Diversity in Catalytic Reactions of Propargylic Diazoesters

Abstract Title of Document: Diversity in Catalytic Reactions of Propargylic Diazoesters Huang Qiu, Doctor of Philosophy, 2016 Directed By: Professor Michael P. Doyle, Department of Chemistry and Biochemistry Propargylic aryldiazoesters, which possess multiple reactive functional groups in a single molecule, were expected to undergo divergent reaction pathways as a function of catalysts. A variety of transition metal complexes including rhodium(II), palladium(II), silver(I), mercury(II), copper(I and II), and cationic gold (I) complexes have been examined to be effective in the catalytic domino reactions of propargylic aryldiazoesters. An unexpected Lewis acid catalyzed pathway was also discovered by using FeCl3 as the catalyst. Under the catalysis of selected gold catalysts, propargylic aryldiazoesters exist in equilibrium with 1-aryl-1,2-dien-1-yl diazoacetate allenes that are rapidly formed at room temperature through 1,3-acyloxy migration. The newly formed allenes further undergo a metal-free rearrangement in which the terminal nitrogen of the diazo functional group adds to the central carbon of the allene initiating a sequence of bond forming reactions resulting in the production of 1,5-dihydro-4H-pyrazol-4-ones in good yields. These 1,5-dihydro-4H-pyrazol-4-ones undergo intramolecular 1,3-acyl migration to form an equilibrium mixture or quantitatively transfer the acyl group to an external nucleophile with formation of 4-hydroxypyrazoles. In the presence of a pyridine-N-oxide, both E- and Z-1,3-dienyl aryldiazoacetates are formed in high combined yields by Au(I)-catalyzed rearrangement of propargyl arylyldiazoacetates at short reaction times. Under thermal reactions the E-isomers form the products from intramolecular [4+2]-cycloaddition with H‡298 = 15.6 kcal/mol and S‡298= -27.3 cal/ (mol•degree). The Z-isomer is inert to [4+2]-cycloaddition under these conditions. The Hammett relationships from aryl-substituted diazo esters ( = +0.89) and aryl-substituted dienes ( = -1.65) are consistent with the dipolar nature of this transformation. An unexpected reaction for the synthesis of seven-membered conjugated 1,4-diketones from propargylic diazoesters with unsaturated imines was disclosed. To undergo this process vinyl gold carbene intermediates generated by 1,2-acyloxy migration of propargylic aryldiazoesters undergo a formal [4+3]-cycloaddition, and the resulting aryldiazoesters tethered dihydroazepines undergo an intricate metal-free process to form observed seven-membered conjugated 1,4-diketones with moderate to high yields.

Assessing the mitochondrial DNA diversity of the Chagas disease vector Triatoma sordida (Hemiptera: Reduviidae)

Triatoma sordida is a species that transmits Trypanosoma cruzi to humans. In Brazil, T. sordida currently deserves special attention because of its wide distribution, tendency to invade domestic environments and vectorial competence. For the planning and execution of control protocols to be effective against Triatominae, they must consider its population structure. In this context, this study aimed to characterise the genetic variability of T. sordida populations collected in areas with persistent infestations from Minas Gerais, Brazil. Levels of genetic variation and population structure were determined in peridomestic T. sordida by sequencing a polymorphic region of the mitochondrial cytochrome b gene. Low nucleotide and haplotype diversity were observed for all 14 sampled areas; π values ranged from 0.002-0.006. Most obtained haplotypes occurred at low frequencies, and some were exclusive to only one of the studied populations. Interpopulation genetic diversity analysis revealed strong genetic structuring. Furthermore, the genetic variability of Brazilian populations is small compared to that of Argentinean and Bolivian specimens. The possible factors related to the reduced genetic variability and strong genetic structuring obtained for studied populations are discussed in this paper.

Europeanization beyond the EU: The case of Georgia.

320 p.

Políticas de geração distribuída e sustentabilidade do sistema elétrico

Tese (doutorado)—Universidade de Brasília, Centro de Desenvolvimento Sustentável, 2015.

A inclusão da diversidade linguística no ensino básico na perspectiva de pais e professores : Um estudo de caso no interior rural

É num quadro internacional caracterizado pela crescente multi/interculturalidade das populações escolares, que se inscreve o presente trabalho de investigação, que tem como tema a inclusão da diversidade linguística no ensino básico, no contexto específico da Escola Básica com Jardim-de-infância de Ammaia, situada no interior rural de Portugal, mais precisamente no Alto Alentejo. A pesquisa, alicerçada no paradigma interpretativo, caracterizou-se por uma investigação de cariz qualitativo, mais precisamente um estudo de caso, que teve como principal fonte de recolha de dados as entrevistas em profundidade, realizadas a quatro docentes e a um encarregado de educação imigrante, as quais foram objecto de análise de conteúdo posterior. Entre os objectivos do estudo encontravam-se a identificação de algumas respostas educativas organizadas pelas escolas, no âmbito da sua autonomia, com vista a inclusão dos alunos migrantes e dos principais factores de favorecimento e de obstrução à inclusão dos mesmos, na perspectiva e concepção dos mais directos intervenientes no processo, nomeadamente os professores e os pais ou encarregados de educação destes alunos. Da análise e interpretação dos resultados ficou expresso o esforço que as comunidades educativas vêm fazendo com vista a adaptarem-se à inclusão da multi/interculturalidade, designadamente a linguística, não obstante as dificuldades com que se debatem, tais como a falta de formação da docente e a escassez de recursos para garantir o sucesso destes alunos. Além disso, permitiu comprovar alguns dados apontados pela investigação, nomeadamente a disseminação desta população por todo o território nacional e a generalização da prática denominada por «desclassificação», através da colocação dos alunos em níveis inferiores aos que frequentavam no estrangeiro. Foi igualmente possível apontar alguns dos factores que mais contribuirão para a sua inclusão, dos quais se destaca o estabelecimento de relações afectivas sólidas por parte destes alunos com os seus pares e a necessidade de fazer uso de métodos progressivos e flexíveis, adaptados às necessidades e capacidades dos alunos, capazes de lhes garantirem um nível adequado de proficiência da língua portuguesa, enquanto factor essencial ao seu sucesso educativo. ABSTRACT: It is in an international context, characterized by the growing cultural, ethnical, linguistic diversity and other aspects of school populations, which lead educational communities to severe changes, that the present investigational work refers to, whose topic is the inclusion of language diversity in the basic teaching, in the specific context of Escola Básica com Jardim de Infância de Ammaia, located in the rural interior of Portugal, to be more accurate, in the North Alentejo region. The research, based on the interpretational paradigm, is characterized by a qualitative investigation, more precisely in a case study, which had as a main source of data gathering the interviews done to four teachers and an immigrant parent, which were subjected to posterior content analysis. Among the aims of the study were the identification of some educational responses organized by schools, in the extent of its autonomy, regarding the inclusion of migrant pupils and the main favoring and obstruction factors to the inclusion of these same pupils, in the perspective, conception and comprehension of the most direct intervenient in the process, namely teachers and parents of these pupils. From the analysis and interpretation of the results it is visible the effort educational communities have been making in order to adapt themselves to the inclusion of the multi/interculturality, namely linguistic, in spite of the difficulties they find, such as the lack of formation of teachers and the scarcity of resources to guarantee the success of this new school population. Likewise, it allowed to prove some data pointed out by the investigation, namely the dissemination of this population throughout the national territory and the generalization of the practice called "disqualification”, by placing pupils in inferior levels to those they attended abroad. It was also possible to point out some of the factors that most contribute to their inclusion, of which stand out the establishment of solid affective relationship between these pupils and their peers and the necessity to use progressive and flexible methods, adapted to the needs and capacities of the pupils, able to guarantee an adequate proficiency level of the Portuguese language, as the key factor to their educational success.

Successional dynamics in inland dune shrub communities drive changes in functional diversity

Communities can be defined as assemblages of species coexisting under particular environments. The relationship between environment and species are regulated by both environmental requirements –which ultimately determine the species capacity to establish and survive in a particular environment– and the ecological interactions occurring during assembly processes –which also determine community composition by conditioning species coexistence. In this context, plant functional traits are attributes that represent ecological strategies and determine how plants respond to environmental factors and interact with other species. Therefore, the analysis of how traits vary through the dynamics of communities, such as along successions, can give insights about how environmental requirements and species interactions may determine the composition and functional structure of these communities. The xerophytic shrub communities inhabiting inland sand dunes in SW Portugal are characterized by successional processes that are mainly driven by local (edaphic gradients and human disturbance) and regional (climate) processes. Therefore, they constitute an appropriate system for studying species interactions and environmentcommunity co-variations based on functional terms. Using these communities as a model, we evaluate the hypothesis that successional community changes in species composition of xerophytic shrub communities can result in concurrent changes in functional diversity

Composite Indicators for the Family Change: ‘Familism' vs ‘Individualism' in the International Context

The aim of this paper is to propose a composite indicator to measure ‘familism’, conformed by two main dimensions: values on one hand (duty to take care of the family, importance of the family, sacrifices for the family...) and behaviours, on the other (predominance of married couples instead of cohabitant couples, high frequency of contact among members, family support…). In contrast to this idea of ‘familism’ we find that of individualism, that defends the independence of family members, tolerance to new family models, cohabitation instead of marriage,… , that implies less frequency of interaction among relatives and more governmental intervention towards children and elderly care. We observe that a higher degree of ‘familism’ does not always match with a lower degree of individualism when both dimensions, attitudes and behaviours, are considered. For instance, we find countries which are individualist in values but not in behaviours (such as Spain), whilst others, such as Japan, are ‘familist’ both in values and behaviours and finally, others, such as Sweden, are individualist with regards to both perspectives. We propose two different methodological approaches to the question. First, we use microdata from the Family, Work and Gender Roles module of the International Social Survey Programme-ISSP (years 1994, 2002 and 2012), in which 45 countries have participated. Information for the three rounds is collected for 17 countries with very different family values and welfare systems (for instance, Sweden, Japan, Russia, Spain, United Kingdom or the United States). From this data source, we create a first index on familism that can be related to individual sociodemographic characteristics. Second, we complete it through the inclusion of macro data (such as the divorce rate per country), in order to refine comparison at a country level by adding new variables to the previous index.

Composite Indicators for the Family Change: ‘Familism' vs ‘Individualism' in the International Context

The aim of this paper is to propose a composite indicator to measure ‘familism’, conformed by two main dimensions: values on one hand (duty to take care of the family, importance of the family, sacrifices for the family...) and behaviours, on the other (predominance of married couples instead of cohabitant couples, high frequency of contact among members, family support…). In contrast to this idea of ‘familism’ we find that of individualism, that defends the independence of family members, tolerance to new family models, cohabitation instead of marriage,… , that implies less frequency of interaction among relatives and more governmental intervention towards children and elderly care. We observe that a higher degree of ‘familism’ does not always match with a lower degree of individualism when both dimensions, attitudes and behaviours, are considered. For instance, we find countries which are individualist in values but not in behaviours (such as Spain), whilst others, such as Japan, are ‘familist’ both in values and behaviours and finally, others, such as Sweden, are individualist with regards to both perspectives. We propose two different methodological approaches to the question. First, we use microdata from the Family, Work and Gender Roles module of the International Social Survey Programme-ISSP (years 1994, 2002 and 2012), in which 45 countries have participated. Information for the three rounds is collected for 17 countries with very different family values and welfare systems (for instance, Sweden, Japan, Russia, Spain, United Kingdom or the United States). From this data source, we create a first index on familism that can be related to individual sociodemographic characteristics. Second, we complete it through the inclusion of macro data (such as the divorce rate per country), in order to refine comparison at a country level by adding new variables to the previous index.

Plant-mediated effects on microbial diversity in mesocosms of an oligotrophic bog

Globally, peatlands occupy a small portion of terrestrial land area but contain up to one-third of all soil organic carbon. This carbon pool is vulnerable to increased decomposition under projected climate change scenarios but little is known about how plant functional groups will influence microbial communities responsible for regulating carbon cycling processes. Here we examined initial shifts in microbial community structure within two sampling depths under plant functional group manipulations in mesocosms of an oligotrophic bog. Microbial community composition for bacteria and archaea was characterized using targeted 16S rRNA Illumina gene sequencing. We found statistically distinct spatial patterns between the more shallow 10-20 cm sampling depth and the deeper 30-40 cm depth. Significant effects by plant functional groups were found only within the 10-20 cm depth, indicating plant-mediated microbial community shifts respond more quickly near the peat surface. Specifically, the relative abundance of Acidobacteria decreased under ericaceous shrub treatments in the 10-20 cm depth and was replaced by increased abundance of Gammaproteobacteria and Bacteroidetes. In contrast, the sedge rhizosphere continued to be dominated by Acidobacteria but also promoted an increase in the relative recovery of Alphaproteobacteria and Verrucomicrobia. These initial results suggest microbial communities under ericaceous shrubs may be limited by anaerobic soil conditions accompanying high water table conditions, while sedge aerenchyma may be promoting aerobic taxa in the upper peat rhizosphere regardless of ambient soil oxygen limitations.

An empirical investigation of the impact of global energy transition on Nigerian oil and gas exports

18 months embargo on the thesis and check appendix for copy right materials

La atención a la diversidad: experiencia del Proyecto UNA Educación de Calidad, de la Universidad Nacional de Costa Rica

Recibido 16 de julio de 2010 • Aceptado 31 de agosto de 2010 • Corregido 04 de octubre de 2010  Debido al marco jurídico actual, en los últimos años, el sistema educativo costarricense ha experimentado cambios significativos, tanto en los niveles internacional como nacional. Estos van desde la promulgación de la Ley 7600 Igualdad de Oportunidades para las Personas con Discapacidad en Costa Rica (Costa Rica, Asamblea Legislativa,1996) hasta el planteamiento de la Ley 8661 Convención sobre los Derechos Humanos de las Personas con Discapacidad (Costa Rica, Asamblea Legislativa, 2008). Por lo anterior, el espacio temporal en el que emergió el Proyecto UNA Educación de Calidad, en 1998 y el contexto en el cual estaba inmerso el Sistema Educativo Nacional, particularmente, en el ámbito universitario, la propuesta pedagógica que se presenta da muestra de una transición entre el modelo rehabilitador y el modelo social, específicamente, dentro de cada uno de estos, el respectivo abordaje educativo, que abarca desde los procedimientos de la integración a los de la educación inclusiva. Desde esta perspectiva, se presenta las vivencias y estrategias desplegadas desde el Proyecto UNA Educación de Calidad. El fin es proporcionar apoyo y seguimiento, en su formación profesional, a un grupo de la diversidad, constituido por los estudiantes con necesidades educativas matriculados en la Universidad Nacional. De esta forma, se pretenden hacer efectivos sus derechos de acceder a una educación superior de calidad, de acuerdo con sus características personales y sociales, y promover su permanencia e inserción socio-laboral. Los retos que impone la atención a la diversidad en el contexto universitario son un desafío plasmado en el quehacer cotidiano del Proyecto UNA Educación de Calidad. Estas transformaciones se vislumbran en la constante reconstrucción de las estrategias utilizadas, al tener, como aspectos esenciales, el empleo de equipo tecnológico y programas de computación especializados. Estos les permitirán a los estudiantes acceder a la información y a la comunicación; la asesoría y la capacitación de los académicos y del personal administrativo; el establecimiento de estrategias de apoyo colaborativo entre los miembros de la comunidad universitaria, así como, la búsqueda de cooperación en el ámbito nacional e internacional para el desarrollo de nueva iniciativas.

Irrigation and drainage canals role for plant diversity and nature conservation

Aims: With this research, we wanted to investigate and promote the conservation of biodiversity in the network of drainage canals of the Po Valley Study area: The canal network of Bologna plain, long more than 1150 km (Po Valley, North Italy) Methods: In Chapter II we analyzed the geographical patterns that characterize our transects, the land use of their upstream basins, the water quality at the closure points of their river basins. In Chapter III we described the plant communities with some ecological information and we also tested the effect of the canal size on the plant communities. In Chapter IV we described the relation beetween some functional traits of the plant species sampled and some environmental parameters Results: A total of 272 species were sampled in 118 transects. The plant communities of the drainage canals have been found to have a significant influence: the geographical pattern "proximity to protected areas", the class of land use "agrozootechnical settlements", and some water parameters. The analysis of the parameter "canal depth" indicated a significant distinction between small and large canals based on plant communities. The functional composition of the plant communities was affected by the bank aspect, the inclusion/exclusion from the protected areas and the upstream basin land uses. Moreover, the functional groups of species responded differently to environmental drivers, water quality gradients and were influenced by a combination of environmental stresses Conclusions: This research confirms the key role of the canals network in sustaining the plant richness in oversimplified landscapes. Considering the fragility of the floodplains and the global warming that is taking place, it is necessary to rethink the role of irrigation canals and their plant communities in the near future. This work reinforces the belief that long-term sampling plans and greater knowledge about canal management practices are needed

Inclusion in an age of mobility

Learning with mobiles in UK universities is not new and is not novel. It is, in fact, at least 10 years old, well-documented and comparable to activity in universities elsewhere in Western Europe, America and Asia Pacific. Continued and dramatic changes in the ownership, access and expectations of mobiles amongst university students and equally across UK society have suddenly propelled learning with mobiles to centre-stage as a feasible proposition but, it is now argued, only if students can bring-your-own-device. This has already catalysed discussion about authority, agency and control within university settings but the equally significant and profound implications for the inclusion agenda have not been articulated. This paper begins that process. A theoretical framework for social inclusion in this context is considered, identified and discussed. The paper reviews the progress and problems of the substantial and unique programme of mobile learning across UK higher education since 2000 in relation to its stance on inclusion, where this is apparent. These are all well-documented in academic and official sources; the paper does however also draw on the author's involvement in many of the events and initiatives. The paper raises however significant questions about this programme's meaning and direction in a world where now there is more, better, cheaper, faster, newer but different digital technology in the hands of students, potential students and everyone else than there is routinely in the educational institutions themselves. This digital technology, mobile technology, now allows learners to create, own, transform, discuss, discard, share, store and broadcast ideas, opinions, images and information, and to create and transform identities and communities. The paper argues that this epistemological revolution may mean that universities and colleges are no longer credible and authoritative gatekeepers to knowledge and its technologies and so the meaning and relevance of inclusion are much less clear. The paper proposes a new stance on inclusion.

Performing inclusion and exclusion in the peer group. Children's social organization and peer socializing practices in the classroom

This PhD thesis investigates children’s peer practices in two primary schools in Italy, focusing on the ordinary and the Italian L2 classroom. The study is informed by the paradigm of language socialization and considers peer interactions as a ‘double opportunity space’, allowing both children’s co-construction of their social organization and children’s sociolinguistic development. These two foci of attention are explored on the basis of children’s social interaction and of the verbal, embodied, and material resources that children agentively deploy during their mundane activities in the peer group. The study is based on a video ethnography that lasted nine months. Approximately 30 hours of classroom interactions were video-recorded, transcribed, and analyzed with an approach that combines the micro-analytic instruments of Conversation Analysis and the use of ethnographic information. Three main social phenomena were selected for analysis: (a) children’s enactment of the role of the teacher, (b) children’s reproduction of must-formatted rules, and (c) children’s argumentative strategies during peer conflict. The analysis highlights the centrality of the institutional frame for children’s peer interactions in the classroom. Moreover, the study illustrates that children socialize their classmates to the linguistic, social, and moral expectations of the context in and through various practices. Notably, these practices are also germane to the local negotiation of children’s social organization and hierarchy. Therefore, the thesis underlines that children’s peer interactions are both a resource for children’s sociolinguistic development and a potentially problematic locus where social exclusion is constructed and brought to bear. These insights are relevant for teachers’ professional practice. Children’s peer interactions are a resource that can be integrated in everyday didactics. Nevertheless, the role of the teacher in supervising and steering children’s peer practices appears crucial: an acritical view of children’s autonomous work, often implied in teaching methods such as peer tutoring, needs to be problematized.

Myanmar higher education in transition: the interplay between state authority, student politics and international actors.

The Myanmar “period of transition” (2011-2021) has often been described as a puzzle. Various scholars have begun to engage with the Myanmar context in an effort to grasp the essence of the transition it underwent during President Thein Sein’s USPD and Aung San Suu Kyi’s NLD governments. My work focuses on a specific policy sector, higher education, with a view to contributing to this scholarly debate regarding what was actually happening inside this complex country “transition”, especially in terms of collective participation in the process of political and social change. Reviewing existing scholarly literature on the politics of higher education, my study employs a triangle of analysis in which higher education reform is framed as the interplay of action on the part of “state authority”, “student politics” and “international actors”. What does this interplay lens reveal if we consider Myanmar’s “period of transition”? I argue that it shows the ambiguity and contradiction of tangible pushes for progressive social change that coexisted with authoritarian currents and the reinforcement of the societal position of dominant elites. At the policy level, ultimately, a convergence of interests between international actors and state authority served as the force driving the new higher education reform towards a neo-liberal model of governance and autonomy. This work unpacks the higher education reform process thanks to qualitative data gathered through extensive participant observation, in-depth interviewing and critical discourse analysis, shedding light on the rich narratives of those involved in the politics of higher education in Myanmar.