In situ dehydration behavior of zeolite-like pentagonite: A single-crystal X-ray study

The structural modifications upon heating of pentagonite, Ca(VO)(Si4O10)·4H2O (space group Ccm21, a=10.3708(2), b=14.0643(2), c=8.97810(10) Å, V=1309.53(3) Å3) were investigated by in situ temperature dependent single-crystal X-ray structure refinements. Diffraction data of a sample from Poona district (India) have been measured in steps of 25 up to 250 °C and in steps of 50 °C between 250 and 400 °C. Pentagonite has a porous framework structure made up by layers of silicate tetrahedra connected by V4+O5 square pyramids. Ca and H2O molecules are extraframework occupants. Room temperature diffraction data allowed refinement of H positions. The hydrogen-bond system links the extraframework occupants to the silicate layers and also interconnects the H2O molecules located inside the channels. Ca is seven-fold coordinated forming four bonds to O of the tetrahedral framework and three bonds to extraframework H2O. The H2O molecule at O9 showing a high displacement parameter is not bonded to Ca. The dehydration in pentagonite proceeds in three steps. At 100 °C the H2O molecule at O8 was released while O9 moved towards Ca. As a consequence the displacement parameter of H2O at O9 halved compared to that at room temperature. The unit-cell volume decreased to 1287.33(3) Å3 leading to a formula with 3H2O per formula unit (pfu). Ca remained seven-fold coordinated. At 175 °C Ca(VO)(Si4O10)·3H2O transformed into a new phase with 1H2O molecule pfu characterized by doubling of the c axis and the monoclinic space group Pn. Severe bending of specific TOT angles led to contraction of the porous three-dimensional framework. In addition, H2O at O9 was expelled while H2O at O7 approached a position in the center of the channel. The normalized volume decreased to 1069.44(9) Å3. The Ca coordination reduced from seven- to six-fold. At 225 °C a new anhydrous phase with space group Pna21 but without doubling of c had formed. Release of H2O at O7 caused additional contraction of TOT angles and volume reduction (V=1036.31(9) Å3). Ca adopted five-fold coordination. During heating excursion up to 400 °C this anhydrous phase remained preserved. Between room temperature and 225 °C the unit-cell volume decreased by 21% due to dehydration. The dehydration steps compare well with the thermo-gravimetric data reported in the literature.

High-temperature induced dehydration, phase transition and exsolution in amicite: A single-crystal X-ray study

Temperature dependent single-crystal X-ray data were collected on amicite K4Na4(Al8Si8O32)·11H2O from Kola Peninsula (Russia) in steps of 25 °C from room temperature to 175 °C and of 50 °C up to 425 °C. At room temperature amicite has space group I2 with a = 10.2112(1), b = 10.4154(1), c = 9.8802(1) Å, β = 88.458(1)°, V = 1050.416(18) Å3. Its crystal structure is based on a Si–Al ordered tetrahedral framework of the GIS type with two systems of eight-membered channels running along the a and c axes. Extraframework K and Na cations are ordered at two fully occupied sites. Above 75 °C amicite was found to partly dehydrate into two separate but coherently intergrown phases, both of space group I2/a, one K-rich ∼K8(Al8Si8O32) ·4H2O (at 75 °C: a = 10.038(2), b = 9.6805(19), c = 9.843(2) Å, β = 89.93(3)°, V = 956.5(3) Å3) and the other Na-rich ∼Na8(Al8Si8O32)·2H2O (at 75 °C: a = 9.759(2), b = 8.9078(18), c = 9.5270(19) Å, β = 89.98(3)°, V = 828.2(3) Å3). Upon further heating above 75 °C the Na- and K-phases lost remaining H2O with only minor influence on the framework structure and became anhydrous at 175 °C and 375 °C, respectively. The two anhydrous phases persisted up to 425 °C. Backscattered electron images of a heated crystal displayed lamellar intergrowth of the K- and Na-rich phases. Exposed to ambient humid conditions K- and Na-rich phases rehydrated and conjoined to the original one phase I2 structure.

In situ dehydration behavior of zeolite-like cavansite: A single-crystal X-ray study

To track dehydration behavior of cavansite, Ca(VO)(Si4O10)·4H2O space group Pnma, a = 9.6329(2), b = 13.6606(2), c = 9.7949(2) Å, V = 1288.92(4) Å3 single-crystal X-ray diffraction data on a crystal from Wagholi quarry, Poona district (India) were collected up to 400 °C in steps of 25 °C up to 250 °C and in steps of 50 °C between 250 and 400 °C. The structure of cavansite is characterized by layers of silicate tetrahedra connected by V4+O5 square pyramids. This way a porous framework structure is formed with Ca and H2O as extraframework occupants. At room temperature, the hydrogen bond system was analyzed. Ca is eightfold coordinated by four bonds to O of the framework structure and four bonds to H2O molecules. H2O linked to Ca is hydrogen bonded to the framework and also to adjacent H2O molecules. The dehydration in cavansite proceeds in four steps.At 75 °C, H2O at O9 was completely expelled leading to 3 H2O pfu with only minor impact on framework distortion and contraction V = 1282.73(3) Å3. The Ca coordination declined from originally eightfold to sevenfold and H2O at O7 displayed positional disorder.At 175 °C, the split O7 sites approached the former O9 position. In addition, the sum of the three split positions O7, O7a, and O7b decreased to 50% occupancy yielding 2 H2O pfu accompanied by a strong decrease in volume V = 1206.89(8) Å3. The Ca coordination was further reduced from sevenfold to sixfold.At 350 °C, H2O at O8 was released leading to a formula with 1 H2O pfu causing additional structural contraction (V = 1156(11) Å3). At this temperature, Ca adopted fivefold coordination and O7 rearranged to disordered positions closer to the original O9 H2O site.At 400 °C, cavansite lost crystallinity but the VO2+ characteristic blue color was preserved. Stepwise removal of water is discussed on the basis of literature data reporting differential thermal analyses, differential thermo-gravimetry experiments and temperature dependent IR spectra in the range of OH stretching vibrations.

Spy: A Flexible Code Profiling Framework

Code profiling is an essential activity to increase software quality. It is commonly employed in a wide variety of tasks, such as supporting program comprehension, determining execution bottlenecks, and assessing code coverage by unit tests. Spy is an innovative framework to easily build profilers and visualize profiling information. The profiling information is obtained by inserting dedicated code before or after method execution. The gathered profiling information is structured in line with the application structure in terms of packages, classes, and methods. Spy has been instantiated on four occasions so far. We created profilers dedicated to test coverage, time execution, type feedback, and profiling evolution across version. We also integrated Spy in the Pharo IDE. Spy has been implemented in the Pharo Smalltalk programming language and is available under the MIT license.

The FORA Framework - A Fuzzy Grassroots Ontology for Online Reputation Management

Online reputation management deals with monitoring and influencing the online record of a person, an organization or a product. The Social Web offers increasingly simple ways to publish and disseminate personal or opinionated information, which can rapidly have a disastrous influence on the online reputation of some of the entities. The author focuses on the Social Web and possibilities of its integration with the Semantic Web as resource for a semi-automated tracking of online reputations using imprecise natural language terms. The inherent structure of natural language supports humans not only in communication but also in the perception of the world. Thereby fuzziness is a promising tool for transforming those human perceptions into computer artifacts. Through fuzzy grassroots ontologies, the Social Semantic Web becomes more naturally and thus can streamline online reputation management. For readers interested in the cross-over field of computer science, information systems, and social sciences, this book is an ideal source for becoming acquainted with the evolving field of fuzzy online reputation management in the Social Semantic Web area. ​

The FORA Framework - A Fuzzy Grassroots Ontology for Online Reputation Management

Online reputation management deals with monitoring and influencing the online record of a person, an organization or a product. The Social Web offers increasingly simple ways to publish and disseminate personal or opinionated information, which can rapidly have a disastrous influence on the online reputation of some of the entities. This dissertation can be split into three parts: In the first part, possible fuzzy clustering applications for the Social Semantic Web are investigated. The second part explores promising Social Semantic Web elements for organizational applications,while in the third part the former two parts are brought together and a fuzzy online reputation analysis framework is introduced and evaluated. Theentire PhD thesis is based on literature reviews as well as on argumentative-deductive analyses.The possible applications of Social Semantic Web elements within organizations have been researched using a scenario and an additional case study together with two ancillary case studies—based on qualitative interviews. For the conception and implementation of the online reputation analysis application, a conceptual framework was developed. Employing test installations and prototyping, the essential parts of the framework have been implemented.By following a design sciences research approach, this PhD has created two artifacts: a frameworkand a prototype as proof of concept. Bothartifactshinge on twocoreelements: a (cluster analysis-based) translation of tags used in the Social Web to a computer-understandable fuzzy grassroots ontology for the Semantic Web, and a (Topic Maps-based) knowledge representation system, which facilitates a natural interaction with the fuzzy grassroots ontology. This is beneficial to the identification of unknown but essential Web data that could not be realized through conventional online reputation analysis. Theinherent structure of natural language supports humans not only in communication but also in the perception of the world. Fuzziness is a promising tool for transforming those human perceptions intocomputer artifacts. Through fuzzy grassroots ontologies, the Social Semantic Web becomes more naturally and thus can streamline online reputation management.

An indicator framework for assessing livelihood resilience in the context of social–ecological dynamics

Livelihood resilience draws attention to the factors and processes that keep livelihoods functioning despite change and thus enriches the livelihood approach which puts people, their differential capabilities to cope with shocks and how to reduce poverty and improve adaptive capacity at the centre of analysis. However, the few studies addressing resilience from a livelihood perspective take different approaches and focus only on some dimensions of livelihoods. This paper presents a framework that can be used for a comprehensive empirical analysis of livelihood resilience. We use a concept of resilience that considers agency as well as structure. A review of both theoretical and empirical literature related to livelihoods and resilience served as the basis to integrate the perspectives. The paper identifies the attributes and indicators of the three dimensions of resilience, namely, buffer capacity, self-organisation and capacity for learning. The framework has not yet been systematically tested; however, potentials and limitations of the components of the framework are explored and discussed by drawing on empirical examples from literature on farming systems. Besides providing a basis for applying the resilience concept in livelihood-oriented research, the framework offers a way to communicate with practitioners on identifying and improving the factors that build resilience. It can thus serve as a tool for monitoring the effectiveness of policies and practices aimed at building livelihood resilience.

Causes, forms and consequences of the professionalization of international sport federa-tions in Switzerland: Conceptual framework and first results

Synopsis: Sport organisations are facing multiple challenges originating from an increasingly complex and dynamic environment in general, and from internal changes in particular. Our study seeks to reveal and analyse the causes for professionalization processes in international sport federations, the forms resulting from it, as well as related consequences. Abstract: AIM OF ABSTRACT/PAPER - RESEARCH QUESTION Sport organisations are facing multiple challenges originating from an increasingly complex and dynamic environment in general, and from internal changes in particular. In this context, professionalization seems to have been adopted by sport organisations as an appropriate strategy to respond to pressures such as becoming more “business-like”. The ongoing study seeks to reveal and analyse the internal and external causes for professionalization processes in international sport federations, the forms resulting from it (e.g. organisational, managerial, economic) as well as related consequences on objectives, values, governance methods, performance management or again rationalisation. THEORETICAL BACKGROUND/LITERATURE REVIEW Studies on sport as specific non-profit sector mainly focus on the prospect of the “professionalization of individuals” (Thibault, Slack & Hinings, 1991), often within sport clubs (Thiel, Meier & Cachay, 2006) and national sport federations (Seippel, 2002) or on organisational change (Griginov & Sandanski, 2008; Slack & Hinings, 1987, 1992; Slack, 1985, 2001), thus leaving broader analysis on governance, management and professionalization in sport organisations an unaccomplished task. In order to further current research on above-mentioned topics, our intention is to analyse causes, forms and consequences of professionalisation processes in international sport federations. The social theory of action (Coleman, 1986; Esser, 1993) has been defined as appropriate theoretical framework, deriving in the following a multi-level framework for the analysis of sport organisations (Nagel, 2007). In light of the multi-level framework, sport federations are conceptualised as corporative actors whose objectives are defined and implemented with regard to the interests of member organisations (Heinemann, 2004) and/or other pressure groups. In order to understand social acting and social structures (Giddens 1984) of sport federations, two levels are in the focus of our analysis: the macro level examining the environment at large (political, social, economic systems etc.) and the meso level (Esser, 1999) examining organisational structures, actions and decisions of the federation’s headquarter as well as member organisations. METHODOLOGY, RESEARCH DESIGN AND DATA ANALYSIS The multi-level framework mentioned seeks to gather and analyse information on causes, forms and consequences of professionalization processes in sport federations. It is applied in a twofold approach: first an exploratory study based on nine semi-structured interviews with experts from umbrella sport organisations (IOC, WADA, ASOIF, AIOWF, etc.) as well as the analysis of related documents, relevant reports (IOC report 2000 on governance reform, Agenda 2020, etc.) and important moments of change in the Olympic Movement (Olympic revenue share, IOC evaluation criteria, etc.); and secondly several case studies. Whereas the exploratory study seeks more the causes for professionalization on an external, internal and headquarter level as depicted in the literature, the case studies rather focus on forms and consequences. Applying our conceptual framework, the analysis of forms is built around three dimensions: 1) Individuals (persons and positions), 2) Processes, structures (formalisation, specialisation), 3) Activities (strategic planning). With regard to consequences, we centre our attention on expectations of and relationships with stakeholders (e.g. cooperation with business partners), structure, culture and processes (e.g. governance models, performance), and expectations of and relationships with member organisations (e.g. centralisation vs. regionalisation). For the case studies, a mixed-method approach is applied to collect relevant data: questionnaires for rather quantitative data, interviews for rather qualitative data, as well as document and observatory analysis. RESULTS, DISCUSSION AND IMPLICATIONS/CONCLUSIONS With regard to causes of professionalization processes, we analyse the content of three different levels: 1. the external level, where the main pressure derives from financial resources (stakeholders, benefactors) and important turning points (scandals, media pressure, IOC requirements for Olympic sports); 2. the internal level, where pressure from member organisations turned out to be less decisive than assumed (little involvement of member organisations in decision-making); 3. the headquarter level, where specific economic models (World Cups, other international circuits, World Championships), and organisational structures (decision-making procedures, values, leadership) trigger or hinder a federation’s professionalization process. Based on our first analysis, an outline for an economic model is suggested, distinguishing four categories of IFs: “money-generating IFs” being rather based on commercialisation and strategic alliances; “classical Olympic IFs” being rather reactive and dependent on Olympic revenue; “classical non-Olympic IFs” being rather independent of the Olympic Movement; and “money-receiving IFs” being dependent on benefactors and having strong traditions and values. The results regarding forms and consequences will be outlined in the presentation. The first results from the two pilot studies will allow us to refine our conceptual framework for subsequent case studies, thus extending our data collection and developing fundamental conclusions. References: Bayle, E., & Robinson, L. (2007). A framework for understanding the performance of national governing bodies of sport. European Sport Management Quarterly, 7, 249–268 Chantelat, P. (2001). La professionnalisation des organisations sportives: Nouveaux débats, nouveaux enjeux [Professionalisation of sport organisations]. Paris: L’Harmattan. Dowling, M., Edwards, J., & Washington, M. (2014). Understanding the concept of professionalization in sport management research. Sport Management Review. Advance online publication. doi: 10.1016/j.smr.2014.02.003 Ferkins, L. & Shilbury, D. (2012). Good Boards Are Strategic: What Does That Mean for Sport Governance? Journal of Sport Management, 26, 67-80. Thibault, L., Slack, T., & Hinings, B. (1991). Professionalism, structures and systems: The impact of professional staff on voluntary sport organizations. International Review for the Sociology of Sport, 26, 83–97.

Comparability of Outcome Frameworks in Medical Education: Implications for framework development

Background: The demand for international harmonization in medical education increases with the growing mobility of students and health professionals. Many medical societies and governmental offices have issued outcome frameworks (OF), which describe aims and contents of medical education based on competencies. These national standards affect the development of curricula as well as assessment and licensing procedures. Comparing OF and identifying factors that limit their comparability may thus foster international harmonization of medical education. Summary of Work: We conducted a systematic search for national OF in MedLine, EmBase and the internet. We included all OF in German or English that resulted from a national consensus process and were published or endorsed by a national society or governmental body. We extracted information in five predetermined categories: history of origin, audience, formal structure, medical schooling system and key terms. Summary of Results: Out of 1816 results, 13 OF were included into further analyses. OF reference each other, often without addressing existing differences (e.g. in target audiences). The two most cited OF are “CanMEDs” and “Scottish Doctor”. OF differ especially in their level of detail as well as in the underlying educational system. Discussion and Conclusions: Based on our results we propose a two-step blueprint for OF, that may help to establish comparability for internationally aligned key features – so-called “core competencies” – while at the same time allowing for necessary regional adaptations in terms of “secondary competencies”. Take-home messages: Considerable differences in at least five categories of OF currently hinder the comparability of outcome frameworks.

Can we constrain the interior structure of rocky exoplanets from mass and radius measurements?

Aims. We present an inversion method based on Bayesian analysis to constrain the interior structure of terrestrial exoplanets, in the form of chemical composition of the mantle and core size. Specifically, we identify what parts of the interior structure of terrestrial exoplanets can be determined from observations of mass, radius, and stellar elemental abundances. Methods. We perform a full probabilistic inverse analysis to formally account for observational and model uncertainties and obtain confidence regions of interior structure models. This enables us to characterize how model variability depends on data and associated uncertainties. Results. We test our method on terrestrial solar system planets and find that our model predictions are consistent with independent estimates. Furthermore, we apply our method to synthetic exoplanets up to 10 Earth masses and up to 1.7 Earth radii, and to exoplanet Kepler-36b. Importantly, the inversion strategy proposed here provides a framework for understanding the level of precision required to characterize the interior of exoplanets. Conclusions. Our main conclusions are (1) observations of mass and radius are sufficient to constrain core size; (2) stellar elemental abundances (Fe, Si, Mg) are principal constraints to reduce degeneracy in interior structure models and to constrain mantle composition; (3) the inherent degeneracy in determining interior structure from mass and radius observations does not only depend on measurement accuracies, but also on the actual size and density of the exoplanet. We argue that precise observations of stellar elemental abundances are central in order to place constraints on planetary bulk composition and to reduce model degeneracy. We provide a general methodology of analyzing interior structures of exoplanets that may help to understand how interior models are distributed among star systems. The methodology we propose is sufficiently general to allow its future extension to more complex internal structures including hydrogen- and water-rich exoplanets.