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Objetivos. Tendo em vista o caráter bidimensional dos fatores psicossociais relacionados ao estresse (CASSEL, 1974), este trabalho teve por objetivos: identificar a interação de fatores psicossociais negativos (estressores) e benéficos (protetores) presente na situação de trabalho de um grupo de operadores de telemarketing, e verificar o potencial do humor como \'recurso psicossocial\' frente ao estresse, como estratégia de coping (dimensão psicológica) e comportamento comunicativo favorecedor do apoio social (dimensão sociológica). Método. Foi realizado um estudo de caso em uma central de tele-atendimento de empresa administradora de planos de saúde pertencente a uma instituição pública, envolvendo doze entrevistas individuais e uma coletiva, semi-estruturadas, observação participante e aplicação de questionário, respondido por 124 operadores de telemarketing de diferentes turnos de trabalho. O questionário, auto-aplicável, constou de dados sócio-demográficos, questões sobre condições de trabalho, estresse no trabalho (KOMPIER & LEVI, 1995), fatores de incômodo e fadiga e satisfação, queixas de saúde e uso do humor. Os dados foram analisados com base no modelo Demanda-Controle (BAKER & KARASEK, 2000; KARASEK & THEORELL, 1990), tendo incluído: análise temática do conteúdo das entrevistas (MINAYO, 1982) e análise descritiva das freqüências obtidas através do questionário. Resultados. A população estudada era predominantemente feminina (72,6 por cento ), jovem (idade média 28 anos), com escolaridade secundária (48,4 por cento ) ou universitária (51,6 por cento ) e salário médio de R$ 600.00. 25,8 por cento eram estudantes. Entre outros, foram identificados fatores psicossociais negativos relacionados: ao ambiente físico; à estrutura temporal (pressão da fila; ritmo elevado externamente imposto; poucas pausas); à latitude decisória: a) falta de controle sobre a tarefa (rigidez da organização do trabalho; fraseologia padrão; falta de oportunidade de tomar decisões individuais, falta de participação); b) baixo grau de arbítrio da habilidade (grande volume de informações a processar, treinamento insuficiente; presença de terminologia médica); interface conteúdo, significado do trabalho e relacionamento com clientes provocando sofrimento emocional via empatia. O relacionamento com os clientes, um dos principais estressores do trabalho dos operadores, por freqüentemente envolver destrato, revelou-se importante fonte de satisfação quando envolve manifestação de reconhecimento. As referências aos fatores de incômodo e ix fadiga e de satisfação foram consistentes, respectivamente, com os fatores psicossociais estressores e benéficos, mostrando-se bons sinalizadores para a identificação daqueles aspectos. Entre os principais fatores de satisfação estavam a jornada de trabalho de seis horas e o relacionamento apoiador e brincalhão entre colegas e com os médicos auditores (apoio social). Quanto às queixas de saúde, 77,4 por cento dos sujeitos referiram sintomas osteomusculares; principais sintomas relacionados ao estresse referidos foram ansiedade (76,6 por cento ) e irritabilidade (66,1 por cento ). O uso do humor como coping foi referido por 78,2 por cento . Quanto a quem ri com quem, os dados indicam que brincadeiras são trocadas durante o trabalho entre os operadores, para 97,6 por cento ; dirigidas pelos operadores aos médicos, para 82,2 por cento ; dirigidas pelos médicos aos operadores, para 66,3 por cento ; pelos operadores aos supervisores, para 59,6 por cento , e pelos supervisores aos operadores, para 58,9 por cento . Conclusões. A situação de trabalho analisada apresentou grande predomínio de fatores psicossociais estressores em relação a \'protetores\' ou \'atenuantes\', representando combinação de intensidade e poucas chances de recuperação psicofisiológica ou, segundo o modelo Demanda-Controle, uma combinação de baixa latitude decisória com altas exigências (pressões psicológicas). O humor constitui um recurso psicossocial potencialmente \'protetor\' (CASSEL, 1974) ou \'modificador\' (BAKER & KARASEK, 2000) do processo de estresse, como estratégia de \'coping\' individual: por favorecer o distanciamento cognitivo; proporcionar alívio de tensão e expressão da subjetividade. Como comportamento comunicativo, o humor pode favorecer o apoio social (por convidar à proximidade; reduzir a distância entre níveis hierárquicos; permitir a expressão de críticas de forma socialmente menos arriscada); mas, acima de tudo, as trocas de humor refletem a dinâmica e a natureza das relações interpessoais, como indica a análise de quem ri com quem, uma das contribuições originais da pesquisa. Esta análise refletiu a presença de forte apoio social entre os operadores e entre estes e os médicos auditores. As brincadeiras \'relâmpago\' que irrompem durante o trabalho são percebidas como fontes de prazer, descarga de tensão e micro-espaços de reequilíbrio psicofisiológico. O humor integra o domínio da liberdade e é fortemente influenciado pelos valores. Se imposto aos trabalhadores, pode ser percebido como um constrangimento psicológico ou moral / Aim. Taking into account the two-dimensional nature of stress-related psychosocial factors (CASSEL, 1974), the study aimed at identifying the interrelation of negative (stressors) and protecting (beneficial) such factors in the work of a group of telemarketing operators, and the potential of humor as a \'psychosocial resource\' in face of stress at work, as a coping strategy (psychological dimension) and communicative behavior favoring social support (sociological dimension). Method. A case study was developed at a call center of the managed care unit of a public institution in São Paulo, Brazil. Data collection involved semi-structured interviews (twelve individual and one collective interview), participatory observation, and an inquiry responded by 124 operators from different work shifts. The inquiry included socio-demographic data, as well as questions on working conditions, factors of discomfort and fatigue and of work satisfaction, stress at work (KOMPIER & LEVI, 1995), health complaints and use of humor. Data analysis was based on the Demand/Control model (BAKER & KARASEK, 2000; KARASEK & THEORELL, 1990), and included content analysis of interviews (MINAYO, 1982), of data gathered through participatory observation, and descriptive analysis of inquiry frequencies. Results. The population studied was predominantly feminine (72.6 per cent ), young (average age 28 years), with high school (48.4 per cent ) or college education (51.6 per cent ) and average monthly wage around US$200.00. 25.8 per cent were students. Among others, negative psychosocial factors identified included: physical environment; time structure (pressure from the queue; high and externally imposed rhythm; few rest breaks); low decision latitude: a) low task control (strict work organization; script; lack of opportunity for individual decision making; lack of participation); and b) low skill discretion (great volume of information to be processed; insufficient training; presence of medical terminology); interrelation of work content, work meaning, and relationship with customers leading to emotional suffering through empathy. The relationship with customers, viewed as an important work-related stressor for often involving rude treatment, is perceived as an important source of satisfaction when involving recognition. Data on factors of discomfort and fatigue showed to be consistent with references to psychosocial stressors and protectors identified. Among protecting factors identified were the 6-hour working period and the supportive relationship among co-workers and with the medical auditors, often involving humor exchanges. Main health complaints were xi musculoskeletal (77.4 per cent ) and stress-related symptoms: anxiety (76.6 per cent ) and irritability (66.1 per cent ). Humor used as coping was referred by 78.2 per cent . Data on who laughs with who indicate that humorous/playful comments are often directed by operators to co-workers, for 97.6 per cent ; by operators to doctors, for 82.2 per cent ; by doctors to operators, for 66.3 per cent ; by operators to supervisors, for 59.6 per cent , and by supervisors to operators, for 58.9 per cent . Conclusions. The work situation of telemarketing operators studied involved a negative balance between psychosocial stressors and beneficial or mitigating factors: a combination of high work intensity and few chances of psycho-physiological recovery or, according to the Demand-Control model, a combination of high demands (psychological pressure) and low decision latitude. Humor is potentially a \'psychosocial resource\' (CASSEL, 1974) or \'modifying factor\' (BAKER & KARASEK, 2000) to the stress process, as an individual coping strategy, for favoring cognitive distancing/re-framing; relief from strain; expression of subjectivity. As a communicative behavior, humor may favor social support (for inviting to proximity; reducing social distance between different hierarchic levels, and permitting the expression of criticisms in less risky ways); but above all, humor as communicative behavior reflects interpersonal relationships dynamics and nature, as it was shown by the analysis of who laughs with who, an original contribution of this research that highlighted the presence of strong social support among operators and between them and the medical doctors. Brief humor events irrupting during work are perceived as a source of pleasure, and micro-spaces of psychophysiological recovery. Humor integrates the domain of freedom and is heavily influenced by cultural values. If it is imposed to workers, it may be perceived as a psychological or moral constraint

Made available in DSpace on 2016-04-26T20:21:20Z (GMT). No. of bitstreams: 1 Carlos Eduardo Afonso Rodrigues.pdf: 2823038 bytes, checksum: a258e5db3ccdadf4928a11019d529822 (MD5) Previous issue date: 2012-10-24 / The purpose of this essay is to reinforce the principle of the minimal intervention of the Criminal Law, placing it as a head principle of the modern environmental crimination and setting it as the last resort, due to its austerity and the selectivity of its penalties and of its stigmatizing character, on the battle against the unbridled consumption of the natural resources which currently occurs. Previously to the concretion of a political-criminal view of the environmental crimination, the legislative instruments used in the environmental protection were subject of a rigorous legitimacy check, finding that, from the analysis of the criminal elements in the Constitution, various are the legal-dogmatic implications that convey and the jeopardy to freedom is great, leading to serious hesitation about the aptitude of the Criminal Law to refrain harmful acts to the environment. The modest contribution that the criminal regulation can offer to the environmental protection, mainly due to the fact that it s a systemic-structural issue demanding broader solutions than the exceptional incidence of the Criminal Law, on one side, and the existence of other mechanisms formal and informal oriented to the effective protection of the environment, on the other side, bind the assumption of measures outside of the Criminal Law that aim to confront the growing environmental degradation, materializing at the same time a serious decriminalizing scheme of the criminal dispositions pertaining Criminal Environmental Law existing today / O objetivo perseguido na presente dissertação é o de fortalecer o princípio da intervenção mínima do Direito Penal, colocando-o como princípio reitor da moderna incriminação ambiental e fincando-o como última alternativa, mercê da severidade e seletividade de suas sanções e de seu caráter estigmatizante, no combate à desenfreada consumação dos recursos naturais que se verifica na atualidade. Antes da concreção de um olhar político-criminal a respeito da incriminação ambiental, os instrumentos legislativos utilizados na proteção do ambiente foram objeto de rigoroso filtro de legitimidade, verificando-se que, à luz da principiologia penal cravada no Texto Maior, são múltiplas as implicações jurídico-dogmáticas que deles advêm e os riscos à liberdade, inúmeros, fazendo pairar forte dúvida sobre o potencial do Direito Penal de refrear atos lesivos ao meio ambiente. A modesta contribuição que a normatividade penal pode oferecer para a tutela do ambiente, sobretudo por se cuidar de problema estrutural sistêmico que demanda soluções mais abrangentes que a excepcional e episódica incidência do Direito Penal, por um lado, e a existência de outros mecanismos formais e informais vocacionados à eficaz do bem jurídico-ambiental, por outro, impõem a adoção de medidas extrapenais com vistas ao enfrentamento da crescente degradação ambiental, concretizando-se ao mesmo tempo um sério programa descriminalizador das disposições penais pertinentes ao Direito Penal Ambiental hoje existentes

Objetivos. Tendo em vista o caráter bidimensional dos fatores psicossociais relacionados ao estresse (CASSEL, 1974), este trabalho teve por objetivos: identificar a interação de fatores psicossociais negativos (estressores) e benéficos (protetores) presente na situação de trabalho de um grupo de operadores de telemarketing, e verificar o potencial do humor como \'recurso psicossocial\' frente ao estresse, como estratégia de coping (dimensão psicológica) e comportamento comunicativo favorecedor do apoio social (dimensão sociológica). Método. Foi realizado um estudo de caso em uma central de tele-atendimento de empresa administradora de planos de saúde pertencente a uma instituição pública, envolvendo doze entrevistas individuais e uma coletiva, semi-estruturadas, observação participante e aplicação de questionário, respondido por 124 operadores de telemarketing de diferentes turnos de trabalho. O questionário, auto-aplicável, constou de dados sócio-demográficos, questões sobre condições de trabalho, estresse no trabalho (KOMPIER & LEVI, 1995), fatores de incômodo e fadiga e satisfação, queixas de saúde e uso do humor. Os dados foram analisados com base no modelo Demanda-Controle (BAKER & KARASEK, 2000; KARASEK & THEORELL, 1990), tendo incluído: análise temática do conteúdo das entrevistas (MINAYO, 1982) e análise descritiva das freqüências obtidas através do questionário. Resultados. A população estudada era predominantemente feminina (72,6 por cento ), jovem (idade média 28 anos), com escolaridade secundária (48,4 por cento ) ou universitária (51,6 por cento ) e salário médio de R$ 600.00. 25,8 por cento eram estudantes. Entre outros, foram identificados fatores psicossociais negativos relacionados: ao ambiente físico; à estrutura temporal (pressão da fila; ritmo elevado externamente imposto; poucas pausas); à latitude decisória: a) falta de controle sobre a tarefa (rigidez da organização do trabalho; fraseologia padrão; falta de oportunidade de tomar decisões individuais, falta de participação); b) baixo grau de arbítrio da habilidade (grande volume de informações a processar, treinamento insuficiente; presença de terminologia médica); interface conteúdo, significado do trabalho e relacionamento com clientes provocando sofrimento emocional via empatia. O relacionamento com os clientes, um dos principais estressores do trabalho dos operadores, por freqüentemente envolver destrato, revelou-se importante fonte de satisfação quando envolve manifestação de reconhecimento. As referências aos fatores de incômodo e ix fadiga e de satisfação foram consistentes, respectivamente, com os fatores psicossociais estressores e benéficos, mostrando-se bons sinalizadores para a identificação daqueles aspectos. Entre os principais fatores de satisfação estavam a jornada de trabalho de seis horas e o relacionamento apoiador e brincalhão entre colegas e com os médicos auditores (apoio social). Quanto às queixas de saúde, 77,4 por cento dos sujeitos referiram sintomas osteomusculares; principais sintomas relacionados ao estresse referidos foram ansiedade (76,6 por cento ) e irritabilidade (66,1 por cento ). O uso do humor como coping foi referido por 78,2 por cento . Quanto a quem ri com quem, os dados indicam que brincadeiras são trocadas durante o trabalho entre os operadores, para 97,6 por cento ; dirigidas pelos operadores aos médicos, para 82,2 por cento ; dirigidas pelos médicos aos operadores, para 66,3 por cento ; pelos operadores aos supervisores, para 59,6 por cento , e pelos supervisores aos operadores, para 58,9 por cento . Conclusões. A situação de trabalho analisada apresentou grande predomínio de fatores psicossociais estressores em relação a \'protetores\' ou \'atenuantes\', representando combinação de intensidade e poucas chances de recuperação psicofisiológica ou, segundo o modelo Demanda-Controle, uma combinação de baixa latitude decisória com altas exigências (pressões psicológicas). O humor constitui um recurso psicossocial potencialmente \'protetor\' (CASSEL, 1974) ou \'modificador\' (BAKER & KARASEK, 2000) do processo de estresse, como estratégia de \'coping\' individual: por favorecer o distanciamento cognitivo; proporcionar alívio de tensão e expressão da subjetividade. Como comportamento comunicativo, o humor pode favorecer o apoio social (por convidar à proximidade; reduzir a distância entre níveis hierárquicos; permitir a expressão de críticas de forma socialmente menos arriscada); mas, acima de tudo, as trocas de humor refletem a dinâmica e a natureza das relações interpessoais, como indica a análise de quem ri com quem, uma das contribuições originais da pesquisa. Esta análise refletiu a presença de forte apoio social entre os operadores e entre estes e os médicos auditores. As brincadeiras \'relâmpago\' que irrompem durante o trabalho são percebidas como fontes de prazer, descarga de tensão e micro-espaços de reequilíbrio psicofisiológico. O humor integra o domínio da liberdade e é fortemente influenciado pelos valores. Se imposto aos trabalhadores, pode ser percebido como um constrangimento psicológico ou moral / Aim. Taking into account the two-dimensional nature of stress-related psychosocial factors (CASSEL, 1974), the study aimed at identifying the interrelation of negative (stressors) and protecting (beneficial) such factors in the work of a group of telemarketing operators, and the potential of humor as a \'psychosocial resource\' in face of stress at work, as a coping strategy (psychological dimension) and communicative behavior favoring social support (sociological dimension). Method. A case study was developed at a call center of the managed care unit of a public institution in São Paulo, Brazil. Data collection involved semi-structured interviews (twelve individual and one collective interview), participatory observation, and an inquiry responded by 124 operators from different work shifts. The inquiry included socio-demographic data, as well as questions on working conditions, factors of discomfort and fatigue and of work satisfaction, stress at work (KOMPIER & LEVI, 1995), health complaints and use of humor. Data analysis was based on the Demand/Control model (BAKER & KARASEK, 2000; KARASEK & THEORELL, 1990), and included content analysis of interviews (MINAYO, 1982), of data gathered through participatory observation, and descriptive analysis of inquiry frequencies. Results. The population studied was predominantly feminine (72.6 per cent ), young (average age 28 years), with high school (48.4 per cent ) or college education (51.6 per cent ) and average monthly wage around US$200.00. 25.8 per cent were students. Among others, negative psychosocial factors identified included: physical environment; time structure (pressure from the queue; high and externally imposed rhythm; few rest breaks); low decision latitude: a) low task control (strict work organization; script; lack of opportunity for individual decision making; lack of participation); and b) low skill discretion (great volume of information to be processed; insufficient training; presence of medical terminology); interrelation of work content, work meaning, and relationship with customers leading to emotional suffering through empathy. The relationship with customers, viewed as an important work-related stressor for often involving rude treatment, is perceived as an important source of satisfaction when involving recognition. Data on factors of discomfort and fatigue showed to be consistent with references to psychosocial stressors and protectors identified. Among protecting factors identified were the 6-hour working period and the supportive relationship among co-workers and with the medical auditors, often involving humor exchanges. Main health complaints were xi musculoskeletal (77.4 per cent ) and stress-related symptoms: anxiety (76.6 per cent ) and irritability (66.1 per cent ). Humor used as coping was referred by 78.2 per cent . Data on who laughs with who indicate that humorous/playful comments are often directed by operators to co-workers, for 97.6 per cent ; by operators to doctors, for 82.2 per cent ; by doctors to operators, for 66.3 per cent ; by operators to supervisors, for 59.6 per cent , and by supervisors to operators, for 58.9 per cent . Conclusions. The work situation of telemarketing operators studied involved a negative balance between psychosocial stressors and beneficial or mitigating factors: a combination of high work intensity and few chances of psycho-physiological recovery or, according to the Demand-Control model, a combination of high demands (psychological pressure) and low decision latitude. Humor is potentially a \'psychosocial resource\' (CASSEL, 1974) or \'modifying factor\' (BAKER & KARASEK, 2000) to the stress process, as an individual coping strategy, for favoring cognitive distancing/re-framing; relief from strain; expression of subjectivity. As a communicative behavior, humor may favor social support (for inviting to proximity; reducing social distance between different hierarchic levels, and permitting the expression of criticisms in less risky ways); but above all, humor as communicative behavior reflects interpersonal relationships dynamics and nature, as it was shown by the analysis of who laughs with who, an original contribution of this research that highlighted the presence of strong social support among operators and between them and the medical doctors. Brief humor events irrupting during work are perceived as a source of pleasure, and micro-spaces of psychophysiological recovery. Humor integrates the domain of freedom and is heavily influenced by cultural values. If it is imposed to workers, it may be perceived as a psychological or moral constraint

This work refers to the area of bio-nanotechnology and concerns the selective immobilization of DNA or other bio-template on microstructured gold contacts and which then permit a coordinated cooperation of several of these nanotemplate, e.g., within a microreactor. The immobilization of such nano-objects should be realized through functional thin polymer films which provide binding groups. Thus, the main aim of this work was the development of polymeric materials for thin functional films which permit to deposit on different substrates a wide variation of functional elements or metal structures and to achieve a pattern formation using optical grid methods. In order to realize this concept it was necessary to design and develop a polymer system based on suitable photolabile units and in addition having anchoring groups which attach on specific substrates like gold. In this terpolymer concept was aimed for which consists of three components with particular functions in suitable molar ratios, which allow the tune the properties of the materials, and provide: amino photolabile protected groups for the photolithographic creation of patterned areas with free amino groups, which are available for further modifications like attachment of colloids, metallization or attachment of DNA strands; disulfide derivative anchor groups providing anchoring capacity for gold surface and spacer groups for adjusting the film quality. These multifunctional terpolymers should be synthesised by free radical polymerisation of suitable monomers. Although these techniques are successful, they are limited by their complexity, rigorous synthetic demands, as well as incompatibility with many functional termolabile and highly reactive functionalities. To overcome these difficulties a polymerisation technique based on “living” free radical polymerisation has been used in this work. A highly efficient polymer-analogous modification allows to introduce the functionalities after the polymer construction reaction. The production of suitable prepolymers [poly(styrene-r-4-propargyl-oxystyrene)] was carried out with the help of a controlled synthesis methodology “nitroxide mediate radical polymerization" followed by polymer analogous reaction using one of the most efficient click reactions, the Cu(I) catalyzed Huisgen 1,3-dipolar cycloaddition between terminal acetylenes and azides to attach further functionalities through the formation of a stable 1,4-disubstituted 1,2,3-triazol ring . The combination of nitroxide mediated radical polymerization (NMRP) and click chemistry was used to produce well-defined random copolymer. It could already be shown that also block copolymers can be prepared which give the chance to combine nanostructure formation in block copolymers with special functionality. Thus, the special properties of these functional polymers like the capability for photopatterning and anchoring onto gold substrates make them very interesting for nanotechnology applications. / Diese Arbeit bezieht sich auf das Gebiet der Bionanotechnologie und betrifft ein neuartiges Verfahren zur selektiven Immobilisierung der DNA oder anderer Biomoleküle auf mikrostrukturierten Goldkontakten, welche dann ein koordiniertes Zusammenwirken von einzelnen Nanomolekülen ermöglichen, z.B. in einem Mikroreaktor. Die Immobilisierung solcher Nanoobjekte soll durch dünne Funktionsschichten realisiert werden, die die Anbindungsgruppen liefern. Folglich war das Hauptziel dieser Arbeit die Entwicklung von Polymermaterialien für dünne Funktionsschichten, die die Aufbringung einer großen Vielzahl von Funktionselementen oder metallischen Strukturen auf verschiedenen Substraten gestatten und die Strukturierung durch den Einsatz von lithographischen Methoden ermöglichen. Um dieses Konzept zu realisieren, war es notwendig, ein Polymersystem zu gestalten und zu entwickeln, welches auf geeignete photolabile Einheiten basiert und zusätzlich Ankergruppen hat, die mit spezifischen Substraten wie Gold verbunden ist. Dieses Terpolymerkonzept wurde gezielt aus drei Komponenten mit speziellen Funktionen in entsprechenden molaren Verhältnissen gebildet, die eine Abstimmung der Materialeigenschaften ermöglicht und folgendes bereitstellt: photolabile geschützte Aminogruppen für die photolitographische Strukturerzeugung mit freien Aminogruppen, welche für weitere Modifikationen verfügbar sind wie das Anhängen von Kolloiden, die Metallisierung oder Anfügung von DNA-Strängen; disulfide Derivate für die kovalente Anbindung auf der Goldoberfläche und Spacer-Gruppe für Verbesserung der Schichtenbildung. Diese multifunktionalen Terpolymere sollen durch eine freie radikalische Polymerisation von entsprechenden Monomeren synthetisiert werden. Obwohl diese Techniken erfolgreich sind, sind sie eingeschränkt durch ihre Komplexität, den strengen synthetischen Anforderungen, sowie der Inkompatibilität mit vielen funktionalen thermolabilen und hochreaktiven Funktionalitäten. Um diese Schwierigkeiten zu überwinden wurde eine Polymerisationstechnik für diese Arbeit genutzt, die auf der „lebenden“ freien radikalischen Polymerisation basiert. Eine hoch effiziente polymeranaloge Modifizierung erlaubt die Einführung von Funktionalitäten nach der Polymeraufbaureaktion. Die Herstellung von entsprechenden Präpolymeren Poly(Styrol-r-4-Propargyl-oxystyrol) wurde mittels einer kontrollierten Synthesemethodik „Nitroxid-mediated controled radical polymerisation“ (NMRP) durchgeführt, gefolgt von der Polymeranalogreaktion, die eine der effizientesten Click-Reaktion - die Cu(I) katalysierte 1,3-dipolar Cycloaddition von terminalen Alkinen an Aziden nach Huisgen nutzt, um weiter Funktionalitäten durch die Bildung eines stabilen 1,4-disubstituierten-[1,2,3]-Triazolringes anzufügen. Die Kombination von NMRP und Click-Chemie wurde zur Herstellung eines exakt definierten Random Copolymers genutzt. Es konnte bereits gezeigt werden, dass auch Blockcopolymere geschaffen werden können, die eine Möglichkeit zur Kombination von Nanostrukturformationen in Blockcopolymeren mit speziellen Funktionaltäten bieten. Folglich sind die speziellen Eigenschaften dieser Funktionalpolymere wie die Fähigkeit zur Photostrukturierung und Verankerung auf Goldsubstraten für nanotechnologische Anwendungen sehr interessant.

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.

Les Acides Peptido-nucléiques (PNA) sont des analogues synthétiques d’oligonucleotides naturels, ils sont constitués d’une répétition d’unités N-(2-aminoethyl)-glycine reliées par une liaison peptidique. Leur stabilité chimique et biologique en font une alternative intéressante pour les assemblages supramoléculaires ayant une application biologique tels que l’encodage de chimiothèques combinatoires de petites molécules et des réactions engendrées par hybridation. Ce travail de thèse avait pour objectif la synthèse d’acides peptido-nucléiques modifiés dans le but d’améliorer leur hybridation, leurs propriétés physico-chimiques ainsi que la synthèse des chimiothèques combinatoires. / Peptide nucleic acids (PNA) are structural analogs of natural nucleic acids composed of repeating units of N-(2-aminoethyl)-glycine residues linked by peptide bonds. Their chemical and biological stability makes them very suitable for supramolecular assemblies with biological applications such as encoding combinatorial libraries of small molecules and for performing templated reactions. This phD project aimed at the synthesis of modified peptide nucleic acids to enhance their physicochemical and hybridization properties as well as for construction of combinatorial libraries.

Ce travail est consacré au développement d’une nouvelle méthode de synthèse d’analogues bioactifs de protéinesen utilisant des réactions successives de cycloaddition entre les alcynes terminaux et les azotures (CuAAC).Pour pouvoir effectuer des cycloadditions itératives, nous avons étudié la stabilité et les conditions de coupure dedifférents groupements masquants des alcynes terminaux. Cette étude a été valorisée par le développement d’unestratégie originale pour réaliser un triple cycloaddition successive une même molécule basée sur la protectiontemporaire de la fonction alcyne.La méthode a été appliquée à la synthèse d'un analogue de la stéfine A humaine, un inhibiteur naturel deprotéases à cystéine d’intérêt thérapeutique. Pour cela, nous avons mis au point des conditions de CuAACsuccessive compatibles avec des peptides déprotégés de façon beaucoup à obtenir in fine un analogue bis-triazolede la stéfine A. Les études par dichroïsme circulaire et d’inhibition de diverses protéases à cystéines confirmentque notre analogue synthétique conserve la structure et l’activité biologique de la protéine native.La stratégie de ligation triazole successive a été étendue par la mise au point de conditions pour réaliser desligations sur phase solide. La méthodologie développée permet la synthèse de protéines de façon plus rapide etplus simple que par des procédés classiques de ligation successive en solution. Dans l’optique de la synthèse destructures glycopeptidiques capables d’induire une réponse immunitaire contre MUC1 tumorale, nous avons réaliséla synthèse d’analogues peptidiques de MUC1 par ligation successive sur phase solide de 160 acides aminés. / The aim of this work was the development of a novel method for the synthesis of triazolo-proteins by multiplesuccessive copper-catalyzed azide-alkyne cycloadditions (CuAAC).In order to achieve several successive cycloadditions, we have studied the stability and cleavage conditions ofseveral alkyne protective groups. This study leaded us to the development of an original strategy in order toachieve three successive cycloadditions on a same scaffold by temporal protection of alkyne functionalities.The method has been applied to the synthesis of an analogue of human stefin A, a natural inhibitor of severaltherapeutically relevant cysteine proteases. Therefore, we have developed CuAAC conditions compatible withunprotected peptide ligation. The strategy allowed us to obtain a bis-triazolo analogue of human stefin A. Circulardichroism and enzymology assays on several cysteine cathepsins revealed that the synthetic analogue hasretained the folding and full biological activity of the native protein.In order to expand the possibilities of this strategy, we have developed reaction conditions allowing us to performsuccessive triazole ligation on solid phase. This methodology avoids the need for a time-consuming and laborintensivepurification step before and after each ligation. With the aim of exploring the use of analogues of thetumor-associated form of the glycoprotein MUC1 to induce a specific immune response, we have synthesized atriazolo-analogue of MUC1 of 160 aminoacids using solid phase peptide ligation.

The main goal of this diploma thesis was to create web applications for issuer, verifier and revocation authority of revocable keyed-verification anonymous credentials system. Applications created in this thesis provide functions for all tasks, that are performed by each entity. Using these applications a global management of RKVAC system is possible. Authentication module created in verifier’s app is universaly usable for access control to any web service. Both issuer’s and revocation authority’s app are compatible with whole RKVAC system and are therefor applicable as central elements of systems.