing consumption of popular music. Different types of consumers respond to different types of guidance that employ a variety of critical approaches. This thesis, therefore, argues that the production of music journalism is one that is influenced by the practices of consumption.