O fator VIII de coagulação (FVIII), recombinante ou purificado de plasma, é o biofármaco necessário para o tratamento da hemofília A, a doença hemorrágica mais freqüente em humanos. O método tradicional para a purificação de FVIII parte de crioprecipitado de plasma e precipitação alcoólica. No Instituto Butantan, foi proposto um método alternativo, utilizando somente cromatografia para esta purificação. Este projeto teve por objetivo comparar dois métodos cromatográficos de purificação do FVIII: 1 - gel filtração direta do plasma e 2 - pré-purificação de FVIII do plasma por cromatografia de troca aniônica, seguida de gel filtração. A purificação foi analisada por dosagens de atividade específica de FVIII e presença de outras proteínas da cascata de coagulação nas frações de cromatografia. Foram realizadas clonagem de fragmentos gênicos de FVIII e expressão de fragmentos protéicos para imunização de animais. Os soros com anticorpos policlonais anti-FVIII foram usados em ensaios de \"western blot\" para detectar as cadeias de FVIII ou degradação. / Coagulation factor VIII (FVIII), recombinant or purified from plasma, is the biopharmaceutical used for treatment of haemophilia A, the most frequent human hemorrhagic disorder. The traditional method used for purification of FVIII starts from plasma cryoprecipitate and alcoholic precipitation. The Instituto Butantan proposed an alternative methodology using only chromatography for FVIII purification. The main objective of this project was to compare two chromatographic methods for FVIII purification: 1 - direct plasma gel filtration and 2 - pre-purification of FVIII by anion exchange chromatography, followed by gel filtration. The purification process was analyzed by determination of FVIII specific activity and detection of other coagulation factors co eluting in chromatographic fractions. Fragments of FVIII gene were cloned and protein fragments were expressed for animal immunization. Sera with polyclonal antibodies anti-FVIII were used in western blots assays to detect FVIII chains or its degradation.

A combinação de célula eletroquímica (EC) com a entrada do equipamento de eletroforese capilar (CE), apesar de recente, tem permitido realizar determinação de ânions radicais; pré-concentração eletroquímica de metais pesados, seguida de redissolução, separação e detecção; bem como monitorar produtos carregados formados por oxidação eletrocatalítica de espécies neutras, como álcoois primários e glicerol. Empregando o sistema EC-CE-C4D desenvolvido pelo grupo, a determinação simultânea de cátions, ânions (no contra fluxo) e espécies neutras (detectadas após derivatização eletroquímica) foi demonstrada pela primeira vez, tendo o antisséptico bucal (Listerine® Tartar Control) como amostra real. Embora constante e reprodutível, a conversão dos álcoois primários nos respectivos carboxilatos apresentou rendimento relativamente baixo, ~16%, nas condições anteriormente adotadas, 1,6 V vs. Ag/AgClKCl 3M empregando eletrodo de platina em meio ácido (HNO3 5 mmol L-1 / HCl 1 mmol L-1). Dessa maneira, avaliou-se a oxidação de álcoois primários de cadeia normal (C2 − C5) sobre diferentes materiais de eletrodo (ouro e platina) em diferentes meios (ácido, neutro e alcalino). Os carboxilatos gerados foram monitorados injetando uma alíquota da amostra derivatizada no capilar (50 µm d.i., 45 cm de comprimento e 20 cm efetivo) aplicando 5 kPa durante 5 s, e durante as separações, 30 kV foi aplicado entre as extremidades do capilar preenchido com Tris 30 mmol L-1 / HCl 10 mmol L-1 usado como BGE. Os resultados obtidos com o sistema EC-CE-C4D apontaram maior conversão dos álcoois nos respectivos ácidos carboxílicos em meio ácido, tanto em ouro quanto em platina. Adicionalmente, em eletrodo de ouro a formação dos carboxilatos apresentou certa seletividade não observada sobre platina, favorecendo a conversão dos álcoois de cadeia menor. Noutra vertente, buscando atender as necessidades atuais por metodologias que possibilitem monitorar a eletrooxidação do glicerol em reatores eletroquímicos, desenvolveu-se um método que permitiu determinar simultaneamente o glicerol e alguns de seus possíveis produtos de oxidação neutros, como gliceraldeído e dihidroxiacetona, explorando a formação de complexo carregado com borato (presente no BGE composto por H3BO3 60 mmol L-1 / LiOH 30 mmol L-1), além dos produtos ionizáveis (ácidos carboxílicos) que são comumente analisados por CE. O equipamento de CE utilizado, munido de dois detectores C4D, também permitiu avaliar a interação de alguns ácidos carboxílicos com os modificadores de EOF, Polybrene® e CTAB, empregando MES 30 mmol L-1 / His 30 mmol L-1 como BGE. Seguindo a atual tendência à miniaturização de sistemas analíticos, avaliou-se a possibilidade de construir um sistema EC-CE-C4D miniaturizado. Para isso, um novo método para fabricação de microdispositivos em vidro, baseado em ablação a laser de CO2 assistida por parafina, como alternativa aos dispendiosos métodos de corrosão por via úmida foi desenvolvido. Os dispositivos obtidos por esse método apresentaram canais de perfil semicircular, e as dimensões puderam ser controladas variando a potência e/ou a velocidade de ablação do laser. Contudo, pelos desafios ainda encontrados para se construir um sistema EC-CE-C4D completo em substrato de vidro por ablação a laser de CO2, optou-se por iniciar a miniaturização do sistema EC-CE-C4D com um sistema híbrido em que se aproveita as características mais bem definidas e favoráveis dos tubos capilares de sílica fundida usados em CE convencional. Esse sistema permitiu a determinação quantitativa de metanol na presença de alta concentração de etanol, possibilitando, numa primeira aplicação, realizar o monitoramento da quantidade de metanol e etanol nas frações iniciais coletada durante o processo de destilação fracionada na produção de uísque de milho (moonshine) feito em laboratório. Visto a maior seletividade para conversão dos álcoois de cadeia menor obtidas em eletrodo de ouro e meio ácido, esse foi escolhido para a presente aplicação. As condições que apresentaram melhores resultados no sistema híbrido EC-CE-C4D abrangeram diluição de 100 vezes da amostra em HNO3 2 mmol L-1, eletrooxidação a 1,4 V vs. Ag durante 60 s, injeção eletrocinética no capilar mediante aplicação de 3 kV durante 4 s, e a separação dos carboxilatos realizada aplicando 3 kV entre as extremidades do capilar (50 µm d.i., 15 cm de comprimento com 12 cm efetivo), preenchido com CHES 10 mmol L-1 / NaOH 5 mmol L-1, usado como BGE. A análise das primeiras frações destiladas da \"labmade moonshine\" apresentou um aumento na concentração de etanol (variando de ~80 % a ~100 %) e simultâneo decréscimo da concentração de metanol (variando de 4 % a ~0,1 %). Em suma, avançou-se tanto no leque de aplicações da derivatização eletroquímica hifenizada com a eletroforese capilar como na miniaturização da instrumentação analítica para EC-CE-C4D, favorecendo a disseminação dessa poderosa combinação de três técnicas eletroquímicas. / The direct couple of electrochemical cell (EC) with the inlet of the capillary electrophoresis (CE) equipment, recently demonstrated, has allowed the determination of radical anions; to perform electrochemical preconcentration of traces of heavy metals, followed by stripping, injection, separation and detection; and the generation of charged species by electrochemical oxidation of neutral molecules, e.g. primary alcohols and glycerol. Employing the EC-CE-C4D system developed by our group, the simultaneous determination of cations, anions (in the counter EOF mode) and neutral species (after electrochemical derivatization) was demonstrated for the first time and a mouthwash (Listerine® Tartar Control) was used as a real sample. Although constant and reproducible, the conversion of primary alcohols into carboxylates had a low yield (~16%), under the adopted conditions, 1.6 V vs. Ag/AgClKCl 3M using platinum electrode in acid medium (5 mmol L-1 HNO3 / 1 mmol L-1 HCl). Thus, the yield of carboxylates was studied for the oxidation of alcohols (C2 − C5) on two electrode materials (gold and platinum) in different media (acid, neutral and alkaline). After the electrooxidation step an aliquot of the derivatized sample was automatically injected into the capillary (50 µm i.d., 45 cm in length and 20 cm up to detector) by applying 5 kPa during 5 s. The separation was carried out applying 30 kV between the capillary ends previously filled with 30 mmol L-1 Tris / 10 mmol L-1 HCl BGE. Cyclic voltammograms show higher current density for alcohols oxidation in alkaline medium than in acid one both on gold and platinum electrodes. On the other hand the yields of carboxylic acids were higher in acidic medium. Besides that, only on gold electrode some selectivity for the carboxylate formation was observed favoring the conversion of the short chain alcohols. In order to meet the current needs for methodologies that allow the monitoring of the electrooxidation of glycerol in electrochemical reactors, a method was also developed that allowed the determination of glycerol and some of its possible neutral oxidation products, such as glyceraldehyde and dihydroxyacetone, by exploring the formation of borate complexes (provided in the BGE composed of 60 mmol L-1 H3BO3 / 30 mmol L-1 LiOH), together with ionizable ones like carboxylic acids. The employed CE equipment with two C4D detectors allowed the evaluation of the interaction between some carboxylic acids and the EOF modifiers, Polybrene® and CTAB, using 30 mmol L-1 MES / 30 mmol L-1 His as BGE. Aligned with a current trend of analytical instrumentation, the miniaturized EC-CE-C4D system was attempted. For that, a new method for manufacturing microdevices in glass, based on paraffin-assisted CO2 laser ablation, was developed as an alternative to costly wet-etching methods. The devices obtained by this method presented channels of semicircular profile and the dimensions could be controlled by varying the laser power and/or ablation velocity. Due to remaining challenges in the construction of a complete laser ablated EC-CE-C4D system on glass, a miniaturized system based on a hybrid approach is presented in the thesis, by taking advantage of the more defined and favorable characteristics of the well known fused silica capillary tubes used in CE. This system allowed the quantitative determination of methanol in the presence of high ethanol concentration by taking advantage of the higher yield of short-chain carboxylic acid formation on gold in acidic medium. The first application was the monitoring of the amount of methanol and ethanol in the initial fractions collected during the fractional distillation process in the production of corn whiskey (moonshine) made in the laboratory. The conditions that showed the best results with the hybrid EC-CE-C4D system included a 100-fold dilution of the sample in 2 mmol L-1 HNO3, electrooxidation at 1.4 V vs. Ag for 60 s, electrokinetic injection into the capillary by applying 3 kV for 4 s and separation of the carboxylates carried out under 3 kV between the ends of the capillary (50 µm i.d., 15 cm in length and 12 cm up to detector) previously filled with 10 mmol L-1 CHES / 5 mmol L-1 NaOH, used as BGE. Analysis of the first distilled fractions of labmade moonshine showed an increase in ethanol concentration (ranging from ~ 80% to ~ 100%) and a simultaneous decrease in methanol concentration (ranging from 4% to ~ 0.1%). In short, both the range of applications of electrochemical derivatization hyphenated with capillary electrophoresis as well the miniaturization of analytical instrumentation for EC-CE-C4D were improved, favoring the dissemination of this powerful combination of three electrochemical techniques.

A combinação de célula eletroquímica (EC) com a entrada do equipamento de eletroforese capilar (CE), apesar de recente, tem permitido realizar determinação de ânions radicais; pré-concentração eletroquímica de metais pesados, seguida de redissolução, separação e detecção; bem como monitorar produtos carregados formados por oxidação eletrocatalítica de espécies neutras, como álcoois primários e glicerol. Empregando o sistema EC-CE-C4D desenvolvido pelo grupo, a determinação simultânea de cátions, ânions (no contra fluxo) e espécies neutras (detectadas após derivatização eletroquímica) foi demonstrada pela primeira vez, tendo o antisséptico bucal (Listerine® Tartar Control) como amostra real. Embora constante e reprodutível, a conversão dos álcoois primários nos respectivos carboxilatos apresentou rendimento relativamente baixo, ~16%, nas condições anteriormente adotadas, 1,6 V vs. Ag/AgClKCl 3M empregando eletrodo de platina em meio ácido (HNO3 5 mmol L-1 / HCl 1 mmol L-1). Dessa maneira, avaliou-se a oxidação de álcoois primários de cadeia normal (C2 − C5) sobre diferentes materiais de eletrodo (ouro e platina) em diferentes meios (ácido, neutro e alcalino). Os carboxilatos gerados foram monitorados injetando uma alíquota da amostra derivatizada no capilar (50 µm d.i., 45 cm de comprimento e 20 cm efetivo) aplicando 5 kPa durante 5 s, e durante as separações, 30 kV foi aplicado entre as extremidades do capilar preenchido com Tris 30 mmol L-1 / HCl 10 mmol L-1 usado como BGE. Os resultados obtidos com o sistema EC-CE-C4D apontaram maior conversão dos álcoois nos respectivos ácidos carboxílicos em meio ácido, tanto em ouro quanto em platina. Adicionalmente, em eletrodo de ouro a formação dos carboxilatos apresentou certa seletividade não observada sobre platina, favorecendo a conversão dos álcoois de cadeia menor. Noutra vertente, buscando atender as necessidades atuais por metodologias que possibilitem monitorar a eletrooxidação do glicerol em reatores eletroquímicos, desenvolveu-se um método que permitiu determinar simultaneamente o glicerol e alguns de seus possíveis produtos de oxidação neutros, como gliceraldeído e dihidroxiacetona, explorando a formação de complexo carregado com borato (presente no BGE composto por H3BO3 60 mmol L-1 / LiOH 30 mmol L-1), além dos produtos ionizáveis (ácidos carboxílicos) que são comumente analisados por CE. O equipamento de CE utilizado, munido de dois detectores C4D, também permitiu avaliar a interação de alguns ácidos carboxílicos com os modificadores de EOF, Polybrene® e CTAB, empregando MES 30 mmol L-1 / His 30 mmol L-1 como BGE. Seguindo a atual tendência à miniaturização de sistemas analíticos, avaliou-se a possibilidade de construir um sistema EC-CE-C4D miniaturizado. Para isso, um novo método para fabricação de microdispositivos em vidro, baseado em ablação a laser de CO2 assistida por parafina, como alternativa aos dispendiosos métodos de corrosão por via úmida foi desenvolvido. Os dispositivos obtidos por esse método apresentaram canais de perfil semicircular, e as dimensões puderam ser controladas variando a potência e/ou a velocidade de ablação do laser. Contudo, pelos desafios ainda encontrados para se construir um sistema EC-CE-C4D completo em substrato de vidro por ablação a laser de CO2, optou-se por iniciar a miniaturização do sistema EC-CE-C4D com um sistema híbrido em que se aproveita as características mais bem definidas e favoráveis dos tubos capilares de sílica fundida usados em CE convencional. Esse sistema permitiu a determinação quantitativa de metanol na presença de alta concentração de etanol, possibilitando, numa primeira aplicação, realizar o monitoramento da quantidade de metanol e etanol nas frações iniciais coletada durante o processo de destilação fracionada na produção de uísque de milho (moonshine) feito em laboratório. Visto a maior seletividade para conversão dos álcoois de cadeia menor obtidas em eletrodo de ouro e meio ácido, esse foi escolhido para a presente aplicação. As condições que apresentaram melhores resultados no sistema híbrido EC-CE-C4D abrangeram diluição de 100 vezes da amostra em HNO3 2 mmol L-1, eletrooxidação a 1,4 V vs. Ag durante 60 s, injeção eletrocinética no capilar mediante aplicação de 3 kV durante 4 s, e a separação dos carboxilatos realizada aplicando 3 kV entre as extremidades do capilar (50 µm d.i., 15 cm de comprimento com 12 cm efetivo), preenchido com CHES 10 mmol L-1 / NaOH 5 mmol L-1, usado como BGE. A análise das primeiras frações destiladas da \"labmade moonshine\" apresentou um aumento na concentração de etanol (variando de ~80 % a ~100 %) e simultâneo decréscimo da concentração de metanol (variando de 4 % a ~0,1 %). Em suma, avançou-se tanto no leque de aplicações da derivatização eletroquímica hifenizada com a eletroforese capilar como na miniaturização da instrumentação analítica para EC-CE-C4D, favorecendo a disseminação dessa poderosa combinação de três técnicas eletroquímicas. / The direct couple of electrochemical cell (EC) with the inlet of the capillary electrophoresis (CE) equipment, recently demonstrated, has allowed the determination of radical anions; to perform electrochemical preconcentration of traces of heavy metals, followed by stripping, injection, separation and detection; and the generation of charged species by electrochemical oxidation of neutral molecules, e.g. primary alcohols and glycerol. Employing the EC-CE-C4D system developed by our group, the simultaneous determination of cations, anions (in the counter EOF mode) and neutral species (after electrochemical derivatization) was demonstrated for the first time and a mouthwash (Listerine® Tartar Control) was used as a real sample. Although constant and reproducible, the conversion of primary alcohols into carboxylates had a low yield (~16%), under the adopted conditions, 1.6 V vs. Ag/AgClKCl 3M using platinum electrode in acid medium (5 mmol L-1 HNO3 / 1 mmol L-1 HCl). Thus, the yield of carboxylates was studied for the oxidation of alcohols (C2 − C5) on two electrode materials (gold and platinum) in different media (acid, neutral and alkaline). After the electrooxidation step an aliquot of the derivatized sample was automatically injected into the capillary (50 µm i.d., 45 cm in length and 20 cm up to detector) by applying 5 kPa during 5 s. The separation was carried out applying 30 kV between the capillary ends previously filled with 30 mmol L-1 Tris / 10 mmol L-1 HCl BGE. Cyclic voltammograms show higher current density for alcohols oxidation in alkaline medium than in acid one both on gold and platinum electrodes. On the other hand the yields of carboxylic acids were higher in acidic medium. Besides that, only on gold electrode some selectivity for the carboxylate formation was observed favoring the conversion of the short chain alcohols. In order to meet the current needs for methodologies that allow the monitoring of the electrooxidation of glycerol in electrochemical reactors, a method was also developed that allowed the determination of glycerol and some of its possible neutral oxidation products, such as glyceraldehyde and dihydroxyacetone, by exploring the formation of borate complexes (provided in the BGE composed of 60 mmol L-1 H3BO3 / 30 mmol L-1 LiOH), together with ionizable ones like carboxylic acids. The employed CE equipment with two C4D detectors allowed the evaluation of the interaction between some carboxylic acids and the EOF modifiers, Polybrene® and CTAB, using 30 mmol L-1 MES / 30 mmol L-1 His as BGE. Aligned with a current trend of analytical instrumentation, the miniaturized EC-CE-C4D system was attempted. For that, a new method for manufacturing microdevices in glass, based on paraffin-assisted CO2 laser ablation, was developed as an alternative to costly wet-etching methods. The devices obtained by this method presented channels of semicircular profile and the dimensions could be controlled by varying the laser power and/or ablation velocity. Due to remaining challenges in the construction of a complete laser ablated EC-CE-C4D system on glass, a miniaturized system based on a hybrid approach is presented in the thesis, by taking advantage of the more defined and favorable characteristics of the well known fused silica capillary tubes used in CE. This system allowed the quantitative determination of methanol in the presence of high ethanol concentration by taking advantage of the higher yield of short-chain carboxylic acid formation on gold in acidic medium. The first application was the monitoring of the amount of methanol and ethanol in the initial fractions collected during the fractional distillation process in the production of corn whiskey (moonshine) made in the laboratory. The conditions that showed the best results with the hybrid EC-CE-C4D system included a 100-fold dilution of the sample in 2 mmol L-1 HNO3, electrooxidation at 1.4 V vs. Ag for 60 s, electrokinetic injection into the capillary by applying 3 kV for 4 s and separation of the carboxylates carried out under 3 kV between the ends of the capillary (50 µm i.d., 15 cm in length and 12 cm up to detector) previously filled with 10 mmol L-1 CHES / 5 mmol L-1 NaOH, used as BGE. Analysis of the first distilled fractions of labmade moonshine showed an increase in ethanol concentration (ranging from ~ 80% to ~ 100%) and a simultaneous decrease in methanol concentration (ranging from 4% to ~ 0.1%). In short, both the range of applications of electrochemical derivatization hyphenated with capillary electrophoresis as well the miniaturization of analytical instrumentation for EC-CE-C4D were improved, favoring the dissemination of this powerful combination of three electrochemical techniques.

A travers l’analyse du fonctionnement de la forme RAZ, qui peut correspondre en russe contemporain soit à un mot autonome, soit à un préfixe, cette thèse se veut une contribution à l’étude de la sémantique des unités polycatégorielles, mais aussi à l’approfondissement des notions d’intensité et de saillance. L’analyse s’appuie sur le modèle général de la construction du sens et de la référence élaboré dans le cadre de la Théorie des Opérations Prédicatives et Enonciatives développée à partir des travaux d’Antoine Culioli et tient compte des conditions discursives (situation, cotexte, contexte) dans lesquelles apparaît RAZ. Elle aboutit à l’élaboration d’une signification invariante pour chacun de ses emplois catégoriels comme mot autonome et comme préfixe. Chaque invariant est défini non comme une valeur abstraite ou une valeur prototypique, mais comme un schéma qui indique le rôle spécifique joué par RAZ dans les interactions avec son cotexte. Les invariants proposés sont élaborés sur des critères distributionnels et formels précis, tels que la sémantique catégorielle de RAZ, sa fonction syntaxique, la nature et la fonction syntaxique de sa portée. On démontre que malgré l’existence de deux étymons à la sémantique différente, une partie des emplois du préfixe raz- est en fait rattachable au mot autonome raz. Ils relèvent d’une même sémantique de l’actualisation, qui est à la base de l’interprétation intensive et des effets de mises en saillance associés à certains emplois de RAZ. De là découle la difficulté à les traiter au niveau lexicographique, car leur description nécessite la prise en compte des facteurs énonciatifs et du contexte d’emploi large. / This thesis analyses the functioning of the form RAZ that in contemporary Russian can be either a word or a prefix, and is intended as a contribution to the study of the semantics of polycategorical lexical items as well as to a better understanding of the notions of intensity and salience. The analysis is based on the model of meaning and reference construction elaborated within the framework of the Theory of the Predicative and Enunciative Operations developed by Antoine Culioli’s associates, and takes into consideration the discursive conditions (situation, co-text, context) under which RAZ occurs. It results in the elaboration of a semantic invariant for each categorical use of RAZ as a word and as a prefix. Each invariant is defined not as an abstract value or a prototypic value, but as a schema that indicates the specific role played by RAZ in the interactions with its co-text. The proposed invariants are developed on the basis of specific distributional and formal criteria, such as the categorical semantics of RAZ, its syntactic function, the nature and the function of its scope. It is demonstrated that despite the existence of two etymons with different meanings, some of the uses of the prefix raz- are, in fact, attachable to the word raz. They emerge from the semantics of actualisation (in Bally’s sense), which is responsible for the intensive interpretation and the effects of salience proper to certain uses of RAZ. Hence the difficulty in treating them on the lexicographic level, since their description requires consideration of enunciative factors and of the wider context.

Cette thèse porte sur l’élaboration d’un modèle de structuration des relations lexicales, fondé sur les fonctions lexicales de la Théorie Sens-Texte [Mel’cuk, 1997]. Les relations lexicales considérées sont les dérivations sémantiques et les collocations telles qu’elles sont définies dans le cadre de la Lexicologie Explicative et Combinatoire [Mel’cuk et al., 1995]. En partant du constat que ces relations lexicales ne sont pas décrites ni présentées de façon satisfaisante dans les bases de données lexicales, nous posons la nécessité d’en créer un modèle de structuration. Nous justifions l’intérêt de créer un système de fonctions lexicales puis détaillons les quatre perspectives du système que nous avons mises au point : une perspective sémantique, une perspective axée sur la combinatoire des éléments d’une relation lexicale, une perspective centrée sur leurs parties du discours, ainsi qu’une perspective mettant en avant l’élément sur lequel se focalise la relation. Le système intègre l’ensemble des fonctions lexicales, y compris les fonctions lexicales non standard, dont nous proposons une normalisation de l’encodage. Le système a été implémenté dans la base de données lexicale du DiCo. Nous présentons trois applications dans lesquelles il peut être exploité. Premièrement, il est possible d’en dériver des interfaces de consultation pour les bases de données lexicales de type DiCo. Le système peut également être directement consulté en tant qu’assistant à l’encodage des relations lexicales. Enfin, il sert de référence pour effectuer un certain nombre de calculs sur les informations lexicographiques, qui pourront, par la suite, être implémentés pour automatiser la rédaction de certains champs de fiches lexicographiques. / This thesis proposes a model for structuring lexical relations, based on the concept of lexical functions (LFs) proposed in Meaning-Text Theory [Mel’cuk, 1997]. The lexical relations taken into account include semantic derivations and collocations as defined within this theoretical framework, known as Explanatory and Combinatorial Lexicology [Mel’cuk et al., 1995]. Considering the assumption that lexical relations are neither encoded nor made available in lexical databases in an entirely satisfactory manner, we assume the necessity of designing a new model for structuring them. First of all, we justify the relevance of devising a system of lexical functions rather than a simple classification. Next, we present the four perspectives developped in the system: a semantic perspective, a combinatorial one, another one targetting the parts of speech of the elements involved in a lexical relation, and, finally, a last one emphasizing which element of the relation is focused on. This system covers all LFs, even non-standard ones, for which we have proposed a normalization of the encoding. Our system has already been implemented into the DiCo relational database. We propose three further applications that can be developed from it. First, it can be used to build browsing interfaces for lexical databases such as the DiCo. It can also be directly consulted as a tool to assist lexicographers in encoding lexical relations by means of lexical functions. Finally, it constitutes a reference to compute lexicographic information which will, in future work, be implemented in order to automatically fill in some fields within the entries in lexical databases. / Thèse réalisée en cotutelle avec l'Université Paris Diderot (Paris 7)

Dans ce travail nous avons tenu à faire une étude comparée des éléments de la formation ainsi que les procédés de formation des adjectifs qualificatifs en français et en lituanien. Nous avons analysé et établi les parentés ainsi que les différences de la formation de l’adjectif dans les deux langues. Ce travail consiste également à faire une petite revue des caractéristiques classificatoires, morphologiques, sémantiques, des nuances de la traduction de l’adjectif français et lituanien. / Šio darbo tikslas buvo ištirti bei palyginti kokybinių būdvardžių darybos elementus prancūzų ir lietuvių kalbose. Norėdamos palyginti šias abi kalbas mes padarėme prielaidą, kad prancūzų kalboje kokybiniai būdvardžiai turi panašių darybos bruožų kaip ir lietuvių kalboje. Tyrimui buvo pasirinkti šie prancūzų rašytojų kūriniai: Albert Camus «L'étranger» («Svetimas»), Honoré de Balzac «Le Père Goriot» («Tėvas Gorijo») ir Gustave Flaubert «Madame Bovary» («Ponia Bovary»). Prancūzų kalbos kokybiniai būdvardžiai buvo lyginami su lietuviško vertimo atitikmenimis. / Objective of this work was to investigate and compare the elements of the formation of Qualitatif adjectif in French and Lithuanian languages.We revewed also the parameters of word's formation and translation specificities in both languages.

H παρούσα διατριβή ανήκει στο πεδίο της συγκριτικής μορφολογίας. Μελετάται η μορφολογική διαδικασία της σύνθεσης στη Νέα Ελληνική και τη Γερμανική, σε δύο γλώσσες που μοιράζονται πολλά κοινά μορφολογικά χαρακτηριστικά και στις οποίες το συγκεκριμένο φαινόμενο είναι ιδιαίτερα παραγωγικό. Συγκεκριμένα, τα θέματα που εξετάζονται είναι τα ακόλουθα: α) τα δομικά χαρακτηριστικά των λεγόμενων «πρωτοτυπικών συνθέτων» σε σύγκριση με τις «οριακές περιπτώσεις», όπου και η διαδικασία της παραγωγής εμπλέκεται στο σχηματισμό τους, β) η εμφάνιση συνδετικού στοιχείου και γ) ο σχηματισμός διαφόρων τύπων συνθέτων, όπως για παράδειγμα των εξωκεντρικών και των παρατακτικών συνθέτων. To θεωρητικό πλαίσιο που υιοθετείται είναι αυτό της γενετικής μορφολογίας. Τα κυριότερα συμπεράσματα της διατριβής αφορούν τον καθορισμό των παραμέτρων, βάσει των οποίων μπορούν να ερμηνευθούν οι διαφορές στο σχηματισμό συνθέτων των δύο αυτών γλωσσών. Οι πιο σημαντικοί παράμετροι που εξηγούν τις διαφορές των νεοελληνικών και γερμανικών συνθέτων είναι α) το είδος της μορφολογίας που προτιμά η κάθε γλώσσα, αν δηλαδή βασίζεται στο θέμα ή στη λέξη και β) τα πλούσια ή περιορισμένα ονοματικά κλιτικά παραδείγματα. Μέσω της συγκριτικής ανάλυσης ήρθαν στο φως και νέα συμπεράσματα που αφορούν επιμέρους ζητήματα της διαδικασίας της σύνθεσης των δύο αυτών γλωσσών, όπως για παράδειγμα ο μορφολογικός χαρακτήρας του συνδετικού στοιχείου και το είδος της κεφαλής των εξωκεντρικών συνθέτων της Γερμανικής, καθώς επίσης και τα μορφολογικά χαρακτηριστικά των ονοματικών παρατακτικών συνθέτων της Νέας Ελληνικής. / This thesis belongs to the field of contrastive morphology: it examines the morphological process of compounding in Modern Greek and German, two languages which share many common morphological features and in which the specific phenomenon is especially productive. In more detail, the topics examined are the following: a) the structural features of the so called “prototypical compounds” in contrast to the “borderline cases”, where the process of derivation is also involved in their formation, b) the appearance of the linking element and c) the formation of different types of compounds as for example the exocentric and the copulative ones. The theoretical framework adopted is that of generative morphology. The main conclusions of the thesis concern the definition of parameters that can explain the differences in the formation of compounds in these two languages. The most important parameters that determine the basic differences in the formation of Modern Greek and German compounds are a) the stem vs. word-based morphology and b) the rich vs. limited nominal inflectional paradigms. Through this contrastive analysis various new outcomes came into light concerning special issues in the process of compounding of these two languages, as for instance the morphological status of the linking element in German, the type of head that the German exocentric compounds display and the morphological features of the nominal copulative compounds in Modern Greek.

Made available in DSpace on 2014-12-17T15:47:57Z (GMT). No. of bitstreams: 1 MarioSST_DISSERT.pdf: 2743049 bytes, checksum: da23e766aa49e7926f3ad6450145c626 (MD5) Previous issue date: 2011-02-17 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Product derivation tools are responsible for automating the development process of software product lines. The configuration knowledge, which is responsible for mapping the problem space to the solution space, plays a fundamental role on product derivation approaches. Each product derivation approach adopts different strategies and techniques to manage the existing variabilities in code assets. There is a lack of empirical studies to analyze these different approaches. This dissertation has the aim of comparing systematically automatic product derivation approaches through of the development of two different empirical studies. The studies are analyzed under two perspectives: (i) qualitative that analyzes the characteristics of approaches using specific criteria; and (ii) quantitative that quantifies specific properties of product derivation artifacts produced for the different approaches. A set of criteria and metrics are also being proposed with the aim of providing support to the qualitative and quantitative analysis. Two software product lines from the web and mobile application domains are targets of our study / Abordagens de deriva??o de produto s?o respons?veis por automatizar o processo de engenharia de aplica??o de linhas de produto de software. O conhecimento de configura??o, que ? respons?vel por relacionar o espa?o do problema com o espa?o da solu??o, desempenha um papel fundamental nas abordagens de deriva??o de produto. Cada ferramenta adota estrat?gias e t?cnicas diferentes para gerenciar o processo de deriva??o de produto e h? uma car?ncia de estudos experimentais para avaliar as diferentes abordagens. Esta disserta??o de mestrado tem como objetivo comparar sistematicamente abordagens de deriva??o autom?tica de produtos, atrav?s do desenvolvimento de estudos emp?ricos. Os estudos s?o desenvolvidos sob duas perspectivas: (i) qualitativa atrav?s da an?lise de caracter?sticas das ferramentas; e (ii) quantitativa atrav?s da quantifica??o de propriedades espec?ficas de artefatos de deriva??o produzidos para as ferramentas. Um conjunto de crit?rios e m?tricas tamb?m ? proposto com o objetivo de oferecer suporte para as an?lises qualitativas e quantitativas. Duas linhas de produto, uma para o dom?nio de sistemas web e outra para o contexto de aplica??es de dispositivos m?veis, s?o alvos do nosso estudo

In this thesis, the phenomenon of intercategorial polysemy is approached from two related but previously unconnected perspectives, namely that of linguistic creativity and mental representation. It is argued that the creativity that is part and parcel of the linguistic abilities of each and every human being, has been neglected in the study of linguistics, and should, in fact, form the basis of studies such as these in cognitive lexical creativity. It is argued that structural productivity (the generative view of linguistic creativity) and conceptual creativity lie on a continuum, the middle ground of which is covered by phenomena which are both productive and creative and which have both a formal and a semantic aspect to them. One such a phenomenon is intercategorial polysemy. Explaining the way in which speakers of a language such as English can systematically and productively produce and interpret words that belong to more than one syntactic category (for example, hammerN - hammerV, tableN - tableV, skyN - skyV), which may range from the conventionalised to the completely innovative, has long been a problem for linguists. Traditional morphological accounts involving theoretical notions such as zero derivation have always been found to be inadequate, mostly because zero derivation does not account for the variation in meaning and the background knowledge that is needed to produce and interpret novel instances. The main problem addressed in this thesis then is the question as to the nature of the lexical knowledge of speakers and its mental representation, so that it can form the basis for the cognitive processes that will enable language users to be linguistically creative. Various theoretical models that have been proposed to account for intercategorial polysemy, namely the representationalderivational model, the network-activation model, as well as the theory of conceptual integration (also called blending), are presented and evaluated in the light of a representative sample of completely novel instances of intercategorial polysemy. / Linguistics and Modern Languages / D. Litt. et Phi. (Linguistics)

Le traitement automatique de la langue quechua (TALQ) ne dispose pas actuellement d'un dictionnaire électronique des verbes, du français-quechua. Pourtant, un projet visant la traduction automatique nécessite au préalable, entre autres, cette importante ressource.Cette thèse consiste à élaborer un dictionnaire électronique français-quechua des verbes. La réalisation d'un tel dictionnaire peut ouvrir également de nouvelles perspectives dans l'enseignement à distance, dans les domaines de l'accès multilingue aux informations, l'annotation/l'indexation des documents, la correction orthographique et pour le TAL en général. La première difficulté consiste à sélectionner un dictionnaire français comme base de travail. Parmi les nombreux dictionnaires français, il en existe très peu en format électronique, et moins encore ceux dont les sources soient en libre accès au public. Parmi ces derniers, l'ouvrage Les verbes français (LVF), contenant 25 610 sens verbaux, que Jean Dubois et Françoise Dubois-Charlier ont publié chez Larousse en 1997, est un dictionnaire particulièrement complet ; de plus il a l 'avantage d'avoir une licence « open source » et un format compatible avec la plateforme NooJ. En tenant en compte ces considérations nous avons choisi traduire ce dictionnaire en quechua.Cependant, cette tâche se heurte à un obstacle considérable : le lexique quechua de verbes simples compte moins de l 500 entrées. Comment faire correspondre 25 610 sens verbaux français avec seulement 1 500 verbes quechua ?Sommes-nous condamnés à utiliser beaucoup de polysémies? Par exemple, dans LVF il y a 27 sens verbaux du verbe « tourner » ; doit-on tous les traduire par muyuy ? Ou bien, pouvons-nous utiliser une stratégie particulière et remarquable de la langue pour répondre à ce défi : la génération de nouveaux verbes par dérivation suffixale ?Nous avons inventorié tous les suffixes du quechua qui permettent d'obtenir une forme dérivée possédant le comportement d'un verbe simple. Cet ensemble de suffixes que nous appelons SIP_DRV, contient 27 éléments. Ainsi chaque verbe quechua transitif ou intransitif donne naissance à au moins 27 verbes dérivés. Il reste cependant à formaliser les paradigmes et grammaires qui vont nous permettre d'obtenir les dérivations compatibles avec la morphosyntaxe de la langue. Cela a été réalisé avec NooJ.L'application de ces grammaires nous a permis d'obtenir 40 500 unités linguistiques conjugables (ULAV) à partir de 1 500 verbes simples quechua. Ce résultat encourageant nous permet d'envisager une solution favorable à notre projet de traduction des 25 000 sens verbaux du français en quechua.À ce stade, une nouvelle difficulté apparaît : la traduction en français de cette quantité énorme des formes verbales conjugables générées, dont sa résolution est essentielle pour notre projet de traduire une partie importante des vingt-cinq mille verbes français en quechua.Afin d'obtenir la traduction de ces ULAV, nous avons besoin d'abord de connaître la modalité d'énonciation qu'apporte chaque SIP quand il s'agglutine au radical verbal pour le transformer. Chaque suffixe peut avoir plusieurs modalités d'énonciation. Nous les avons obtenus à partir du corpus, de notre propre expérience et quelques enregistrements dans le terrain. Nous avons ainsi construit un tableau indexé contenant toutes ces modalités. Ensuite, nous utilisons des opérateurs de NooJ pour programmer les grammaires qui présentent la traduction automatique en une forme glosés de modalités d'énonciation.Finalement, nous avons développé un algorithme qui nous a permis d'obtenir la traduction réciproque du français vers le quechua de plus de 8 500 sens verbaux de niveau 3 et un certain nombre de sens verbaux de niveau 4 et 5. / The automatic processing of the Quechua language (APQL) lacks an electronic dictionary of French­ Quechua verbs. However, any NLP project requires this important linguistic resource.The present thesis proposes such a dictionary. The realization of such a resource couId also open new perspectives on different domains such as multilingual access to information, distance learning,inthe areas of annotation /indexing of documents, spelling correction and eventually in machine translation.The first challenge was the choice of the French dictionary which would be used as our basic reference. Among the numerous French dictionaries, there are very few which are presented in an electronic format, and even less that may be used as an open source. Among the latter, we found the dictionary Les verbes français (LVF}, of Jean Dubois and Françoise Dubois-Charlier, edited by Larousse en 1997. lt is a remarkably complete dictionary. lt contains 25 610 verbal senses and with open source license. lt is entirely compatible with the Nooj platform. That's why we have chosen this dictionary to be the one to translate into Quechua.However, this task faces a considerable obstacle: the Quechua lexicon of simple verbs contains around 1,500 entries. How to match 25,610 French verbal senses with only 1,500 Quechua verbs?Are we condemned to produce many polysemies? For example, in LVF, we have 27 verbal senses of the verb "tourner" to turn; should we translate them all by the Quechua verb muyuy to turn? Or, can we make use of a particular and remarkable Quechua strategy that may allow us to face thischallenge: the generation of new verbs by suffix derivation?As a first step, we have inventoried ail the Quechua suffixes that make possible to obtain a derived verbal form which behaves as if it was a simple verb. This set of suffixes, which we call IPS_DRV, contains 27 elements. Thus each Quechua verb, transitive or intransitive, gives rise to at least 27 derived verbs. Next, we need to formalize the paradigms and grammars that will allow us to obtain derivations compatible with the morphology of the language. This was done with the help of the NooJ platform.The application of these grammars allowed us to obtain 40,500 conjugable atomic linguistic units (CALU) out of 1,500 simple Quechua verbs. This encouraging first result allows us to hope to get a favorable solution to our project of translation of the 25,000 verbal senses of French into Quechua.At this point, a new difficulty appears: the translation into French of this enormous quantity of generated conjugable verbal forms. This work is essential if we want to obtain the translation of a large part of the twenty-five thousand French verbs into Quechua. ln order to obtain the translation of these CALUs, we first needed to know the modalities of enunciation that each IPS have and transmits to the verbal radical when it is agglutinated to it. Each suffix can have several modalities of enunciation. We have obtained an inventory of them from the corpus, our own experience and some recordings obtained in fieldwork. We constructed an indexed table containing all of these modalities.Next, we used NooJ operators to program grammars that present automatic translation into a glossed form of enunciation modalities.Finally, we developed an algorithm that allowed us to obtain the reciprocal translation from French to Quechua of more than 8,500 Verbal senses of Level 3 and a number of verbal senses of Levels 4 and 5.