Les carbapénèmes occupent actuellement une place centrale dans la lutte contre les bactéries résistantes aux antibiotiques classiques de type pénicilline. Notre thèse a pour objectif de développer une synthèse de leurs intermédiaires dans l'optique d'une application à l'échelle industrielle. Nous avons exploité, comme stratégie de fermeture de l'hétérocycle, la formation du lien C-3/C-4 par attaque nucléophile intramoléculaire sur un époxyde. Celui-ci est obtenu à partir de la L thréonine qui fournit deux stéréocentres et permet d'induire le troisième carbone asymétrique. Nous avons utilisé le groupe benzhydryle comme groupe protecteur, nouveau dans cette chimie, pour remplacer le groupe para-anisyle habituel qui pose des problèmes industriels. Ce nouveau groupe change fortement la réactivité de l'époxyamide impliquant une optimisation délicate des conditions et un choix judicieux des substituants. De plus, une nouvelle méthode de déprotection par bromation photochimique a été mise au point, complètement compatible avec la fragilité du cycle beta-lactame. Enfin, pour générer le groupe partant en C-4, nous avons utilisé une oxydation de Baeyer-Villiger. La régiosélectivité de cette étape dépend fortement des substituants et apparaît contradictoire avec les exigences de la fermeture de cycle. L'étude de l'influence des substituants sur ces deux étapes nous a permis de sélectionner le substituant optimal. Dans la seconde partie de cette thèse, nous nous intéressons à l'introduction du 4e centre asymétrique caractéristique des carbapénèmes. Nous avons étudié la possibilité de l'effectuer avec des dérivés de l'acide de Meldrum pour substituer la position C-4 de l'intermédiaire-clef, suivi d'une décarboxylation asymétrique. Nous clôturons ce travail par une évaluation économique de notre synthèse d'un précurseur équivalent à l'acétoxyazétidinone. /Carbapenems occupy a central role in the fight against bacteria that are resistant to classical antibiotics such as penicillins. Our thesis has the aim to develop a synthesis of their principal intermediates with the objective to apply it at the industrial scale. We have explored, as strategy of the heterocycle closing, the formation of the C-3/C-4 bond by a nucleophilic attack on an epoxide. This one was obtained from L-threonine which brings two stereocenters and allows the induction for the creation of the third asymmetric carbon. We used the benzhydryl group as protecting group, new in this chemistry, to replace the usual para-anisyl group which causes industrial problems. This new group strongly affects the reactivity of the epoxyamide imposing a fine optimization of the conditions and an adequat choice of substituents. Furthermore, a new deprotection method by photochemical bromination was developed, entirely compatible with the fragility of the beta-lactam ring. Finally, to create the leaving group in C-4, we used a Baeyer-Villiger oxidation. Regiochemistry of this step strongly depends on substituents and appears contradictory with the requirements of the ring closing. The study of the influence of the substituents on these two steps permits us to choose the optimal substituent. In a second part of the work, we were interested in the introduction of the fourth asymmetric center of carbapenems. We studied the feasibility to perform it with Meldrum's acid derivatives by substituting the C-4 position of the key-intermediate, followed by an asymmetric decarboxylation. We ended this work by an economic evaluation of the synthesis of our precursor similar to acetoxyazetidinone.

The first part of the work describes a procedure of oligonucleotide purification using a reversed-phase cartridge. The developed method employs a very efficient yet mild oligonucleotide detritylation on the cartridge support allowing fast purification of oligonucleotides regardless of their 5´-modification. Thiol- and amino-modified oligonuc-leotides were detritylated and purified with the same high efficiency as non-modified oligonucleotides. The method enables fast, parallel and automated purification of many oligonucleotide probes that was not possible before. In combination with the method of removal of tritylated failure fragments oligonucleotides were produced with purity superior to that of oligonucleotides purified using RP HPLC. In the second part of the present study a method of solid-phase RNA synthesis using 2´-tert-butyldithiomethyl (2´-O-DTM) is discussed. The stability of the DTM group during oligonucleotide assembly and deprotection in ammonia, together with its ability for rapid deprotection under mild conditions, allowed the synthesis of RNA with the quality similar to that of synthetic DNA oligonucleotides. The advantage of the 2´-O-DTM group is that it is completely orthogonal to all protecting groups used for the traditional solid-phase DNA synthesis. Therefore, the synthesis can be performed using a standard DNA synthesis procedure – no changes are needed for the product assembly. RNA oligonucleotides synthesized with retained 5´-terminal trityl group can be subjected to a cartridge-based purification using the procedure described in the first part of the study. The phosphoramidite synthesis was optimized for a large scale preparation and gives versatility for introduction of other alkyldithiomethyl groups according to the preference to their certain properties. The third part of the thesis describes the synthesis of a dithiomethyl linker and its utility for reversible conjugation of oligonucleotides. A dithiomethyl group, cleavable under mild conditions, was introduced onto 3´-OH of tritylated nucleosides via 3´-O-methylthiomethyl derivatives. The influence of different alkyl substituents on the disulfide bond stability was investigated, and stable analogues were employed in oligosyntheses. Two applications were developed using the present linker: 1) purification of oligonucleotides linked to the solid support; and 2) cartridge-based purification of tritylated oligonucleotides having an additional hydrophobic group on their 3´- terminus.

Gemäß der Zielstellung der Dissertation wurden verschiedene partiell tert.-Butyl- (TBU) und tert.-Butyloxycarbonyl- (Boc) geschützte Blockcopolymere auf der Basis von Poly(4-hydroxystyrol) mit engen Molmassenverteilungen sowie mit verschiedenen Blockzusammensetzungen dargestellt. Die Synthese dieser partiell TBU- und Boc-geschützten Blockcopolymere umfasste drei wesentliche Schritte: 1) Darstellung von Makroinitiatoren mittels NMRP, 2) Synthese von orthogonal geschützten Precursor-Blockcopolymeren durch Reinitiierung der Makroinitiatoren in Gegenwart eines weiteren orthogonal geschützten Monomeren und 3) orthogonale und quantitative polymeranaloge Umsetzungen ausgehend von den orthogonal geschützten Precursor-Blockcopolymeren. Mit den partiell TBU- und Boc-geschützten Blockcopolymeren wurden dünne Polymerfilme mittels „dip-coating“ präpariert. Die Untersuchung der Topographie und Morphologie der Filme erfolgte mit dem AFM. Aus den erhaltenen Topographie- und Phasenverschiebungsbildern ging eindeutig hervor, dass die verschiedenen Blöcke der jeweiligen partiell TBU- und Boc-geschützten Blockcopolymere in allen Polymerfilmen phasensepariert vorlagen. Reguläre Mikrostrukturen konnten allerdings nur bei den Polymerfilmen erhalten werden, deren Blockcopolymere sich allesamt durch asymmetrische Blockzusammensetzungen auszeichnen. Auf der Grundlage des statistischen Modellpolymeren Poly(styrol-r-4-hydroxystyrol) konnte ferner gezeigt werden, dass sich die phenolischen Hydroxylgruppen durch die Umsetzung mit Propargylbromid quantitativ in Propargylether-Gruppen umwandeln lassen und diese dann ihrerseits mit Hilfe der Cu(I)-katalysierten 1,3-dipolaren Cycloaddition (Click-Chemie) weiter mit einer Reihe von verschiedenen Aziden funktionalisiert werden können.

This thesis analyses minority shareholder protection in common law and civil law systems. Principally, this is done by examining closely-held corporations created under Canadian, Ukrainian and German laws. It examines minority shareholder protection by critically analyzing voting and related rights, the right to information; withdrawal from the company, expulsion right, the dissolution of a company, derivative action and direct action. The thesis also summarizes problems in the civil law system that cannot be solved in favor of minority shareholders. In addition to the above-mentioned, it provides possible solutions to the problems of minority shareholder protection in the civil law system, that is, methods by which to increase protection for minority shareholders against the majority and/or directors. Specifically, it focuses on cumulative voting, common law director’s duties, derivative action and the oppression remedy. Moreover, this thesis analyzes the possibility of incorporating some institutions into civil law legislation and considers obstacles to implementing them.

The graduation theses gives the general information about people´s protection in extraordinary situations at home, where the offender is a member of the family. It aims at police strategy by protection the victim of some crime. The key role in the system belongs to the Police of the Czech Republic, who is in most cases the first one who meet the victim and the offender and who has authority to control and to stop the social unacceptable behaving. Part of the graduated theses is to explain what is dangerous persecution-stalking. Also the kinds and victims of dangerous persecution, assessing og dangerousness. The problem of a victim is a very important part which was neclegted in the past. Also the fact that a deep knowledge in this problems is very important for the Police is written in my theses. Next part of my theses is explanation of victimology and characterization of the key word ?victim?. The role of the intervention center and their cooperation with the Police of the Czech Republic by protecting the victim and solving the extraordinary situations at home. The protecting the victim can be done uder the low § 50 NO.273/2008 about Police of the Czech republic and because of that there is methodology of police´s procedure by giving the protection to person who need it in my theses.

Air pollution is extensive problem throughout Moravian-Silesian Region and in addition impacts many lives in so settled agglomeration. Harmful substances that here aloft occur often in several fold go beyond limit for health protection, are toxic to environment and people who live there, therefore it is so important for protection of people to deal with this topic. It is necessary to determine, how much actually air pollution affects the health of the people. Hypothesis H1 deals with question. In cooperation with the Department of Air Protection Hydro meteorological Institute in Ostrava and Regional hygiene station of Moravian-Silesian region, were compared data of the current PM10 pollution particles weekly morbidity and acute respiratory diseases. If condition of the air worsens, sickness does not improve and when air quality is improving, declining disease and acute respiratory infections in the region - between air pollution and health status of the population is correlation. For hypothesis H2 was created questionnaire, and was distributed to resident of region with rate of return of 87 %. The most general questions were answered correctly. The issue came to the question of determining current situation, so H2 hypothesis was confirmed only partially. The only way how to do protecting the population it is functional warning. Also it was investigated by a special comparative method, when resident were warned in which value of the PM10. 38 % residents say, that they were never warned, so the hypothesis H3 was also confirmed partly. After analyzing the problem was created proposal how to deal with this situation in ORP Bohumín case. Inhabitants of the region were divided into two groups. Active group, it is a group of people who have internet connection and do not use it. It was therefore created information leaflet and stickers, whose main task is to attract attention and show the population, where information about current pollution can be found. Part of this leaflet is also notes, in which people were less informed in questionnaire. The second group is passive then ? residents who do not have internet access or they cannot us it. So it was crated a system of rotating information board, and design its location in the ORP Bohumín in an public areas, where accumulate a larger number of people. On such a board could be automatically sent actual time data through network communication. It would be also appropriate add alarm warning system, but its execution would have to be limited to a certain level due to the frequent exceed in most municipalities in the region. There would be also possibility to benefit a warning to citizens through the fire protection of Volunteer firefighter. Especially if was declared by smog situation. Of course there is a also the option to use warning sirens, but I think it such a way of warning could cause unnecessary panic. The following suggestions are valid for both groups. It was displayed map of Low Emission Zone form information available in ORP Bohumín. System of isolation green spaces.. It was also examined whether the type of activity plan prepared long-term inverse situation in the region, but according to HZS does not pose a threat to the region, which would require the declaration of emergency state. So developments of operational plan isn´t necessary yet. However, the time is main aspect for gradual improvement of the warning and informing the population. The results showed that the general awareness of the issue is sufficient, but is also necessary to pay attention to the current situation in order to reduce the health risks to the lowest level. I am not sure that citizens must learn how to reconcile with living in conditions, but they should be patient, of course contribute to improve this situation by for example informing themselves about current pollution.

Made available in DSpace on 2016-04-18T21:06:36Z (GMT). No. of bitstreams: 3 Lidiane Aparecida Longo Garcia Goncalves1.pdf: 2577954 bytes, checksum: d8d639743559d333157f28bcb8793fef (MD5) Lidiane Aparecida Longo Garcia Goncalves2.pdf: 4181689 bytes, checksum: f216a534c6c8d562e49e84ce660b7996 (MD5) Lidiane Aparecida Longo Garcia Goncalves3.pdf: 3585457 bytes, checksum: 37c34552a2cade0a7f20a3895c352fb9 (MD5) Previous issue date: 2010-08-30 / Fundo Mackenzie de Pesquisa / The Brazilian Constitution establishes as a rule for appointment to public offices and positions the previously approvation by the tender, under penalty of nullity. The fixedterm contract to meet the temporary need of exceptional public interest is an exception, but there are two situations that lead its declaration: the extension of contracts beyond the time limit allowed by law, when there is no more the aspect of temporary need or hiring to work on activities that are not included on the exhaustive list of the law authorizing. In these cases, the majority jurisprudential understanding is that the contract must be declared invalid retroactively and the worker has only the right entitled to payment of the consideration agreed, upon in relation to the number of hours worked, respected the value of the minimum wage, and the values related to FGTS deposits. This placement, however, forsake an employee who acted in good faith and relied on the legitimacy of actions taken by the state, besides did not do reference about the punishment of the agent responsible for the unlawful administrative act. The systematic reading of the constitutional text reveals the necessity to maintain legal certainty, which is effective, in this case, with the protection of the worker in the face of the nullity of recruitment by the Public Administration. To do so, must be declared the invalidity of the contract with effects ex nunc, preserving the factual situation to the past tense statement, with the State ordered to compensate the work done with all sums, other than those typical of remission without cause, because the termination of the contract was made by virtue of its declaration of invalidity. / A Constituição brasileira estabelece como regra para investidura em cargos e empregos públicos a aprovação prévia em concurso público, sob pena de nulidade. O contrato por tempo determinado para atender a necessidade temporária de excepcional interesse público é uma exceção, mas há duas hipóteses que ensejam sua nulidade: a prorrogação dos contratos para além dos prazos autorizados pela legislação, quando não mais existe o aspecto temporário da necessidade ou a contratação para atuar em atividades que não estão relacionadas no rol taxativo da lei que a autoriza. Nestes casos, o entendimento jurisprudencial majoritário é de que o contrato deve ser declarado nulo retroativamente e o trabalhador tem direito apenas ao pagamento da contraprestação pactuada, em relação ao número de horas trabalhadas, respeitado o valor da hora do salário mínimo, e dos valores referentes aos depósitos do FGTS. Este posicionamento, contudo, desampara o trabalhador que agiu de boa-fé e confiou na legitimidade dos atos praticados pelo Estado, além de ser omisso no tocante à punição do agente responsável pelo ato administrativo inválido. A leitura sistemática do texto constitucional revela a necessidade de manutenção da segurança jurídica, o que se efetiva, nesta hipótese, com a proteção deste trabalhador em face da nulidade de contratação pela Administração Pública. Para tanto, deve-se declarar a invalidade da contratação com efeitos ex nunc, resguardando a situação fática pretérita à declaração, sendo o Estado condenado a indenizar o trabalho prestado com todas as verbas contratuais trabalhistas, excluindo-se aquelas típicas da dispensa imotivada, pois a extinção do contrato se deu em virtude de sua declaração de nulidade.

Diese Arbeit beschäftigt sich mit der Synthese neuer photoreaktiver Polymere, die bei Bestrahlung mit Licht (Hg-Dampflampe, fs-gepulster Ti:Sa-Laser) definierte Reaktionen durchlaufen. Mittels kontrolliert-radikalischer Polymerisation und anschließender polymeranaloger Reaktion wurden verschiedene Azobenzen-Derivate, Arylazosulfonat-Derivate und photolabil geschützte Aminogruppen (Nitroveratryloxycarbonyl, Nvoc) in Methacrylat-Polymere eingeführt. Diese Strukturen wurden ausführlich hinsichtlich ihrer Struktur und vor allem ihrer photochemischen Eigenschaften (Extinktionskoeffizienten, Zerfallskinetik) untersucht. Dünne Schichten (d<30nm) der so hergestellten Materialien wurden bei der Entwicklung einer neuen photolithographischen Methode, der plasmonischen Nanolithographie, eingesetzt.:INHALTSVERZEICHNIS ABBILDUNGSVERZEICHNIS TABELLENVERZEICHNIS ABKÜRZUNGS- UND SYMBOLVERZEICHNIS 1 EINLEITUNG UND ZIELSTELLUNG 2 THEORETISCHE GRUNDLAGEN 2.1 PHOTOREAKTIVE POLYMERE 2.1.1 Azobenzenhaltige Polymere und deren Anwendungen 2.1.2 Arylazosulfonathaltige Polymere und deren Anwendungen 2.1.3 Photolabil geschützte Amine in Polymeren und zur Oberflächenstrukturierung 2.2 NICHT-LINEAR OPTISCHE EFFEKTE - FREQUENZVERDOPPLUNG 2.3 OBERFLÄCHENPLASMONENRESONANZ UND SHG AN METALLISCHEN NANOPARTIKELN 2.4 PHOTOCHEMISCHE STRUKTURIERUNG DÜNNER SCHICHTEN 2.5 NANOLITHOGRAPHISCHE STRUKTURIERUNG MITTELS PLASMONISCHER EFFEKTE AN METALLNANOSTRUKTUREN 3 ERGEBNISSE UND DISKUSSION 3.1 AZOBENZENHALTIGE POLYMERE 3.1.1 Synthese niedermolekularer Azobenzen-Derivate 3.1.2 Anbindung an Polymermatrix 3.1.3 Photochemische matrixabhängige Untersuchung der Isomerisationskinetik 3.1.4 Bestrahlung in dünnen Schichten mit gepulstem Femtosekunden-Laser 3.2 ARYLAZOSULFONATHALTIGE POLYMERE 3.2.1 Kontrolliert-radikalische Polymerisation von Arylazosulfonat-Monomeren 3.2.1.1 Synthese der arylazosulfonathaltigen Monomere 3.2.1.2 RAFT-Polymerisation von (AS-Mon2) 3.2.2 Polymeranaloge Einführung von Arylazosulfonateinheiten 3.2.3 Präparation und Bestrahlung dünner Schichten 3.3 PHOTOLABIL GESCHÜTZTE AMINOPOLYMERE 3.3.1 Synthese von statistischen Nvoc-geschützten Aminocopolymeren 3.3.1.1 Anbindung des Nvoc-geschützten Amins über Esterbindung 3.3.1.2 Anbindung des Nvoc-geschützten Amins über Reaktion mit Nvoc-Cl 3.3.2 Nvoc-haltige Diblockcopolymere 3.3.2.1 Synthese von P(MMA-co-GMA)-b-P(MMA-co-NvocCMS) 3.3.2.2 Synthese von P(MMA-co-MAA)-b-P(MMA-co-NvocAEMA) 3.3.3 Präparation dünner Schichten der (Block-)Copolymere 3.3.4 Bestrahlung mit gepulstem Femtosekunden-Laser 4 ZUSAMMENFASSUNG UND AUSBLICK 5 EXPERIMENTALTEIL 5.1 ANALYTISCHE METHODEN 5.2 AUFBAU FÜR DIE FS-LASER-BESTRAHLUNG 5.3 VERWENDETE CHEMIKALIEN 5.4 SYNTHESEN 5.4.1 Azobenzen-Derivate 5.4.1.1 Niedermolekulare Verbindungen 5.4.1.2 Polymerisationen und polymeranaloge Reaktionen 5.4.2 Arylazosulfonate 5.4.2.1 Niedermolekulare Verbindungen 5.4.2.2 Freie radikalische Polymerisation 5.4.2.3 RAFT-Polymerisationenen 5.4.2.4 Polymeranaloge Reaktion 5.4.3 Nvoc-geschützte (Block-)Copolymere 5.4.3.1 Niedermolekulare Verbindungen 5.4.3.2 Polymerisationen 5.4.3.3 Polymeranaloge Reaktionen 5.5 WAFERREINIGUNG UND PRÄPARATION DÜNNER SCHICHTEN LITERATURVERZEICHNIS DANKSAGUNG VERSICHERUNG

Gemäß der Zielstellung der Dissertation wurden verschiedene partiell tert.-Butyl- (TBU) und tert.-Butyloxycarbonyl- (Boc) geschützte Blockcopolymere auf der Basis von Poly(4-hydroxystyrol) mit engen Molmassenverteilungen sowie mit verschiedenen Blockzusammensetzungen dargestellt. Die Synthese dieser partiell TBU- und Boc-geschützten Blockcopolymere umfasste drei wesentliche Schritte: 1) Darstellung von Makroinitiatoren mittels NMRP, 2) Synthese von orthogonal geschützten Precursor-Blockcopolymeren durch Reinitiierung der Makroinitiatoren in Gegenwart eines weiteren orthogonal geschützten Monomeren und 3) orthogonale und quantitative polymeranaloge Umsetzungen ausgehend von den orthogonal geschützten Precursor-Blockcopolymeren. Mit den partiell TBU- und Boc-geschützten Blockcopolymeren wurden dünne Polymerfilme mittels „dip-coating“ präpariert. Die Untersuchung der Topographie und Morphologie der Filme erfolgte mit dem AFM. Aus den erhaltenen Topographie- und Phasenverschiebungsbildern ging eindeutig hervor, dass die verschiedenen Blöcke der jeweiligen partiell TBU- und Boc-geschützten Blockcopolymere in allen Polymerfilmen phasensepariert vorlagen. Reguläre Mikrostrukturen konnten allerdings nur bei den Polymerfilmen erhalten werden, deren Blockcopolymere sich allesamt durch asymmetrische Blockzusammensetzungen auszeichnen. Auf der Grundlage des statistischen Modellpolymeren Poly(styrol-r-4-hydroxystyrol) konnte ferner gezeigt werden, dass sich die phenolischen Hydroxylgruppen durch die Umsetzung mit Propargylbromid quantitativ in Propargylether-Gruppen umwandeln lassen und diese dann ihrerseits mit Hilfe der Cu(I)-katalysierten 1,3-dipolaren Cycloaddition (Click-Chemie) weiter mit einer Reihe von verschiedenen Aziden funktionalisiert werden können.

Syftet med den här studien är att få en djupare inblick i hur några få svenska folkmusiker resonerar kring begreppen bevarande, förankring och interpretation i den svenska folkmusikaliska traditionen – i det egna musicerandet såväl som i den egna undervisningen. Definitioner av och resonemang kring traditionsbegreppet i relation till begreppen bevarande, förankring och interpretation utgör studiens teoretiska utgångspunkter. För att få svar på mina forskningsfrågor har jag intervjuat fyra av Sveriges, i olika mån erfarna och framträdande musiker och lärare inom den folkmusikaliska genren, med kvalitativ intervju som metod. Genom att analysera resonemang kring dessa begrepp är avsikten att presentera en sammanställning av vad som är av störst betydelse i det egna musicerandet samt i den egna undervisningen för dessa personer.  Samtliga informanter värderar interpretation mycket högt såväl i det egna musicerandet som i den egna undervisningen. Vidare fann jag vissa skillnader i hur informanterna uttryckte sig om värdet av bevarandet och förankringen i den folkmusikaliska traditionen. Samtliga informanter var dock överens om att förankringen i någon mån finns med såväl i det egna musicerandet som i den egna undervisningen. Tankarna som berör traditionsbevarande presenteras och i studien går att få en bild av ett visst avståndstagande från begreppet. Informanterna talar hellre om förankring, förmedling och förvaltande än bevarande av musiken. / The goal with this study is to illuminate the thoughts of a selected number of Swedish folk musicians and teachers regarding conservation, anchoring and interpretation in the Swedish folk music tradition – in their own music making as well as in their own teaching. Definitions of and reasoning around the terms of traditions in relation to the concepts mentioned above, is the basic theoretical principles of the study. In order to get answers to my research questions I have interviewed four Swedish folk musicians and teachers with different experience, with qualitative interview as my method. The intention of analyzing the informants’ thoughts related to these concepts is to present a compilation of what is most significant in their own music making and in their own teaching.  All informants value interpretation very high in their own music making and teaching. Further, I also found certain differences in how the informants express themselves regarding the value of conservation and anchoring in the folk musical tradition. Nevertheless, all informants agreed upon that the anchoring is included in their own music making and their own teaching to some extent. When questions concerning the concept of conserving traditional music is presented to the informants in the study, a certain amount of distancing towards the concept itself is clear; the informants rather talk about anchoring, conveying and preservation of the music.