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.

[ES] El espectro de la luz solar está compuesto por una amplia gama de radiaciones electromagnéticas las cuales tienen diferentes impactos sobre la vida en la tierra. Entre ellas, las pertenecientes a la región ultravioleta toman un papel principal cuando nos referimos a la fotobiología, ya que pueden interactuar con las biomoléculas por medio de procesos tanto directos como fotosensibilizados. Como resultado, estas biomoléculas pueden sufrir modificaciones que no siempre tienen efectos beneficiosos. En este contexto, los daños fotoinducidos al ADN son de gran relevancia ya que están estrechamente relacionados con la creciente incidencia de cáncer de piel. Por ello, es necesario investigar tanto los mecanismos involucrados en dichos procesos como el desarrollo de nuevas estrategias para combatirlos. En la presente tesis se da respuesta a estas necesidades mediante el desarrollo y empleo de grupos protectores fotolábiles (PPG). En una primera parte se avanza en el desarrollo de nuevos PPG basados en filtros solares. Estos ofrecen la ventaja de actuar, una vez liberados, como un escudo protector frente a la radiación ultravioleta. En este contexto, en el Capítulo 3 se profundiza en las propiedades fotofísicas y fotoquímicas de los sistemas formados por la avobenzona como PPG de ácidos carboxílicos, más concretamente del ketoprofeno (KP) y del naproxeno (NPX). En este estudio se analiza por medio de modelado molecular y técnicas espectroscópicas la influencia que tiene la energía relativa del triplete de la avobenzona en su forma dicetónica, 3AB(K)*, respecto a la de los compuestos protegidos en el proceso de liberación. Siguiendo en esta misma línea de trabajo, en el Capítulo 4 se ha desarrollado un nuevo PPG capaz de liberar el filtro solar oxibenzona (OB) junto con compuestos carbonílicos. En una segunda parte, el foco de atención se ha puesto en el concepto de "Caballo de Troya", el cual establece que ciertas lesiones del ADN pueden actuar a su vez como fotosensibilizadores endógenos generando así nuevas lesiones en su entorno. En este contexto, en el Capítulo 5 se han estudiado, mediante métodos tanto experimentales como teóricos, las propiedades fotosensibilizantes de dos de los daños oxidativos del ADN, el 5-formiluracilo (ForU) y la 5-formilcitosina (ForC), poniendo especial énfasis en la capacidad de estos para poblar sus estados tripletes, así como de inducir la formación fotosensibilizada de dímeros ciclobutánicos de pirimidina (CPD). Por último, en el Capítulo 6 se ha desarrollado una nueva alternativa sintética para la incorporación del ForU en oligonucleótidos. Debido a la inestabilidad del grupo aldehído, esta síntesis se lleva a cabo generalmente mediante la incorporación de un precursor el cual es posteriormente convertido en el ForU mediante la acción de un agente oxidante. Por el contrario, en la nueva alternativa planteada el aldehído es protegido con un PPG, de manera que una vez insertado en el ODN, el aldehído es liberado de forma selectiva mediante el empleo de luz. Este trabajo supone un avance en el estudio de las propiedades fotosensibilizantes del ForU ofreciendo una nueva herramienta para la evaluación de las mismas en un entorno más cercano al del ADN. / [CA] L'espectre de la llum solar està compost per una àmplia gamma de radiacions electromagnètiques les quals tenen diferents impactes sobre la vida en la terra. Entre elles, les pertanyents a la regió ultraviolada prenen un paper principal quan ens referim a la fotobiologia, ja que poden interactuar amb les biomolècules per mitjà de processos tant directes com fotosensibilitzats. Com a resultat, aquestes biomolècules poden patir modificacions que no sempre tenen efectes beneficiosos. En este context, els danys fotoinduits a l'ADN són de gran rellevància ja que estan estretament relacionats amb la creixent incidència de càncer de pell. Per això, és necessari tant d'investigar els mecanismes involucrats en els processos com el desenvolupament de noves estratègies per a combatre'ls. En la present tesi es dóna resposta a aquestes necessitats per mitjà del desenvolupament i ús de grups protectors fotolàbils (PPG). En una primera part s'avança en el desenvolupament de nous PPG basats en filtres solars. Estos ofereixen l'avantatge d'actuar, una vegada alliberats, com un escut protector enfront de la radiació ultraviolada. En este context, en el capítol 3 s'aprofundeix en les propietats fotofísiques i fotoquímiques dels sistemes formats per l'avobenzona com PPG d'àcids carboxílics, més concretament del ketoprofé (KP) i del naproxé (NPX). En este estudi s'analitza per mitjà de modelatge molecular i tècniques espectroscòpiques la influència que té en el procés d'alliberament l'energia relativa del triplet de l'avobenzona en la seua forma dicetònica, 3AB(K)*, respecte a la dels compostos protegits. En esta mateixa línia de treball, en el capítol 4 s'ha desenvolupat un nou PPG capaç d'alliberar el filtre solar oxibenzona (OB) junt amb compostos carbonílics. En una segona part, el focus d'atenció s'ha posat en el concepte de "Cavall de Troia", el qual estableix que certes lesions de l'ADN poden actuar al seu torn com fotosensibilitzadors endògens generant així noves lesions en el seu entorn. En este context, en el capítol 5 s'han estudiat, per mitjà de mètodes tant experimentals com teòrics, les propietats fotosensibilitzants de dos dels danys oxidatius de l'ADN, el 5-formiluracil (ForU) i la 5-formilcitosina (ForC), posant especial èmfasi tant en la capacitat d'estos per a poblar els seus estats triplet, com d'induir la formació fotosensibilitzada de dímers ciclobutànics de pirimidina (CPD). Finalment, en el capítol 6 s'ha desenvolupat una nova alternativa sintètica per a la incorporació del ForU en oligonucleòtids. A causa de la inestabilitat del grup aldehid, esta síntesi es duu a terme generalment per mitjà de la incorporació d'un precursor el qual és posteriorment convertit en el ForU per mitjà de l'acció d'un agent oxidant. Al contrari, en la nova alternativa plantejada l'aldehid és protegit amb un PPG, de manera que una vegada inserit en l'oligonucleòtid, l'aldehid és alliberat de forma selectiva per mitjà de l'ús de llum. Este treball suposa un avanç en l'estudi de les propietats fotosensibilitzants del ForU i ofereix una nova ferramenta per a l'avaluació de les mateixes en un entorn més pròxim al de l'ADN. / [EN] The solar spectrum is composed of a wide range of electromagnetic radiations which have different impacts on life on earth. Among them, those belonging to the ultraviolet region are of utmost importance when we refer to photobiology, since they can interact with biomolecules through both direct and photosensitized processes. As a result, these biomolecules can undergo modifications that do not always have beneficial effects. In this context, photoinduced DNA damage is of great relevance as it is closely related to the increasing incidence of skin cancer. Therefore, it is necessary both to investigate the mechanisms involved in these processes and to develop new strategies to avoid them. In this Thesis these issues have been addressed through the development and use of photolabile protecting groups (PPG). The first part of this Thesis involves the development of new PPG based on solar filters. Once released, these PPG offer the advantage of acting as ultraviolet shields. In this context, Chapter 3 looks into the photophysical and photochemical properties of those systems formed by avobenzone as PPG of carboxylic acids, more specifically ketoprofen (KP) and naproxen (NPX). In this study, the influence on the photorelease process of the relative energetic location of the avobenzone triplet manifold in its diketo form, 3AB(K)*, with respect to that of its caged compound, is duly analyzed by means of molecular modeling and spectroscopic techniques. Following this same line of work, a new PPG capable of releasing oxybenzone (OB) solar filter along with carbonyl compounds has been developed in Chapter 4. The second part of this Thesis focuses on the "Trojan Horse" concept, which establishes that certain DNA lesions can act as endogenous photosensitizers, thus generating new lesions in their neighborhood. In this context, in Chapter 5 the photosensitizing properties of two oxidatively generated DNA damages, namely 5-formyluracil (ForU) and 5-formylcytosine (ForC), have been studied by means of experimental and theoretical approaches. Here, special emphasis has been placed on unraveling their capacity to photoinduce the formation of cyclobutane pyrimidine dimers (CPD). Finally, in Chapter 6 a new synthetic alternative for the incorporation of ForU into oligodeoxynucleotides (ODN) has been developed. Due to the instability of the aldehyde group, this synthesis is generally carried out by incorporating a precursor which is subsequently converted into ForU by the action of an oxidative agent. On the contrary, in the new approach, the aldehyde is protected with a PPG, so that once inserted into the ODN, the aldehyde is selectively released through the use of light. This work entails a step forward in the study of the photosensitizing properties of ForU, offering a new tool for their evaluation within the DNA environment. / Lineros Rosa, M. (2021). Photoremovable protecting groups for carbonyl compounds of biological interest [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/167764 / TESIS

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.