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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
601

Quando a violência política entra em cena / The mise-en-scène of the political violence

Gilberto Tedeia 17 May 2011 (has links)
Tendo como fio condutor o uso da violência política em sua relação com o poder soberano, a Tese decifra um percurso que leva da crítica ao terror ao esvaziamento da política. O temor da transformação de questões sociais em questões políticas inaugura a desqualificação da ação política que busque instaurar outra hierarquia de valores e outros lugares às categorias e grupos sociais vítimas de uma ordem instituída. Como se essa decisão de exclui-los fosse expressão da vontade da maioria, a abstração que permite excluir grupos humanos inteiros no pós-Primeira Guerra Mundial, ao transformar direito em privilégio de alguns como no caso em que apátridas e desnacionalizados foram vítimas, é encontrada também no movimento que transforma a política em gestão e administração, e criminaliza as tentativas de ruptura da ordem vigente. No termo desse percurso, os limites à liberdade prático-política são pensados tanto sob o registro da luta emancipatória radical quanto sob o da criminalização da ação violenta como terrorismo a ser neutralizado ou exterminado. / This Thesis main focus is the analysis of the ways in which political violence can be used and its relations with the Sovereign Power. I argue that there is a link build by the years between the Terrors critics and the emptying of politics, alloying the creation of the idea that one must fear the transformation of social questions into political questions. Because of this situation, all political actions seeking another values hierarchy and another place to the status quos victims tend to be disqualified. Also, since the post-I Great War, the mass exclusion of entire social groups not only became possible but could be shared as a decision of the majority of the people, through the transformation of common wrights into privileges of some, as can be observed in the homelandless and stateless cases. I aim to demonstrate the functioning of the abstraction working in that process, and to sustain that is the same abstraction that gives basis to transform politics into management and administration, and to criminalize the ones who fight to disrupt the established order. Thus, the limits of the practical political freedom will be examined under the clash of two registers: one belonging to radical emancipatory fights and the other one to the movement that enforces violent political actions criminalization as terrorism needed to be neutralized or terminated.
602

Design and Utilization of New Organotellurium Chain Transfer Agents for Advanced Polymer Synthesis / 先進高分子合成のための新規有機テルル連鎖移動剤の設計と利用

Fan, Weijia 23 May 2019 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21963号 / 工博第4618号 / 新制||工||1720(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 辻井 敬亘, 教授 大内 誠 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM
603

Mobiltelefonen som lärverktyg - En studie med fokus på matematiska lärandekontexter i grundskolans årskurs 3

Lundgren, Elin, Marjeta, Josefina January 2021 (has links)
Mobiltelefoner används i dagsläget knappt som lärverktyg i matematikundervisningen trots att den digitala tekniken är en stor del av det svenska samhället. Genom mobile learning ges elever möjlighet att utnyttja mobiltelefonen som lärverktyg både i formella och informella sammanhang. Syftet med studien är att öka kunskapen om huruvida lärare ser mobiltelefonen som ett potentiellt lärverktyg i grundskolans tidigare år. Studien besvarar frågor om elva lärares inställning till och kunskap om mobiltelefonen, vad de ser som möjligheter och svårigheter med verktyget samt deras syn på mobile learning i utomhusmatematik. För att besvara dessa frågor används kvalitativa intervjuer och teorierna Technological Pedagogical and Content Knowledge och Radical-local teaching and learning. Resultatet visar att lärare generellt är positivt inställda till mobiltelefonen som lärverktyg och mobile learning, dock i olika utsträckning. Utifrån resultatet kan slutsatsen dras att lärare behöver fortbildning för att bli mer förtrogna med mobiltelefonens användning som lärverktyg i matematikämnet. / Cellphones are currently barely used as a learning tool in mathematics education, even though digital technology is a large part of the Swedish society. Through mobile learning, students are given the opportunity to use the cellphone as a learning tool in both formal and informal contexts. The purpose of the study is to increase knowledge about whether eleven teachers see the cellphone as a potential learning tool in the previous years of primary school. The study answers teachers' attitudes to and knowledge of the cellphone, what they see as opportunities and difficulties with the tool and their view of mobile learning in outdoor mathematics. To answer these questions, qualitative interviews and the theories Technological Pedagogical and Content Knowledge and Radical-local teaching and learning are used. The results show that the teachers in general are positive to the cellphone as a learning tool and the concept of mobile learning, but in varying degrees. Based on the results, it can be concluded that teachers need further training to become more confident to use cellphones as a learning tool in the subject of mathematics.
604

Polyesters Fonctionnels par Polymérisation Radicalaire par Ouverture de Cycle, une Plateforme Nanoparticulaire pour la Délivrance de Principe Actif pour les Maladies Cardiovasculaires / Functionalized Polyesters by Radical Ring-Opening Polymerization as a Nanoparticle-based Platform for Drug Delivery in Cardiovascular Diseases

Tran, Johanna 17 December 2018 (has links)
D’après l’Organisation Mondiale de la Santé (OMS), les maladies cardiovasculaires (CVDs) sont la cause majeure de morbidité et de mortalité dans le monde. Dans un contexte où les thérapies non chirurgicales impliquent une administration de molécules actives à hautes doses, limiter les effets secondaires et augmenter l’efficacité thérapeutique est un enjeu majeur. Une possible réponse à cette problématique est l’utilisation de nanoparticules polymères encapsulant des molécules actives. Pour des applications de délivrance de principe actif et/ou de génie tissulaire, les polymères utilisés doivent suivre certains critères : (i) la biodégradabilité ; (ii) la biocompatibilité ; (iii) l’uniformité des chaînes polymères et (iv) une fonctionnalisation aisée par les molécules d’intérêt. Dans ce contexte, des copolymères dégradables obtenus par polymérisation radicalaire par ouverture de cycle (rROP) entre les acétals de cétène cyclique (CKAs) et des monomères vinyliques semblent satisfaire à ces critères. En effet, les CKAs sont des monomères cycliques qui s’ouvrent par voie radicalaire et permettent la formation de fonctions esters dans le squelette polymère au cours de la polymérisation. Hormis les CKAs bien connus (e.g., 2-methylene-1,3-dioxepane (MDO), et 2-methylene-4-phenyl-1,3-dioxolane (MPDL)), un besoin de nouveaux CKAs plus hydrophiles et/ou avec de nouvelles fonctionnalités est récemment apparu. Par conséquent la synthèse de nouveaux CKAs a été étudiée.Par ailleurs, les calculs par la théorie de la fonctionnelle de la densité (DFT) ont démontré que la copolymérisation radicalaire du MDO avec des dérivés d’éther de vinyle (VE) était quasi idéale, ce qui fut par la suite confirmé expérimentalement. Ainsi, ce système a permis l’obtention via un mécanisme radicalaire de copolymères similaires à des polyesters, en particulier à la polycaprolactone (PCL), hautement fonctionnels via l’utilisation de divers VE. La dégradation hydrolytique des P(MDO-co-VE) ainsi obtenus a été étudiée en conditions accélérées et physiologiques. Les copolymères ont montré une vitesse de dégradation dépendant du taux de MDO et de la nature du VE. L’hydrolyse en conditions physiologiques des P(MDO-co-VE) a donné des taux de dégradation comparables à ceux obtenus pour l’acide polylactique (PLA) et la PCL, tous deux approuvés par l’agence américaine des produits alimentaires et médicamenteux (FDA). La dégradation enzymatique assistée par les lipases Candida antartica a également été étudiée, donnant une dégradation quasi complète des copolymères en 48 h. En plus d’être biodégradables, l’avantage des P(MDO-co-VE) est que les fonctions portées par les VE ont permis une fonctionnalisation aisée des copolymères via le greffage de petites molécules ou des macromolécules telles que des chaînes de poly(éthylène glycol) (PEG) ; soit après polymérisation (approche “grafting to”) soit avant polymérisation (approche “grafting through”). Les propriétés physico-chimiques ont pu être finement ajustées, permettant ainsi la formulation de nanoparticules stables convenant à des applications de délivrance de principes actifs. / According to the World Health Organization (WHO), cardiovascular diseases (CVDs) are the major cause of morbidity and mortality in the world. In a context where non-surgical therapy involves active molecules administration at high doses, circumventing possible toxic side effects and increasing the therapeutic effect is a major challenge. Thus, the use of drug-loaded polymeric nanoparticles may represent a potential solution to this problem. For drug delivery and/or tissue engineering applications, polymers should follow some criteria: (i) biodegradability; (ii) biocompatibility; (iii) uniformity of the polymer chain and (iv) possibility of functionalization with molecules of interest. As such, degradable copolymers were obtained by radical ring-opening copolymerization (rROP) between cyclic ketene acetals (CKAs) and vinylic monomers and fulfilled all those criteria. Indeed, CKAs are cyclic monomers which open through a radical mechanism and give degradable ester functions in the polymer backbone upon polymerization. Besides well-known CKAs (e.g., 2-methylene-1,3-dioxepane (MDO), and 2-methylene-4-phenyl-1,3-dioxolane (MPDL)), a crucial need for new CKAs that would be more hydrophilic and/or with new functionalities has recently emerged. Therefore, synthesis of new CKAs was investigated.In addition, the rROP of MDO and vinyl ether (VE) derivatives was predicted to be quasi-ideal by Density Functional Theory (DFT) calculations and subsequently confirmed experimentally. Thus, this system gave the opportunity to obtain polyester-like copolymers, especially polycaprolactone-like polymers, highly functional from the use of functional VE derivatives. Hydrolytic degradation of the resulting P(MDO-co-VE) was investigated under accelerated and physiological conditions. Copolymers showed tunable degradation rate as a function of the MDO content and of the nature of the VE. Hydrolysis in physiological conditions of P(MDO-co-VE) copolymers led to a degradation rate comprised between those obtained for polylactide (PLA) and PCL, both approved by the Food and Drug Administration (FDA). Enzymatic degradation by lipases Candida antartica was also studied, leading to nearly complete degradation in 48 h. In addition to be hydrolytically and enzymatically degradable, a strong advantage of P(MDO-co-VE) copolymers rely in their easiness of functionalization via the use of various VE moieties, leading to efficient grafting by small molecules or macromolecules such as poly(ethylene glycol) (PEG) chains; either after polymerization (“grafting to” approach) or before polymerization (“grafting through” approach). Physicochemical properties were finely tuned enabling the formulation of stable nanoparticles suitable for drug delivery purpose.
605

Les bactériocines RumC, une nouvelle famille de peptides antimicrobiens comme alternative aux antibiotiques conventionnels / RumC peptides, a new family of bacteriocins as viable alternative to conventional antibiotics

Chiumento, Steve 11 October 2019 (has links)
Les antibiotiques sont des médicaments qui ont changé notre manière d’aborder les infections bactériennes et sont devenus l’un des symboles de la médecine moderne. Cependant leur utilisation massive a conduit à l'émergence de souches bactériennes multirésistantes. Ce problème est sans aucun doute un des grands défis que la médecine actuelle doit relever. Sachant que les bactéries évoluent à un rythme plus rapide que la production de nouveaux antibiotiques, il est urgent de trouver des approches alternatives. Il a été mis en évidence que ces mêmes bactéries sont capables de sécréter différents peptides antimicrobiens, ou bactériocines. Ces macromolécules présentent une grande diversité structurale et sont très efficaces pour combattre un grand nombre de souches pathogènes de façon spécifique. Les bactériocines ont un immense potentiel dans les domaines agroalimentaire et pharmaceutique. Notre projet s’intéresse aux bactériocines RumCs produites par une souche dérivée de Ruminococcus gnavus, une bactérie anaérobie stricte, membre dominant du microbiote intestinal humain. Le travail présenté dans ce manuscrit concerne la mise au point d’un système d’expression et de maturation hétérologue chez E. coli de la bactériocine RumC1. La caractérisation biochimique du peptide RumC1 montre que les bactériocines RumCs appartiennent à la famille des sactipeptides pour laquelle l’étape de biosynthèse fait intervenir une enzyme radical-SAM. Les sactipeptides présentent dans leurs séquences peptidiques un ou plusieurs ponts thioéther entre une cystéine et le carbone alpha d’un acide aminé partenaire. RumC1 renferme 4 ponts thioéther ce qui lui confère une structure originale en double épingle à cheveux. L’activité biologique de RumC1 montre que ce peptide est efficace contre un large spectre de bactéries à Gram positif incluant des pathogènes résistants tels que S.aureus et E. faecalis. Dans ces études nous n’avons pas noté de toxicité significative de RumC1 sur différentes lignées cellulaires humaine ni observé de phénomène de résistance. Les travaux en cours visent notamment à définir le mode d’action de RumC1 et à évaluer l’activité biologique de RumC1 dans un contexte d’infection in vivo chez la souris. / Antibiotics are drugs that have changed the way we approach bacterial infections and have become one of the symbols of modern medicine. However, their widespread use has led to the emergence of multiresistant bacterial strains. This problem is undoubtedly one of the major challenges facing today's medicine. Knowing that bacteria evolve at a faster rate than the discovery of new antibiotics, it is urgent to find alternative approaches. It has been shown that these same bacteria are capable of secreting antimicrobial peptides, the bacteriocins. These macromolecules have a high structural diversity and are very effective in combating a large number of pathogenic strains in a specific way. Bacteriocins have immense potential in the agro-food and pharmaceutical sectors. Our project focuses on the bacteriocins RumCs produced by a strain derived from Ruminococcus gnavus, a strict anaerobic bacterium of the human intestinal microbiota. The work presented in this manuscript concerns the development of a heterologous expression and maturation system in E. coli of the bacteriocin RumC1. The biochemical characterization of the RumC1 peptide shows that the RumCs bacteriocins belong to the family of sactipeptides for which the biosynthesis step involves a radical-SAM enzyme. The sactipeptides have in their peptide sequences one or more thioether bridges between a cysteine and the alpha carbon of a partner amino acid. RumC1 contains 4 thioether bridges which gives it an original structure in double hairpin. The biological activity of RumC1 shows that this peptide is effective against a broad spectrum of Gram-positive bacteria including resistant pathogens such as S.aureus and E. faecalis. In these studies, we did not note any significant toxicity of RumC1 on different human cell lines nor observed resistance phenomena. Current work aims to define the mode of action of RumC1 and to evaluate the biological activity of RumC1 in an in vivo context of infection in mice.
606

Dégradation atmosphérique d’une série d’alcools, d’esters et de l’hexafluoroisobutène / Atmospheric chemistry of oxygenated VOCs : atmospheric degradation of a series of Alcohols, Esters and hexafluoroisobutene

Lendar, Maria 08 October 2012 (has links)
Cette thèse présente le devenir atmosphérique de trois alcools saturés CH3(CH2)4OH, CH3CH2CH2CH(OH)CH3 et (C2H5)2CHOH, de trois esters CH3CH2CH2C(O)OC2H5, CH3CH2C(O)OC2H5 et CH3CH2C(O)OCH2CH2CH3 ainsi que d’un HFC insaturé (CF3)2C=CH2 avec OH et Cl. La constante de vitesse de la réaction avec OH de ces composés a été déterminée en fonction de la température (253 – 373 K), en utilisant la technique Photolyse Laser Pulsée couplée à la Fluorescence Induite par Laser (PLP-FIL). La constante de vitesse de la réaction de OH et de Cl avec les alcools, les esters et l’hexafluoroisobutène (HFIB) a été également déterminée à température ambiante en utilisant la chambre de simulation atmosphérique. Pour la réaction du radical OH avec le HFC et de l’atome Cl avec les esters et le HFC, il s’agit d’une première détermination des constantes de vitesse. Les constantes de vitesse obtenues sont comparées à la littérature, la réactivité des alcools et des esters a été discutée. Enfin, le calcul des durées de vie de ces composés ainsi que la recherche de leurs produits éventuels ont permis d’évaluer l’impact atmosphérique de ces composés sur l’environnement. / In this thesis we report the atmospheric fate of three saturated alcohols: CH3(CH2)4OH, CH3CH2CH2CH(OH)CH3 and (C2H5)2CHOH, three esters: CH3CH2CH2C(O)OC2H5, CH3CH2COOC2H5 and CH3CH2COOCH2CH2CH3 and an unsaturated HFC with OH radicals and Cl atoms. The rate coefficients of OH reactions with these compounds have been measured over the temperature range 253 – 373 K, using the Pulsed Laser Photolysis – Laser Induced Fluorescence technique (PLP-LIF). Moreover the rate coefficients of OH and Cl reactions with alcohols, esters and hexafluoroisobutene (HFIB) have been determined at room temperature, using smog chambers. For the reaction of OH radicals with HFIB and Cl atoms with esters and HFIB, the rate coefficients obtained in this study present the first determination. The results have been compared with the literature and the reactivity of the compounds has been discussed. Finally, the atmospheric lifetimes of these compounds have been determined and the OH oxidation products have been identified, which allows us to estimate the atmospheric impact of these compounds.
607

Facilitating Radical Collaboration in Open Innovation : A case study in collaboration with IKEA / Möjliggöra radikala samarbeten i öppna innovationslandskap : En fallstudie i samarbete med IKEA

Strömstedt, Linnéa, Vaagenes Rehmberg, Erik January 2021 (has links)
The increased customer demand for innovative and sustainable solutions implies that companies need to seek knowledge, and insights, beyond their traditional business models. This by opening up barriers and collaborating with other stakeholders. Using this approach is referred to in the literature as practicing open innovation. There is however a lack of research on open innovation concerning radical innovation and collaboration. The purpose of this report is to fill this research gap by investigating how a large incumbent company can set up radical collaboration in an open innovation space. The gap will be filled by conducting a qualitative and explorative cross-case analysis with the hosting company of this study, IKEA, and the research questions presented in this report aims to assist IKEA in the set of radical collaboration. The research question and related results were divided into four parts; Strategy implications, partner selection criteria, challenges and success factors. Regarding the first sub-research question, the strategy of the OIS should be aligned to the long-term goals of the parent firm but the short-term targets should not be controlled. This in order to give the OIS mandate to come up with unexpected and radical solutions. Moreover, in the partner selection process, important criteria to consider for radical collaboration are shared values, culture, and commitment to the project. Concerning challenges with radical collaboration, these are: Clear expectations, Contracts, Identifying focus areas, Implementation of the innovations, Innovation strategy renewal, Introduction of a new concept, NDA’s, Outsourcing and Organizational behavior. Lastly, the findings show that autonomy, self-control, communication, and structure are important success factors. The related recommendation of this thesis is that large established companies, looking to pursue radical collaboration in an open innovation format, should consider these insights to be successful. It should however be made clear that radical innovation practices tend to be more complex and time-consuming. Thus, KPIs for success may need to be revisited in firms traditionally seeking incremental innovations with in-house innovation practices. / Med en ökande efterfrågan från kunder på innovativa och hållbara lösningar behöver företag söka kunskap och resurser utanför sina traditionella affärsmodeller. Detta genom att öppna upp sina interna processer och samarbeta med andra. Att använda detta tillvägagångssätt hänvisas till i litteraturen som att utöva “öppen innovation”. Det saknas dock forskning i ämnet som rör radikal innovation och samarbete. Syftet med denna rapport är att fylla detta forskningsgap genom att undersöka hur ett stort etablerat företag kan starta upp radikala samarbeten i ett öppet innovationslandskap. Gapet kommer att fyllas genom att utföra en kvalitativ och explorativ flerfallsstudie med ett värdföretag, IKEA, och forskningsfrågorna som presenteras i denna rapport har som mål att skapa ett ramverk för att hjälpa IKEA introducera radikala samarbeten. Forskningsfrågan och relaterade resultat delades in i fyra delar; Strategi implikationer, partnervalskriterier, utmaningar och framgångsfaktorer. När det gäller den första forskarfrågan bör innovationsstrategin anpassas till moderföretagets långsiktiga mål, men de kortsiktiga målen bör inte kontrolleras. Detta för att ge initiativet mandatet att komma med oväntade och radikala lösningar. Dessutom är viktiga kriterier att ta hänsyn till, för radikala samarbeten i urvalsprocessen av partners, att de samarbetande parterna delar värderingar, kultur och engagemang för projektet. Vad gäller utmaningar för radikalt samarbete är dessa de mest kritiska: Tydliga förväntningar, Kontrakt, Identifiera fokusområden, Implementering av innovationer, Förnyelse av Innovationsstrategi, Introduktion av ett nytt koncept, Sekretessavtal, Outsourcing och Organisatoriskt beteende. Slutligen visar resultaten att autonomi, självkontroll, kommunikation och struktur är viktiga framgångsfaktorer. Den avslutande uppmaningen är att stora etablerade företag, som vill sträva efter radikalt samarbete i ett öppet innovationslandskap, bör ha dessa insikter i beaktning för att initiativet ska bli framgångsrikt. Det bör dock klargöras att radikala innovationsmetoder tenderar att vara mer komplexa och tidskrävande. Därför kan KPI:er för framgång behöva ses över hos företag som traditionellt söker inkrementell innovation med interna innovationsmetoder.
608

Lebensqualität nach robotisch-assistierter und konventioneller laparoskopischer radikaler Prostatektomie: Ergebnisse der multizentrischen, randomisiert-kontrollierten LAP-01 Studie

Lemaire, Emilie 06 February 2023 (has links)
Background: To explore cross‐sectional and longitudinal differences in general health‐related and prostate cancer‐specific quality of life (QoL) after robotic‐assisted (RARP) and laparoscopic (LRP) radical prostatectomy and to analyze predictive variables for QoL outcomes. Methods: In this multicenter, randomized controlled trial, prostate cancer patients were randomly assigned 3:1 to undergo either RARP or LRP. Patient‐reported outcomes were prospectively collected before and 1, 3, 6, 12 months after radical prostatectomy and included QoL as a secondary outcome. Validated questionnaires were used to assess general health‐related (EORTC QLQ‐C30) and prostate cancerspecific (QLQ‐PR25) QoL. Cross‐sectional and longitudinal contrasts were analyzed through linear mixed models. Predictive variables for QoL outcomes were identified by general linear modeling. Results: Of 782 randomized patients, QoL was evaluable in 681 patients. In terms of general QoL, the cross‐sectional analysis showed only small differences between study arms, whereas longitudinal comparison indicated an advantage of RARP on recovery: RARP patients reported an earlier return to baseline in global health status (3 vs. 6 months) and social functioning (6 vs. 12 months). In role functioning, only the RARP arm regained baseline scores. Regarding prostate‐specific QoL, LRP patients experienced more urinary symptoms and reported 3.2 points (95% confidence interval 0.4–6, p = 0.024) higher mean scores at 1‐month follow‐up and in mean 2.9 points (0.1–5, p = 0.042) higher urinary symptoms scores at 3‐month follow‐up than RARP patients. There were no other significant differences between treatment groups. Urinary symptoms, sexual activity, and sexual function remained significantly worse compared with baseline at all time points in both arms. Conclusions: Compared with LRP, the robotic approach led to an earlier return to baseline in several domains of general health‐related QoL and better short‐term recovery of urinary symptoms. Predictive variables such as the scale‐specific baseline status and bilateral nerve‐sparing were confirmed.:1 Abkürzungsverzeichnis 3 2 Einführung 4 2.1 Das Prostatakarzinom 4 2.1.1 Vorsorge und Diagnostik 4 2.1.2 Grundsätze der Therapie 5 2.1.3 Die radikale Prostatektomie 6 2.2 Lebensqualität 8 2.2.1 Gesundheitsbezogene Lebensqualität 8 2.2.2 Lebensqualität von Prostatakarzinompatienten 9 2.2.3 Prädiktoren der Lebensqualität nach radikaler Prostatektomie 12 2.3 Die LAP-01 Studie 13 2.3.1 Studiendesign 13 2.3.2 Lebensqualität im Rahmen der LAP-01 Studie 15 2.4 Zielsetzung und Fragestellung 16 3 Publikationsmanuskript 17 4 Zusammenfassung der Arbeit 28 5 Literaturverzeichnis 33 6 Anlagen 39 6.1 EORTC QLQ-C30 39 6.2 EORTC QLQ-PR25 42 7 Darstellung des eigenen Beitrags 44 8 Selbstständigkeitserklärung 45 9 Lebenslauf 46 10 Danksagung 48
609

Ciclorreversión de iones radicales de oxetanos

Pérez Ruiz, Raúl 07 May 2008 (has links)
La ciclorreversión (CR) oxidativa ó reductiva de oxetanos por transferencia electrónica fotoinducida (TEF), no ha sido estudiada en profundidad, a pesar de que este proceso ha despertado un gran interés en la última década en relación con la exploración de nuevas rutas sintéticas y con la reparación fotoquímica del ADN. Respecto a la via fotooxidativa, teniendo en cuenta los cálculos teóricos y los datos experimentales ya publicados sobre su naturaleza se ha considerado interesante realizar un estudio experimental que aporte nuevos conocimientos acerca del mecanismo de reacción. En este contexto, se ha elegido como sustrato modelo el trans,trans-2-ciclopropil-3-fenil-4-metiloxetano (1) que ha permitido aclarar aspectos mecanísticos de la CR oxidativa de oxetanos. La escisión de 1 por ruptura inicial del enlace C2-C3 da lugar a los compuestos utilizados en la fotocicloadición de Patero-Büchi para la síntesis de 1. Por el contrario, la formación de un fotoproducto nuevo debido a la captura nucleofílica intermolecular del intermedio resultante de la fragmentación al enlace O-C2 por acetonitrilo está de acuerdo con un mecanismo por pasos. Respecto a la via fotorreductiva, se ha estudiado la CR del sustrato modelo trans,trans-2-(4-cianofenil)-3-fenil-4-metiloxetano (4) usando el 1-metoxinaftaleno como fotosensibilizador. Los datos experimentales son consistentes con que la reacción tiene lugar desde el estado singlete del sensibilizador. La fragmentación del anión radical de 4 ocurre por ruptura de los enlaces O-C2 y C3-C4 dando lugar a productos (acetaldehído y 4-cianoestilbeno) diferentes a los usados para la síntesis de 4 por medio de la fotociloadición de Paterno-Büchi. El proceso transcurre a través del anión radical del trans-4-cianoestilbeno, que se ha detectado mediante FDL (?max = 500 nm). Además, se ha estudiado la CR reductiva intramolecular utilizando como sustratos el (2S)-2-(6-metoxinaft-2-il)propanoato de (2R,3S,4S)-[2-(4-cianofenil)-3-feniloxetano-4-il / Pérez Ruiz, R. (2006). Ciclorreversión de iones radicales de oxetanos [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/1925
610

Calcul de la puissance annulatrice du radical à partir du carquois ordinaire

Henry, Marion January 2015 (has links)
Dans ce mémoire, on commence par introduire le radical de la catégorie mod A pour une algèbre donnée A de dimension finie sur un corps algébriquement clos, avant d'en définir la puissance annulatrice dans le cas où A est de représentation finie. On calcule ensuite cette puissance annulatrice en fonction du nombre de cordes dans le carquois ordinaire Q_A, dans le cas où A est une algèbre inclinée itérée de type A.

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