Diese Arbeit gibt neue Einblicke in die kinetischen und mechanistischen Aspekte der konventionellen radikalischen und der Reversible-Addition–Fragmentation-chain-Transfer- (RAFT-)Polymerisation von der Oberfläche von Silica-Nanopartikeln. Die Terminierungskinetik der oberflächeninitiierten Polymerisation von n-Butylmethacrylat (n-BMA) wurde mit Hilfe der Single-pulse–pulsed-laser-Polymerisation (SP–PLP) in Kombination mit der Elektronenspinresonanzspektroskopie (ESR-Spektroskopie) analysiert. Die Polymerisation wurde dabei durch den neu entwickelten oberflächengebundenen Photoinitiator 2,2-Dimethoxy-2-phenyl-1-(2-(2-(trimethoxysilyl)-ethyl)phenyl)-1-on (DMPTS) initiiert. Die erhaltenen Geschwindigkeitskoeffizienten der Terminierung kt, die ausschließlich der Terminierungsreaktion zwischen zwei oberflächengebundenen Radikalen zugeordnet werden konnten, waren signifikant kleiner als die Literaturwerte für das entsprechende homogene Polymerisationssystem. Erstaunlicherweise konnte außerdem keine Kettenlängenabhängigkeit von kt gefunden werden. Dies zusammen mit der Tatsache, dass bei temperaturabhängigen Untersuchungen eine Aktivierungsenergie für kt gefunden wurde, die in exzellenter Übereinstimmung mit der des Propagationsgeschwindigkeitskoeffizienten von n-BMA ist, lässt das Bild einer reaktionsdiffusionskontrollierten Terminierung oberflächengebundener Makroradikale entstehen. Die Entwicklung des oberflächengebundenen Photoinitiators DMPTS erlaubte weiterhin neue Einblicke in die Propagationskinetik – insbesondere deren Temperaturabhängigkeit betreffend – oberflächengebundener Makroradikale. Mittels der PLP von n-BMA in Kombination mit der Größenausschlusschromatographie (engl. size-exclusion chromatography, SEC) wurden Werte für den Geschwindigkeitskoeffizienten der Propagation kp und die entsprechende Aktivierungsenergie ermittelt, die exzellent mit den Daten der International Union of Pure and Applied Chemistry (IUPAC) für die Polymerisation von n-BMA in homogenem Reaktionsmedium übereinstimmen, sodass kein Einfluss der Oberflächenverankerung der Makroradikale auf die Propagationskinetik ersichtlich ist. Weiterhin wurde die Kinetik der RAFT-Polymerisation von n-Butylacrylat (BA) von Oberflächen bei –40 °C mit Hilfe verschiedener ESR-spektroskopischer Methoden für den R- und den Z-Gruppen-Ansatz unter Verwendung oberflächengebundener Trithiocarbonate als RAFT-Agenzien untersucht. Die kinetischen Analysen des R-Gruppen-Ansatzes mittels stationärer ESR-Experimente lieferten Gleichgewichtskonstanten Keq, die um eine Größenordnung kleiner sind als die Literaturwerte für entsprechende homogene Polymerisationssysteme, was darauf hindeutet, dass die Oberflächenverankerung des RAFT-Agens einen signifikanten Einfluss auf die Kinetik der RAFT-Polymerisation hat. Durch die Aufnahme zeitlicher Konzentrationsverläufe der Intermediatspezies und der propagierenden Radikale nach Einzelpulsinitiierung mittels der hochaufgelösten zeitabhängigen ESR-Spektroskopie (SP–PLP–ESR–RAFT) in Kombination mit PREDICI®-Simulationen wurden diese Ergebnisse bestätigt, da eine Abnahme des Geschwindigkeitskoeffizienten der Addition eines Makroradikals an die RAFT-Gruppe mit zunehmender Anzahl beteiligter oberflächengebundener Makromoleküle gefunden wurde. Dieser Befund ist im Einklang mit der Vorstellung, dass die Additionsreaktion bei Beteiligung verankerter Makromoleküle diffusionskontrolliert abläuft, was auf die unterdrückte Translations- und die eingeschränkte Segmentdiffusion oberflächengebundener Polymerketten zurückzuführen ist. Ein noch kleinerer Wert von Keq wurde für den Z-Gruppen-Ansatz gefunden und kann darauf zurückgeführt werden, dass die in Lösung wachsenden Ketten für die Additionsreaktion mit der RAFT-Gruppe, die sich über den gesamten Verlauf der Polymerisation in unmittelbarer Nähe zur Partikeloberfläche befindet, durch die Polymerschicht auf der Oberfläche diffundieren müssen. Die Wahrscheinlichkeit dafür, dass eine Additionsreaktion stattfindet, nimmt mit zunehmender Polymerschichtdicke ab, was durch einen kleineren Wert von Keq bei Verwendung von einem RAFT-Agens, das über die Z-Gruppe verankert war und über eine makromolekulare anstatt einer niedermolekularen R-Gruppe verfügte, gezeigt werden konnte. Die vorgestellten Ergebnisse geben einen umfangreichen Überblick über den Einfluss der Oberflächenverankerung von Komponenten, die am Prozess der radikalischen Polymerisation beteiligt sind, auf die Kinetik der oberflächeninitiierten radikalischen Polymerisation und ebnen den Weg für detaillierte, systematische Untersuchungen der Zusammenhänge zwischen der Kinetik von radikalischen Polymerisationen an Oberflächen und der molekularen Struktur der erhaltenen oberflächengebundenen Polymere.

Magistrinio darbo problema kaip buvo skleidžiama Japonijos propaganda dėl Š. Korėjos įvykdytų pagrobimų ir kokios jos sklaidos pasekmės išryškėjo. Baigiamojo darbo objektas - Japonijos propaganda 2002 – 2011 m. Š. Korėjos inicijuotų pagrobimų atveju. Šio darbo tikslas išanalizuoti Š. Korėjos įvykdytus Japonijos piliečių pagrobimus ir atskleisti Japonijos propagandos dėl šių pagrobimų organizacijos struktūrą, sklaidos priemones ir rezultatus. Šiam tikslui pasiekti išsikelti tokie uždaviniai: 1.Remiantis teorinės literatūros šaltinių analize apibrėžti propagandos sampratą ir jos skaidos priemones bei parengti Japonijos propagandos analizės modelį; 2. Išryškinti prielaidas Japonijos vyriausybės propagandos formavimui1970 – 2005 m.;3. Atlikti propagandos modelio taikymo Japonijoje analizę.; 4. Išnagrinėti Japonijos vyriausybės propagandos dėl Š. Korėjos įvykdytų pagrobimų poveikį Japonijos visuomenei. Baigiamajame darbe naudojami šie metodai: Lyginamasis, aprašomasis ir analitinis. Atlikus tyrimą prieita prie tokių išvadų: 1. Remiantis užsienio ir Lietuvos autorių propagandos sąvokos lyginamąja analize, iškirtais propagandos tipais ir jos sklaidos priemonėmis bei G.S. Jowett ir V. O‘Donnell propagandos analizės 10 žingsnių metodu buvo sudarytas 7 žingsnių Japonijos propagandos analitinis modelis. 2. Įvertinus propagandos formavimosi kontekstą ir atskleidus Japonijos ir Š. Korėjos santykius 1971 – 2005 m., pavyko identifikuoti pagrindinius propagandos šaltinius Japonijoje: neo... [toliau žr. visą tekstą] / Problem of this master thesis is how propaganda of Japan regards North Korea initiated Japanese abductions is distributed and what are the consequences of this propaganda is in general. Subject in the final thesis is propaganda of Japan in 2002 – 2011: North Korea initiated Japanese abduction case. Objective of this research is to analyze North Korea initiated Japanese abductions and following it clarify structure of Japanese government propaganda, its distribution techniques and results. To reach this objective these following tasks are made: 1. define propaganda concept and ways of propaganda distribution based on theoretic scientific literature analysis and prepare model of Japanese propaganda analysis. 2. Highlight assumptions of Japanese governmental propaganda development in 1971 – 2005. 3. Accomplish research analysis based on model of propaganda of Japan. 4. Analyze Japanese government propaganda on North Korea initiated Japanese abduction case influence to Japanese society. In this research three methods are used: description, comparative and analytical methods. Accomplished Japanese propaganda analysis of this research led to these conclusions: 1. based on comparative analysis of Lithuanian and foreign authors on concept, sorts and ways of distributing propaganda, and G.S. Jowett ir V. O‘Donnell 10 steps of propaganda analysis method, 7 steps model of propaganda of Japan is shaped. 2. From propaganda development context based on Japan’s and North Korea‘s relation... [to full text]

Self-assembled microsphere monolayers (SMMs) hold significant promise for micro- and nanopatterning. Here we exploit, for the first time, SMMs as stamps for microcontact printing (μCP) and demonstrate this to fabricate patterned initiator templates that can subsequently be amplified into polymer brushes by surface initiated atom transfer radical polymerization (SI-ATRP). SMM stamps avoid the need for expensive and sophisticated instrumentation in pattern generation, and provide a broad range of accessible surface chemistries and pitch size control.

Ce travail porte sur des aspects souvent oubliés de l'expatriation : les réactions des individus. A partir des théories du « coping » (faire face), et de la collecte de 559 questionnaires, les actions et cognitions des expatriés sont examinées au sein de trois essais – deux portants sur les facteurs qui affectent ces réactions, et le troisième sur leurs conséquences.Le premier essai étudie le soutien social organisationnel et révèle que le supérieur de l'expatrié possède une influence émotionnelle : son soutien facilite l'acceptation et la réinterprétation positive des difficultés auxquelles l'expatrié fait face. L’aide provenant des pairs a des conséquences plus instrumentales, favorisant la recherche d’informations et de conseils.Le second essai montre que différentes catégories d’expatriés réagissent différemment aux défis de l’expatriation : les femmes ont davantage recours à du soutien social, et ont plus de facilité à accepter leur expérience et à la voir de manière positive que les hommes. Les jeunes ont davantage de risque de consommer alcool et drogues que leurs aînés, et les expatriés ayant initiés eux-mêmes leur expatriation ont des réactions plus émotionnelles que les expatriés classiques. Enfin, dans un troisième travail l’influence des réactions des expatriés sur leur adaptation est examinée. Il en ressort notamment le rôle positif des réactions d’acceptation, ainsi que les risques à limiter ou arrêter ses efforts. / Some individuals enjoy their expatriation to the point of being reluctant to eve come back to their home country, but some experience terribly hard times. This research seeks to advance knowledge in the understanding of this variance by applying coping theory and methodologies. Three essays based on 559 questionnaires. Filled out by expatriates examine expatriate reactions. The first two aim to uncover antecedents of individual behavior ad cognitions abroad, while the third essay investigates the effectiveness of these reactions.The first essay focuses on the role of organizational social support and shows that supervisor’s influence is emotional, facilitating emotion-focused engagement coping reactions, such as acceptance or positive reappraisal, whereas peer support is more instrumental, easing the search for useful information and advice.The second essay focuses on expatriate categories that have been neglected for a long time in research: the self-initiated, female and young. This work shows that women use more social support and display more acceptance and positive reappraisal to face the problems of expatriation, the young are more at risk of drinking alcohol and taking drugs, and self-initiated expatriates have more emotional reactions than organizational ones.Finally, the third essay analyzes coping consequences. It notably shows that being able to realize and accept expatriation hardships (acceptance) facilitates adjustment. It also appears that giving up trying to solve the problems one is face with a dangerous reaction, jeopardizing professional and cross-cultural adjustment.

Les cellules souches embryonnaires (ESCs) sont issues de la masse cellulaire interne (ICM) de blastocystes préimplantatoires. Elles sont pluripotentes c'est-à-dire capables de se différencier dans les trois lignages embryonnaires (ectoderme, mésoderme et endoderme) et de s'autorenouveller, c'est-à-dire de se multiplier indéfiniment en culture. Chez la souris, ces cellules (mESCs) sont à la base des techniques de transgénèse permettant des modifications génétiques ciblées. Chez l'Homme ces cellules (hESCs) représentent un grand espoir en médecine régénérative pour traiter des maladies dégénératives comme les maladies de Parkinson ou de Huntington. Le modèle le plus pertinent de l'espèce humaine est le singe. Cependant l'expérimentation sur cette espèce est soumise à une réglementation très stricte. C'est pourquoi il est nécessaire de développer des modèles alternatifs. C'est dans ce cadre que s'inscrit le lapin, qui est phylogénétiquement plus proche de l'Homme que ne l'est la souris. Mon projet de thèse a eu pour but d'étudier la pluripotence dans les ESCs de lapin (rESCs), afin de pouvoir les utiliser en transgénèse et produire des animaux transgéniques, modèles de maladies humaines. La première partie de ces analyses est regroupée au sein de l'article que notre laboratoire a publié en 2013 dans Biology Open (Osteil et al. 2013). D'autres analyses ont abouti à la dérivation de nouvelles lignées stabilisées dans un état plus proche de celui des cellules de l'ICM. L'ensemble des résultats a permis d'établir des bases solides pour la compréhension de la pluripotence et pour la dérivation d'ESCs dites naïves chez un autre mammifère que la souris / Embryonic stem cells (ESCs) result from cultures of inner cell masses (ICMs) isolated at preimplantation blastocyst stage. ESCs are defined by their self-renewal capacity, characterized by robust proliferation while maintaining plutipotent potential, the ability to give rise to cells from all three germ layers mesoderm, endoderm and ectoderm. Mouse ESCs (mESCs) allow the production of transgenic models by site-specific mutagenesis. Human ESCs (hESCs) represent major hope for regenerative medicine in order to treat degenerative diseases like Parkinson or Huntington. The more relevant model of Human is monkey. However, working on this specie is subjected to extremely strict regulation. Consequently it is very important to develop alternative animal models. Rabbit appears to be a very good candidate, because he is phylogenetically closer to Human than the mouse. My thesis project aimed to study the pluripotency mechanism of rabbit ESCs (rESCs), in order to use these cells for the production of transgenic animal models for human diseases. First part of theses analyses is synthesized in a publication into Biology Open in 2013 (Osteil et al. 2013). Other analyses produced new rESCs lines stabilized in a closer state compared to ICM state. All these results led to obtain solid knowledge on pluripotency and derivation on so-called naïve ESCs in a non-rodent specie

The performance and life time of organic solar cells are critically dependent on the properties of active layer materials and device interfaces. In this manuscript, we developed new organic-inorganic hybrid materials to create intimate contact between donor and acceptor phases and facilitate the interfacial electronic charge transfer through the device. First, the synthesis of versatile triethoxysilane-terminated poly(3-hexylthiophene) P3HT for direct anchoring (grafting-onto) in one step procedure to various metallic oxides was reported. Electro-optical analysis showed an efficient charge transfer from the polymer to nanoparticles; suggesting that these materials are suitable candidates for photovoltaic application. In the second part, we demonstrate for the first time the elaboration of low band gap polymer brushes on metallic oxide surfaces via surface initiated step growth polymerization (grafting-through). In both cases, a higher grafting density, better packing of polymer chains and enhanced optical properties were observed due to the grafting methodology and polymer characteristics. Finally, P3HT brushes were elaborated on indium tin oxide surface (ITO) as hole transporting layer of organic solar cells. Photovoltaic performances showed that P3HT self-assembled monolayer (SAMs) could be promising alternatives to PEDOT:PSS. / Les performances et la durée de vie des cellules solaires organiques sont fortement dépendantes de la qualité des matériaux de la couche active et des interfaces dans le dispositif. Dans ce manuscrit, nous avons développé des nouveaux matériaux hybrides organiques-inorganiques pour favoriser le contact entre les matériaux donneur/accepteur d’électrons et ainsi faciliter le transfert de charges à travers le dispositif. Tout d'abord, la synthèse de poly(3-hexylthiophène) P3HT fonctionnalisé par le triéthoxysilane a permis le greffage direct (« grafting-onto ») sur des oxydes métalliques. L’analyse des propriétés électro-optiques montre un transfert de charge efficace du polymère aux nanoparticules; ce qui suggère que ces matériaux sont des candidats potentiels pour l'application photovoltaïque. Dans la deuxième partie, nous avons montré pour la première fois, l’élaboration de brosses de polymères dits à faible bande interdite sur des surfaces d’oxydes métalliques par la technique « grafting-through ». Une densité de greffage élevée, un meilleur empilement des chaines de polymères et des propriétés optiques améliorées ont été obtenus grâce à la technique de greffage et aux caractéristiques du polymère greffé. Enfin, des brosses de P3HT ont été élaborées sur la surface d’oxyde d'indium et d’étain (ITO) en tant que couche de transport de trous de cellules solaires organiques. Les performances photovoltaïques ont montré que les monocouches auto-assemblées de P3HT (SAM) peuvent être une alternative au PEDOT: PSS.

This thesis deals with what happens linguistically and interactionally in naturally occurring bilingual talk-in-interaction between Danes and Swedes. In the data – collected within the elderly care in a Danish municipality – three Swedish caregivers interact with Danish pensioners and colleagues. Previous research on inter-Scandinavian interaction has mostly been concerned with talk-in-interaction in arranged situations and/or situations where the participants do not interact regularly with other Scandinavians. The talk-in-interaction in the present data, however, has a clear activity context, and the participants are used to talking to people speaking the neighbour language. The aim of this study was to examine how comprehension, understanding and social affiliation were achieved and demonstrated across differences in language, age, nationality and institutional roles. The theoretical and methodological framework includes accommodation theory and conversation analysis. The linguistic aspects of the Swedish speakers’ accommodation to Danish were studied both in a detailed analysis of accommodation on five linguistic levels, and quantitatively in a study of five linguistic variables. One result was that the Swedish caregivers had individual ways of accommodating their language to Danish. The linguistic analyses also indicated that one reason for this accommodation was to make communication flow more efficiently. A CA-study of other-initiated repair showed that four factors in the interactional situation influenced understanding: context, physical distance and orientation, clearness of speech, and neighbour language and accommodation. It could, however, not be shown that the speakers’ use of different linguistic varieties caused a significant number of problems in understanding, or that the participants frequently oriented to such linguistic differences as part of the problem. Compliment sequences and their role in creating social affiliation were studied in another CA-study. They often played the role of introducing a new topic and leading the talk away from the practical chores at hand, thereby reducing the institutional aspect of the situation. The interactional ways of creating comprehension, understanding and social affiliation are likely to be at least as important as linguistic convergence in achieving these goals.

The purpose of this study was to investigate perceptions of self-initiated professional development of English language teachers at English Language School of BaSkent University. Within this framework, teachers&amp / #8217 / attitudes towards their professional development, their perceptions of major professional development activities, and the factors that hinder change and growth in teachers were investigated. The data collection instrument used was a questionnaire administered to 110 English language teachers at BaSkent University. The questionnaire consisted of both open-ended and close-ended items and the data collected were analyzed descriptively to understand the general trends and differences among teachers. The data analysis revealed that the teachers agreed with most of the concepts that reflect the importance of professional development. In addition, they were aware of the importance of major professional development activities for their growth. However, peer observation and action research, which are developmental activities, were not favoured as much as the other activities. In addition, it was found that the teachers did not make use of the activities as much as they gave importance to. Furthermore, teachers showed significant differences in importance given to and making use of the activities by the background variables. Female teachers, young teachers and the teachers who do not have much experience seemed to give more importance to and actualize some of the professional development activities more than the other teachers. Meanwhile, it was also noted that the listed factors that hinder growth were all found important by the teachers. The most important impediments to growth were indicated as excessive workload, lack of self-motivation and lack of institutional support for professional development.

This dissertation examines the life stories of Marsha Ethridge (all names are pseudonyms), a teacher who has taught for 46 years in one urban elementary school. The stories Marsha tells about her life are used as lenses to consider the following: (1) What influences most shaped Marsha’s practices and stories to live by as a teacher? (2) What has it been like for Marsha teaching reading in an urban elementary school for 46 years? and (3) What is the nature of caring in Marsha’s stories? The study draws on life story and portraiture methods. Data were collected over a period of three years and includes life story interviews, one focus group interview, observations, and artifacts. Through the process of constant comparative method, three themes emerged: literacy and accountability, teacher development and identity, and caring and connecting. The most salient theme was caring and connecting throughout Marsha’s stories, and it served as a unifying thread to pull her stories together. This study found that in Marsha’s first years of teaching there were few forms of accountability. She felt that this was the primary reason many of her sixth graders had made it through school without learning to read. In the following years she used a variety of measures for accountability, including high-stakes accountability, which caused her to experience increasing professional dissonance. The form of accountability she believed improved her teaching practices the most was accountability situated in the context of caring relationships and it led to hope for future success. Marsha experienced this face-to-face accountability in the teacher-initiated group she had been meeting with for 27 years. Research implications from this study include the need to further explore discourse in teacher-initiated groups over time and in different contexts, as well as consider how the relational dynamics and accountability within collaborative teacher groups contribute to teacher growth. Additionally, the analysis of Marsha’s life stories indicate a need for teachers, parents, researchers, and policy makers to lay aside discourse of blaming and shaming to create opportunities for extended conversations about alternatives to high-stakes accountability. / text

The need for health informatics education is recognized by many countries which are now engaged in introducing technology to healthcare. Universities have been slow to respond to the need for health informatics professional education. Governments are also involved in initiatives to fund the development of curricula and programs in this area. Entry level and generic courses in health informatics are being developed in order to start education programs. There are now a number of such programs being initiated in some of the developing countries. To meet this demand there is need for individuals who are educated in health informatics. These individuals should be able to perform health informatics related tasks and activities in order to serve the healthcare community better. The focus of their work should be on producing effective leaders in health informatics through formal educational programs and professional education. The purpose of this research is to answer the following research questions: 1) Is there a perceived demand for health informatics professionals in the healthcare institutions of Karachi as expressed by administrators of healthcare institutions? 2) Is there a perceived need for post-secondary Health Informatics education in Karachi as expressed by directors of academic institutions? 3) What types of skills and competencies will health informatics professionals need to acquire through educational programs in Karachi? Setting: This research was conducted in Karachi, Pakistan in 2010 to determine the demand for health informatics education by interviewing representatives from academic and healthcare institutions in Karachi. Participants: A snowball sampling methodology was used. Participants from different types of healthcare centers were interviewed including public and private healthcare centers, nongovernmental organizations, primary healthcare centers of Karachi, and academic institutions that include private and government institutes which are representative of the entire city. Method: Approval was elicited from Human Research Ethics Board of University of Victoria to conduct the study in Karachi, Pakistan. The study described in this thesis used a qualitative design. Thirty participants including fifteen directors of academic institutions and fifteen head of administration of healthcare institutions participated in the study. The sampling methodology used was snowball sampling, which is a non-probability type of sampling. This is the type of sampling where samples are gathered in a process that does not give all the individuals in the population equal chances of being selected [92]. The researcher identified an expert who provided the contacts of academic directors who were invited to participate in the study. The researcher conducted face-to-face interviews with them. Findings: There are many educational gaps and there is also a lack of resources needed to fulfill the demand for health informatics education in healthcare institutions. Ways to improve education in health informatics were discussed and competencies required for health informaticians were established. By obtaining understanding about health informatics, the need for health informatics education to meet the demand of healthcare institutions of Karachi was identified. After reviewing details and results from the research, institutions can make an independent decision regarding choosing an appropriate approach to health informatics education that blends in with the culture of the target population. The most important themes that were derived from the responses of directors of academic institutions fall under a number of different categories. Understanding of health informatics was expressed by participants as representing an integration of computer science and healthcare. It was also clear that subjects felt that capacity building was required for the development of skill sets related to data and system management. The status of HI education in Karachi was noted as being in its infancy, which was a constant theme in all the responses of the participants. Additionally, limited resources available along with a lack of financial assistance, lack of knowledge, manpower, educators and awareness were also a few prominent themes. The administrators had hands-on experience in managing healthcare institutions and they expressed important themes with regard to understanding health informatics as being the management of data and the maintenance of patient records through computer science. The collection of encounters and compilation of clinical documentation was seen as the key concept behind medical records. Themes related to job market requirements included critical thinking, computer knowledge, understanding of medical terminology and specific expertise related to the HI field. Limited resources and scarcity of funds were seen as themes reflecting barriers for health informaticians in the healthcare organizations. Administrators expressed the need for developing academic programs to address manpower training for prospective employees. Conclusion: This paper presents results that could be a major contribution towards enhancing the approach of training professionals in the field of health informatics in Pakistan. This research will hopefully help educators adopt health informatics in their curricula and will encourage educators in the field to impart their knowledge to local people. / Graduate