Many known synthetic methods enable the hydrolysis of alkynes with Markovnikov regioselectivity. In contrast, the synthetic chemist’s toolbox lacks broadly effective processes for the hydrolysis of alkynes with anti-Markovnikov regioselectivity. This thesis describes the development of new synthetic method that will help address this deficiency. This document begins with a review of the concepts of Markovnikov and anti-Markovnikov regioselectivity and an explanation of the broad extension of this terminology that is applied throughout the remainder of this thesis to encompass all alkyne substrates. Next, a review of the published methods of alkyne hydrolysis is presented, with emphasis on the internal alkyne substrates. The remainder, and bulk, of this thesis details the development of a new synthetic methodology that leverages regioselective radical thiolation chemistry to achieve anti-Markovnikov hydrolysis of alkynes. Internal alkynes are first converted to oxathiolanes or vinyl sulfides with anti-Markovnikov regioselectivity followed by hydrolysis of these moieties to the corresponding anti-Markovnikov ketones. In the case of aryl-alkyl alkyne substrates, complete anti-Markovnikov selectivity is demonstrated with a broad range of examples. Aryl-aryl alkyne substrates offer a mixture of regioisomers favoring anti-Markovnikov products. Finally, the utility of this methodology is demonstrated with its application to the successful first total synthesis of the bioactive natural product isomeranzin. / Thesis / Master of Science (MSc)

Patchy particles are patterned particles with at least one well-defined patch that can have highly directional and strongly anisotropic interactions with other particles or surfaces. Multiple theoretical studies point to interesting self-assembly of these particles into superstructures and, as a result, a multitude of possible applications. However, reliable synthetic methods for patchy particles, especially at the sub-micron level, are still a challenge and an active area of research. This work presents a novel synthesis route for making patchy particles at the sub-micron level that involves the use of capillary condensation. Colloidal silica particles of various sizes were synthesized and ordered into closely-packed arrays via evaporative self-assembly. Various chemical agents were capillary condensed into the voids of this assembly which, due to the face-centered cubic structure of the crystallized colloidal silica, produced distinct \patches" on the particle surface. The patches on these particles were successfully functionalized with gold nanoparticles. This method was shown to provide control over the patch size by modifying the silica particle radius, which thermodynamically changes the amount of capillary condensation. The patchy nature of the resultant particles was confirmed using infrared spectroscopy, scanning electron and optical microscopies, energy dispersive x-ray analysis and zeta potential measurements.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20946号 / 理博第4398号 / 新制||理||1632(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 依光 英樹, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The work described in this thesis was aimed at understanding the reactions taking place on heating Y2O3:Eu3+ phosphor precursors in the nano particle size regime. Herein combustion syntheses to prepare nanometer sized crystallites of cubic Y2O3:Eu3+ using precursors containing sacrificial long chain alkylammonium cations (the fuel) are reported. Using this method it proved possible to produce cubic Y2O3:Eu3+ crystallites in the 20-70nm size range. The presence of CO2 bands in the infra red spectra of the surface of the cubic Y2O3:Eu3+ crystallites are also reported. These bands are identical in position to those found in [(Y, Eu)OHCO3.H2O], and are explained as arising from the spontaneous reaction of the surface of the nanometer sized particles of cubic Y2O3:Eu3+ with atmospheric CO2 and water vapour. This indicates that nanometer sized particles of cubic Y2O3:Eu3+ are thermodynamically unstable in the atmosphere and must be protected against such back reactions. This could be done with surface coatings. Precursors of the products were prepared from methanolic and ethanolic solutions and then these were fired at temperatures of 650 and 900°C. Products (samples) prepared at a temperature of 900°C were observed to be all white powders in colour. Under 254nm uv excitation the samples prepared at 650°C displayed a weak red luminescence which was in contrast to the strong red luminescence from the samples prepared at 900°C that is characteristic of the Eu3+ ion in cubic Y2O3. The strongest red luminescence comes from 1:3 material sample ratios prepared at 900°C. The understanding of the chemistry behind the reactions and the characterisation and properties of the products formed are the major aims of the work reported here.

<p>Sammanfattning</p><p>Detta arbete handlar om hur den första undervisningen av läs- och skrivinlärning kan bedrivas. Utgångspunkter för undersökningen var att jag anser att det är av stor vikt att lära sig läsa och skriva i dagens samhälle och det är ett högt prioriterat mål i läroplanen. Eftersom jag i mitt yrke ska arbeta med läs- och skrivinlärning tänkte jag att jag behövde mer kunskap om hur den egentligen går till. Jag ville också veta hur man kan bedriva undervisning på ett sätt som gynnar alla elever, eftersom alla lär på olika sätt. Jag har undersökt hur pedagoger som arbetar med elever i förskoleklass och klass 1 kan bedriva sin undervisning i ämnet.</p><p>Min problemprecisering lyder:</p><p>Hur kan man utforma läs- och skrivundervisningen i förskoleklass och klass 1?</p><p>Detta område har i arbetet diskuterats utifrån olika litteraturstudier. Jag har också gjort intervjuer med tre pedagoger; en förskollärare, en lågstadielärare och en 1-7 lärare.</p><p>Det viktigaste som kom fram i min undersökning är att undervisningen kan bedrivas på flera olika sätt och att varje lärare måste hitta sin egen fungerande metod. Man bör dock använda sig av en blandning av syntetiska och analytiska metoder och arbeta med bokstavsljud istället för namnen på bokstäverna. Man bör också ha en undervisning som är varierande och lustfylld för eleverna och det är viktigt att man individualiserar undervisningen efter elevers olika behov.</p><p>Nyckelord: analytisk metod, läsinlärning, skrivinlärning, syntesisk metod, undervisning</p> / <p>Abstract</p><p>This document is about how the first teaching of literacy learning can be done. I think that it is very important to learn how to read and write in the society of today and it´s clearly written in the curriculum that it is important for the pupils to learn how to read and write, this is the starting point of this examination. Since my profession means that I will be teaching literacy learning I felt that I needed more knowledge in the subject. I also wanted to know how to teach in a way that favour all pupils, since every child learn in different way. I did study how teachers that works with pupils in their first years at school can run their teaching in the subject.</p><p>My question at issue is:</p><p>How can the teaching of literacy learning be done with pupils in their first years at school?</p><p>This subject has in this document been discussed out of different literature. I have also done intervjues with three teachers.</p><p>The most important that I learned from this examination is that the teaching can be done in many different ways, every teacher needs to find their own way of working. You should however use a mixture of synthetic and analytic methods and work with the sounds of the letters instead of their names. You should also make the teaching varying and pleasurable for the pupils and it is important that you individualize the teaching to the different needs your pupils have got.</p><p>Keywords: literacy learning, synthetic method, analytic method, teaching</p>

Sammanfattning Detta arbete handlar om hur den första undervisningen av läs- och skrivinlärning kan bedrivas. Utgångspunkter för undersökningen var att jag anser att det är av stor vikt att lära sig läsa och skriva i dagens samhälle och det är ett högt prioriterat mål i läroplanen. Eftersom jag i mitt yrke ska arbeta med läs- och skrivinlärning tänkte jag att jag behövde mer kunskap om hur den egentligen går till. Jag ville också veta hur man kan bedriva undervisning på ett sätt som gynnar alla elever, eftersom alla lär på olika sätt. Jag har undersökt hur pedagoger som arbetar med elever i förskoleklass och klass 1 kan bedriva sin undervisning i ämnet. Min problemprecisering lyder: Hur kan man utforma läs- och skrivundervisningen i förskoleklass och klass 1? Detta område har i arbetet diskuterats utifrån olika litteraturstudier. Jag har också gjort intervjuer med tre pedagoger; en förskollärare, en lågstadielärare och en 1-7 lärare. Det viktigaste som kom fram i min undersökning är att undervisningen kan bedrivas på flera olika sätt och att varje lärare måste hitta sin egen fungerande metod. Man bör dock använda sig av en blandning av syntetiska och analytiska metoder och arbeta med bokstavsljud istället för namnen på bokstäverna. Man bör också ha en undervisning som är varierande och lustfylld för eleverna och det är viktigt att man individualiserar undervisningen efter elevers olika behov. Nyckelord: analytisk metod, läsinlärning, skrivinlärning, syntesisk metod, undervisning / Abstract This document is about how the first teaching of literacy learning can be done. I think that it is very important to learn how to read and write in the society of today and it´s clearly written in the curriculum that it is important for the pupils to learn how to read and write, this is the starting point of this examination. Since my profession means that I will be teaching literacy learning I felt that I needed more knowledge in the subject. I also wanted to know how to teach in a way that favour all pupils, since every child learn in different way. I did study how teachers that works with pupils in their first years at school can run their teaching in the subject. My question at issue is: How can the teaching of literacy learning be done with pupils in their first years at school? This subject has in this document been discussed out of different literature. I have also done intervjues with three teachers. The most important that I learned from this examination is that the teaching can be done in many different ways, every teacher needs to find their own way of working. You should however use a mixture of synthetic and analytic methods and work with the sounds of the letters instead of their names. You should also make the teaching varying and pleasurable for the pupils and it is important that you individualize the teaching to the different needs your pupils have got. Keywords: literacy learning, synthetic method, analytic method, teaching

Den här studien går ut på att undersöka vilka arbetssätt lärare använder sig av när det gäller undervisningen i läsutveckling i skolans tidigaste åldrar, samt varför de väljer just dessa. Studien bygger på kvalitativa intervjuer med fyra verksamma lärare i förskoleklass och årskurs 1. Resultatet av undersökningen är att lärarna blandar flera olika metoder, och arbetssätt, för att individanpassa sin undervisning och nå varje enskild elev. / This study aims to examine the working methods that teachers use in reading development in the early years education, as well as why they choose these methods. The study is based on qualitative interviews with four active teachers in preschool-class and first grade. The result of the study says that teachers mix different methods, and approaches, to individualize their teaching and reach each individual student at their level.

The aim of this thesis is to assess the reading comprehension of pupils in the second grade of elementary school. This work focuses on possible existence of differences in reading comprehension of children taught using analytic-synthetic and genetic method. The content of this thesis is also a reading self-evaluation of these students. The theoretical part acquaints readers with the main topics related to the issue, with the help of available literature sources. It focuses particularly on issues of literacy, reading, reading comprehension, reading teaching methods, self-evaluation of reading, reader environment or reading diagnostics. Due to the research goals, for the practical part, quantitative methodology was used. The test battery includes two tests of reading comprehension and self-assessment questionnaire. Examination "We're going on a trip" is taken from a research project Reading comprehension- typical development and its risk. Other used methods are test "Hedgehog" and "Questionnaire reading for pupils in second year". These methods were created under the project Development of the reading literacy competencies in the inclusive education. The research sample includes 155 children attending the second grade of primary school (66 taught analytic-synthetic reading method and 89 genetic...

O perigo geológico de escorregamentos é a probabilidade da ocorrência de eventos ou fenômenos desta natureza, induzidos ou não pela atividade humana que podem causar danos humanos, socioeconômicos e ambientais. A cartografia de perigos geológicos de escorregamentos é um importante instrumento para gestão dos territórios para Estados Nacionais, setor privado, ONGs, comunidades locais, organizações científicas, etc. O desenvolvimento da ciência e das técnicas fez surgir diversos métodos de avaliação de perigos de escorregamento. No presente trabalho, o método sintético e o método analítico foram comparados com base em Sistemas de Informação Geográfica (SIG), técnicas de geoprocessamento e modelagem de dados cartográficos. Os atributos utilizados, na forma de matrizes numéricas foram declividade do terreno, densidade de drenagem e de lineamentos, excedente hídrico e cobertura vegetal e uso da terra (índice NDVI). Por meio de procedimentos de álgebra de mapas foi obtido o índice de perigo e elaborados os mapas de perigo de escorregamento. No método analítico o mapa de perigo ficou com uma textura mais granulada e no método sintético aparentou uma textura mais homogênea. A comparação da medida de classes em m² dos métodos coincidiu em 92% na classe muito alto, 90% na classe alto, 89% na classe médio e 90% na classe baixo. Já na tabulação cruzada a porcentagem de intersecção foi de 50% para a classe muito alto, 41% para a classe alto, 52% para a classe médio e 68% para a classe baixo. Concluiu-se que ao invés de opostos, os métodos se mostram adequados para um uso complementar. / Geological hazard due landslides is the likelihood of occurrence of such events or phenomena, either induced or not by human activities that can cause human, social-economic or environmental loss. Landslide hazard maps are important tools for territory management among government, private sector, Non-Governmental Organizations (NGO), local communities and academy. The development of science and techniques brought about many methods for landslide assessment. This work aims to compare two approaches: the syntethic and analytical methods based on Geographical Information Systems (GIS), geoprocessing and cartographic data modeling. The used attributes, organised in numeric rasters were declivity, drainage and lineaments density, water excess and vegetation cover and land use (NDVI). Procedures of map algebra resulted in the Landslide Hazard Indexes, from which the hazard maps were generated. The maps were compared and validated across previous risk and suscetibility maps with high correlation results. It was concluded that rather than opposites both methods are suitable for an complementary use.

This study centres on learning to read and methods for teaching reading skills. The aim is to provide a survey of the concept reading skills and the methods developed on the basis of different theories and the methods preferred when teaching children in primary school and why. The study is based on interviews with eight teachers who are working on a daily basis teaching Swedish in preschool class or lower primary school. The result of my study is that the majority of teachers do not use a specific method, but rather combine several different methods, thus adapting instruction to each individual pupil.