本論文旨在描述並嘗試以優選詞彙功能語法理論(OT-LMT)處理雅美語的論旨角色與語法功能的連結。雅美語的論旨角色與語法功能連結呈現出作格語言的特性，以致跟中文或英文有很大的差別。並且雅美語的連結又受到了焦點系統的影響，所以更加的複雜。現存的連結理論無論是以變換語法理論為基礎或以詞彙語法為基礎的，似乎都無法很直接簡潔的描述雅美語。本論文嘗試架構一個以優選理論為基礎的新連結模型，並且除了將之使用在雅美語上之外，也同時以這個新的模型來處理中文和英文中的連結。由於優選理論具有彈性的特性，這三種語言不同的連結模式，都可以被包含在這個新的模型當中。 / This thesis studies the problem of argument-function linking in Yami and makes the fundamental claim that linking in Yami shows an ergative pattern, quite different from that in accusative languages, such as Mandarin and English. The linking phenomenon in Yami is complicated by its special voice system. Existing linking theories do not account for Yami straightforwardly. In trying to find a framework that can handle the Yami data, we find the flexibility of Optimality Theory a promising solution. The first part of this thesis is a description of the argument-function linking pattern in Yami and the proper place of the voice system is also discussed. And then we review several grammatical theories on linking. Both transformation-based theories and lexicalist theories are examined. We will demonstrate how these theories fail to account for linking in Yami in a straightforward manner. Thus we provide an optimality-theoretic account based on the lexical mapping theory of Lexical-Functional Grammar. This newly developed framework is applied not only to the Yami data but also to the relevant Mandarin and English data. It is claimed that this framework can accommodate all three different languages.

Σκοπός της παρούσας εργασίας είναι να δώσει μια ανάλυση των ρημάτων ψυχικού πάθους της Νέας Ελληνικής βασισμένη σε δύο σημαντικούς παράγοντες: α) την συντακτική πραγμάτωση των ορισμάτων του κατηγορήματος και β) την μορφολογία της φωνής του ρήματος. Πιο συγκεκριμένα, εξετάζω την κατηγορία ρημάτων ψυχικού πάθους που παρουσιάζει την εναλλαγή μεταξύ των δύο συντακτικών δομών Object Experiencer και Subject Experiencer με ταυτόχρονη εναλλαγή στην μορφολογία της φωνής του ρήματος μεταξύ της ενεργητικής και της μεσοπαθητικής. Το βασικό ερώτημα στο οποίο επιχειρώ να απαντήσω είναι εάν οι δομές Subject Experiencer με μεσοπαθητική μορφολογία στο ρήμα αποτελούν παθητικοποιημένες δομές των αντίστοιχων δομών Object Experiencer με ενεργητική μορφολογία στο ρήμα. Αρχικά, στο κεφάλαιο 1 συζητώ το πρόβλημα σύνδεσης των θεματικών ρόλων και των συντακτικών θέσεων που εμφανίζουν τα ρήματα ψυχικού πάθους γενικά, καθώς και τον τρόπο με τον οποίο τα ρήματα ψυχικού πάθους της Νέας Ελληνικής εκδηλώνουν αυτό το πρόβλημα. Στο πλαίσιο αυτό υποστηρίζω ότι ένας σημαντικός παράγοντας που πρέπει να μελετηθεί είναι η μορφολογία της φωνής του ρήματος. Έπειτα, στο κεφάλαιο 2 που αποτελεί το θεωρητικό πλαίσιο, παρουσιάζω α) τις σημαντικότερες συντακτικές αναλύσεις που έχουν προταθεί για την ερμηνεία της συμπεριφοράς των ρημάτων αυτών και, β) τις ιδιότητες και ερμηνείες της μεσοπαθητικής μορφολογίας της φωνής στην Νέα Ελληνική που αποτελεί σημαντικό παράγοντα για την μελέτη των ρημάτων αυτών. Στο κεφάλαιο 3 επεκτείνω την κατηγοριοποίηση που έχει προταθεί για τα ρήματα ψυχικού πάθους, με βάση την συντακτική προβολή των ορισμάτων του κατηγορήματος και την μορφολογία της φωνής στα ρήματα αυτά και συζητώ την συντακτική συμπεριφορά κάθε κατηγορίας. Στο κεφάλαιο 4 εξετάζω σε βάθος μια συγκεκριμένη κατηγορία ρημάτων ψυχικού πάθους της Νέας Ελληνικής η οποία παρουσιάζει την εξής συμπεριφορά: τα ρήματα αυτά μπορούν να εμφανίζουν την εναλλαγή μεταξύ Object Experiencer και Subject Experiencer συντακτικών δομών, η οποία συνοδεύεται από εναλλαγή στην ρηματική μορφολογία της φωνής. Αρχικά, ελέγχω την δυνατότητα συντακτικής παθητικοποίησης των Object Experiencer ρημάτων κι έπειτα, εξετάζω την ερμηνεία των δομών Subject Experiencer με ρήμα μεσοπαθητικής μορφολογίας. Καταλήγω στο συμπέρασμα ότι μια Subject Experiencer δομή με ρήμα μεσοπαθητικής μορφολογίας μπορεί να έχει α) την παθητική δομή και ερμηνεία, και σε αυτή την περίπτωση παράγεται από την αντίστοιχη Object Experiencer ενεργητική δομή, β) την μέση δομή και ερμηνεία, όταν το ποιητικό αίτιο παραλείπεται και, γ) την αυτοπαθή δομή και ερμηνεία όταν η προθετική φράση που εμφανίζεται σε αυτή δηλώνει την αιτία. Αυτό εξαρτάται από την θέση στην όποια παράγεται το μεσοπαθητικό μόρφημα στην βαθεία δομή, στην παρουσία η όχι προσαρτήματος και στο είδος του προσαρτήματος αυτού. Στο κεφάλαιο 5 κάνω μια ανασκόπηση όλης της εργασίας και συνοψίζω τα συμπεράσματα που προέκυψαν από την ανάλυση που έγινε στο τέταρτο κεφάλαιο. / The purpose of the present study is to provide an analysis of the psych verbs in Modern Greek which is based on two significant factors: a) the syntactic realization of the arguments of the predicate and b) the voice morphology of the verb. More specifically, I am examining a particular category of the Greek psych verbs: the category that involves at the same time an alternation between two syntactic structures, the Object Experiencer and the Subject Experiencer structures and an alternation between the active and the mediopassive voice morphology. The basic question which I will try to answer is whether the Subject Experiencer structures with the mediopassive voice morphology on the verb are the passivized forms of the corresponding Object Experiencer structures with the active voice morphology on the verb. First of all, in the first chapter I am discussing the linking problem between thematic roles and syntactic positions that the psych verbs generally pose, as well as the way in which this problem is manifested by the Greek psych verbs in particular. In this context, I claim that a very important factor that has to be investigated is the voice morphology of the verb. Moreover, in chapter 2, that is the theoretical background of the present study, I am presenting a) the most important syntactic analyses that have been proposed for the explanation of the behavior of these verbs and b) the properties and interpretations of the mediopassive voice morphology of the verb in Modern Greek that is a very significant factor for the study of these verbs. In chapter 3 I am expanding the categorization of the psych verbs that has been proposed, on the basis of the syntactic projection of the arguments of the predicate and the voice morphology of these verbs and I am discussing the syntactic behavior of each category. In chapter 4 I am examining in deep a specific category of psych verbs in Modern Greek which presents the following behavior: these verbs can involve the alternation between the Object Experiencer and the Subject Experiencer syntactic structures, which is combined with an alternation in the voice morphology of the verb. To begin with, I am examining the possibility of syntactic passivization of Object Experiencer verbs and then, I am investigating the interpretation of Subject Experiencer structures with a verb that has the mediopassive morphology. The conclusion to which I am reaching is that a Subject Experiencer structure with a verb that has the mediopassive morphology can have a) the passive structure and interpretation, and in this case the structure is derived by the corresponding Object Experiencer active structure, b) the middle structure and interpretation, when the agent is omitted and, c) the reflexive structure and interpretation when the prepositional phrase that is present in it expresses the cause. The aforementioned depends on the position in which the mediopassive morpheme is derived in the Deep Structure, on the presence or not of an adjunct and on the nature of this adjunct. In chapter 5 I am summarizing the whole study and providing a synopsis of the main conclusions of the analysis that was depicted in the fourth chapter.

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.

Casein is the major protein fraction in milk, and its cross-linking has been a topic of scientific interest for many years. Enzymatic cross-linking has huge potential to modify relevant techno-functional properties of casein, whereas non-enzymatic cross-linking occurs naturally during the storage and processing of milk and dairy products. Two size separation techniques were applied for characterisation of these reactions: gel electrophoresis and size exclusion chromatography. This review summarises their separation principles and discusses the outcome of studies on cross-linked casein from the last ~20 years. Both methods, however, show limitations concerning separation range and are applied mainly under denaturing and reducing conditions. In contrast, field flow fractionation has a broad separation range and can be easily applied under native conditions. Although this method has become a powerful tool in polymer and nanoparticle analysis and was used in few studies on casein micelles, it has not yet been applied to investigate cross-linked casein. Finally, the principles and requirements for absolute molar mass determination are reviewed, which will be of increased interest in the future since suitable calibration substances for casein polymers are scarce.

Le travail présenté dans ce manuscrit s’intéresse au mode d’action des résines thermodurcissables utilisées pour conférer au matériau papier des propriétés spécifiques. En effet, certains papiers sont destinés, au cours de leur usage, à être en contact avec des liquides et en particulier de l’eau. C’est le cas, par exemple, des papiers absorbants, de certains papiers filtres, mais aussi de papiers pour étiquettes ou pour billets de banque. En présence d’eau, les papiers perdent rapidement leur résistance mécanique, essentiellement due à la présence en grand nombre de liaisons hydrogène, d’où la nécessité d’un traitement : l’objectif est de maintenir un certain niveau de résistance des papiers saturés en eau. Ces traitements consistent à introduire dans la suspension fibreuse, en cours d’élaboration, des pré-polymères cationiques s’adsorbant à la surface des fibres. Après la formation de la feuille de papier, la feuille humide est séchée et c’est au cours de cette étape que s’amorce la réticulation de ces polymères. Elle conduit à la formation d’un réseau tridimensionnel de polymère dans le matelas fibreux. Ce réseau permet au papier de conserver ses propriétés mécaniques lorsqu’il est en contact avec de l’eau. Il présente ce que l’on appelle communément une résistance à l’état humide (REH). Un des inconvénients de ce type de traitement est lié aux difficultés de recyclage des papiers obtenus. Il nécessite un traitement particulièrement intensif et coûteux qui couple une action mécanique (désintégration, dépastillage) à une action chimique (utilisation d’hydroxyde de sodium, par exemple). Même si ces produits sont largement utilisés, les mécanismes mis en jeu que ce soit pour le développement des propriétés de REH ou pour le recyclage ne sont pas totalement compris. Dans ce contexte, ce travail a pour objectif d’étudier le mode d’action de pré-polymères de polyamideamine épichlorhydrine (PAE), couramment utilisés en papeterie pour conférer au matériau papier une résistance à l’état humide (REH). Il s’intéresse à la caractérisation de solutions commerciales de PAE et à l’étude des mécanismes réactionnels de ces pré-polymères. Il traite également de l’effet de certains paramètres de production du papier sur l’efficacité des traitements. Enfin, il apporte de éléments nouveaux sur la compréhension de l’étape de recyclage. / Polyamideamine epichlorohydrin (PAE) resin is a water soluble additive and the most used permanent wet strength additive in alkaline conditions for preparing wet strengthened papers. In this thesis, we studied some properties of PAE resins and wet strengthened papers prepared from them. In order to elucidate PAE structure, liquid state, 1H and 13C NMR was performed and permitted signals assignment of PAE structure. PAE films were prepared to study cross-linking reactions and then thermal and ageing treatments were performed. According to our results, the main PAE cross-linking reaction occurs by a nucleophilic attack of N atoms in the PAE and/or polyamideamine structures forming 2-propanol bridges between PAE macromolecules. A secondary contribution of ester linkages to the PAE cross-linking was also observed. However, this reaction, which is thermally induced, only occurs under anhydrous conditions. The mechanism related to wet strength development of PAE-based papers was studied by using CMC as a model compound for cellulosic fibres and PAE-CMC interactions as a model for PAE-fibres interactions. Based on results from NMR and FTIR, we clearly showed that PAE react with CMC that is when carboxylic groups are present in great amounts. Consequently, as the number of carboxylic groups present in lignocellulosic fibres is considerably less important and the resulting formed ester bonds are hydrolysable, we postulate that ester bond formation has a negligible impact on the wet strength of PAE-based papers. In the second part of this work, a 100% Eucalyptus pulp suspension was used to prepare PAE-based papers. PAE was added at different dosages (0.4, 0.6 and 1%) into the pulp suspension and its adsorption was indirectly followed by measuring the zeta potential. Results indicate that the adsorption, reconformation and/or penetration phenomena reach an apparent equilibrium between 10 and 30 min. Moreover, we showed that the paper dry strength was not significantly affected by the conductivity level (from 100 to 3000 µS/cm) of the pulp suspension. However, the conductivity has an impact on the wet strength and this effect seems to be enhanced for the highest PAE dosage (1%). We also demonstrated that storing the treated paper under controlled conditions or boosting the PAE cross-linking with a thermal post-treatment does not necessarily lead to the same wet strength. Degrading studies of cross-linked PAE films showed that PAE degradation in a persulfate solution at alkaline medium was more effective. A preliminary study of industrial PAE-based papers (coated and uncoated papers) was also performed. For uncoated paper, persulfate treatment was the most efficient. For coated papers, all treatments were inefficient in the used conditions, although a decrease of the wet tensile force of degraded samples was observed. The main responsible of the decrease of persulfate efficiency for coated papers was probably related to side reactions of free radicals with the coating constituents.

Made available in DSpace on 2014-12-17T14:13:33Z (GMT). No. of bitstreams: 1 ElquioEO_TESE.pdf: 1649953 bytes, checksum: 1098cd34b1d3e6c9a180949d25fa8185 (MD5) Previous issue date: 2010-06-07 / Universidade Federal do Rio Grande do Norte / The aim of this work was to perform the extraction and characterization of xylan from corn cobs and prepare xylan-based microcapsules. For that purpose, an alkaline extraction of xylan was carried out followed by the polymer characterization regarding its technological properties, such as angle of repose, Hausner factor, density, compressibility and compactability. Also, a low-cost and rapid analytical procedure to identify xylan by means of infrared spectroscopy was studied. Xylan was characterized as a yellowish fine powder with low density and poor flow properties. After the extraction and characterization of the polymer, xylan-based microcapsules were prepared by means of interfacial crosslinking polymerization and their characterization was performed in order to obtain gastroresistant multiparticulate systems. This work involved the most suitable parameters of the preparation of microcapsules as well as the study of the process, scale-up methodology and biological analysis. Magnetic nanoparticles were used as a model system to be encapsulated by the xylan microcapsules. According to the results, xylan-based microcapsules were shown to be resistant to several conditions found along the gastrointestinal tract and they were able to avoid the early degradation of the magnetic nanoparticles / O presente trabalho teve como objetivo a extra??o e caracteriza??o do pol?mero de xilana a partir de res?duos de sabugo de milho e a produ??o de microc?psulas a partir deste pol?mero. O primeiro passo foi a extra??o da xilana em meio alcalino e caracteriza??o deste pol?mero quanto as suas propriedades tecnol?gicas (?ngulo de repouso, fator de Hausner, densidade, compressibilidade e compactabilidade), bem como a elabora??o de uma procedimento r?pido e barato para a identifica??o deste pol?mero atrav?s de espectroscopia de absor??o na regi?o do infravermelho. O pol?mero de xilana foi caracterizado como sendo um p? de cor amarelada de baixa densidade e com propriedades de escoamento pouco favor?veis. Ap?s a obten??o e caracteriza??o do pol?mero, microc?psulas de xilana foram preparadas atrav?s da reticula??o polim?rica interfacial e caracterizadas a fim de se obter sistemas multiparticulados gastroresistentes. O trabalho foi delineado buscando-se os melhores fatores na t?cnica de prepara??o das microc?psulas, assim como o estudo do processo, aumento de escala e avalia??o biol?gica. Nanopart?culas magn?ticas foram utilizadas como sistema modelo a ser encapsulado pelas microc?psulas ? base de xilana. Os resultados obtidos demonstraram que as microc?psulas de xilana s?o resistentes ?s diversas condi??es encontradas ao longo do trato gastrintestinal e foram capazes de evitar a degrada??o pr?via das nanopart?culas magn?ticas in vitro

Užití biologických materiálů k náhradě tkání v plastické chirurgii ! Abstrakt v angličtině Background: Biological meshes are biomaterials consisted of extracellular matrix and used in surgery particularly for hernia treatment or thoracic wall reconstruction. They are capable of vascularization, that decreases risk of infection, expecially when used in contaminated fields. This study compared the strength of incorporation and biocompatibility of two porcine-derived grafts (cross-linked and non-cross-linked) in a rat hernia model. In addition, we hypothesized that combination of extracellular matrices with autologous mesenchymal stem cells used for hernia repair would result in increased vascularization and increased strength of incorporation. Methods: Standardized 2 x 4 cm fascial defect was created in 42 Wistar rats and repaired with a cross-linked or a non-cross-linked graft either enriched or non-enriched with stem cells. The rats were sacrificed 3, 6 and 12 months later. The strength of incorporation, vascularization, cellular invasion, foreign body reaction and capsule formation were evaluated. Results: Comparison of stem cell enriched and non-enriched groups showed no significant differences in the capsule thickness, foreign body reaction, cellularization or vascularization. In the non-cross-linked...

In the present work, a super water-absorbent poly(acrylic acid) was synthetized by inverse suspension polymerization, using Span60 as the dispersant, toluene as the dispersing organic phase, trimethylolpropane triacrylate as the crosslinking agent, and sodium persulfate as the initiator. The synthesis was conducted in a small-scale glass reactor operated in semi-batch mode. The following reaction conditions were evaluated: effects of initiator concentration, temperature, percentage of multifunctional cross-linker agent and monomer concentration. Also, two important properties were determined, conversion and gel fraction. A kinetic model including a population balance was employed to simulate the process. The proposed model uses the numerical fractionation technique and is capable of predicting the pre-gel and post-gel properties, the effect of the crosslinking agent level on the polymer properties and the dynamic of gelation. The model was compared with the experimental results and showed a satisfactory representation of the system after parameter adjusting. / No presente trabalho, o poli (ácido acrílico) super-absorvente foi sintetizado por polimerização em suspensão inversa, usando Span 60 como o dispersante, tolueno como fase orgânica, trimetilolpropano triacrilato como agente de reticulação e persulfato de sódio como iniciador. A síntese foi conduzida num reator de vidro em escala de bancada, operado em modo semi-batelada-batelada. As seguintes condições da reação foram avaliadas: os efeitos da concentração de iniciador, a temperatura, a porcentagem de agente de reticulação multifuncional e a concentração de monómero. Além disso, foram determinadas propriedades importantes, como a conversão e a fração de gel. Da mesma forma, foi desenvolvido um modelo de balanço populacional para simular o processo em conjunto com a técnica de fracionamento numérico, que é capaz de prever as propriedades pré-gel e pós-gel, o efeito do nível do agente de reticulação no polímero e as propriedades da dinâmica de gelificação. O modelo foi comparado com os resultados experimentais e mostrou uma representação satisfatória do sistema após o ajuste dos parâmetros.

L’objectif de ce travail est de qualifier l’utilisation du collage structural en remplacement des solutions d’assemblage conventionnel dans les applications lanceur spatiaux. Si les gains potentiels tant en terme opérationnel qu’en terme de performance ne sont plus à démontrer il reste à mettre en place une démarche de dimensionnement qui garantisse le niveau important de fiabilité requis. Deux adhésifs structuraux de types époxydes ont été étudiés : l’EA9394 et le SW2216. Un travail important d’analyse physico-chimique des surfaces a été mené pour mettre en place un procédé d’assemblage stable et performant. L’analyse mécanique des liaisons collées a montré que l’adhésif subit en situation des sollicitations combinées de traction et de cisaillement. Un dispositif dérivé des essais Arcan à été proposé qui permet d’obtenir la réponse du film de colle sous forme de courbe contrainte déplacement relatif des substrats. La résistance mécanique mesurée au moyen des essais Arcan mais également sur le matériau adhésif montre une forte dispersion liée à un taux de porosité important mais également à une microstructure très hétérogène constituée d’une matrice époxyde et mélangée à des particules d’aluminium (adhésif EA9394). Enfin, le collage a été étudié à une échelle plus macroscopique en tentant de proposer un dimensionnement de liaison pour le lanceur démonstrateur Arcadia. Les lanceurs étant des structures à symétrie de révolution, un modèle semi-analytique de liaison collée axisymétrique a été développé.Ce travail a permis la mise en place d’une démarche d’analyse mettant en avant les analyses à l’échelle du film, de la liaison et de la structure pour mettre en évidence les nombreux phénomènes à l’origine d’une ruine prématurée de la liaison. Cette optimisation multiéchelle doit être conduite pour maximiser la résistance spécifique de la liaison en assurant le niveau de fiabilité requis pour cette application spatiale. / The objective of this study is to qualify the use of structural bonding as a replacement for conventional assembly solutions in space launcher applications. Potential benefits in fabrication and of final performance are already known, but it remains to establish a design approach to guarantee the high level of reliability required. Two epoxy structural adhesives have been studied: EA9394 and SW2216. A study of the physico-chemistry of surfaces has been effected in order to find a stable and strong bonding process. Mechanical analysis of bonded connections revealed that the adhesives could be subjected in use to mixed loadings in tension and shear. A device derived from Arcan tests has been proposed in which it is possible to obtain adhesive layer responses as stress/relative deformation for different substrates. Mechanical strength measured with the Arcan device and also on the bulk adhesive material revealed a high variability coming from a significant porosity fraction but also due to a highly heterogeneous microstructure constituted of epoxy matrix and aluminium particles (EA9394adhesive). Bonding has been studied on a macroscopic scale proposing connection design for the demonstration Arcadia launcher. A rocket being an axially symmetrical structure, a semi-analytical model of axisymmetric bonded connections has been developed. This study resulted in the finalisation of an analysis approach pointing to scale analysis of the adhesive layer, connection and structure in order to emphasise the many phenomena which could cause early bond failure. This multiscale approach should be effected to increase specific assembly strength while assuming the required reliability level for this spatial application.

L’élucidation des interactions non-covalentes des complexes biologiques revêt d’une importance majeure dans la compréhension du fonctionnement cellulaire. L’objectif de ce travail de thèse est d’approfondir les développements de la spectrométrie de masse (MS) pour l’étude de ces complexes, que ce soit par MALDI-MS (la désorption-ionisation laser assistée par matrice) ou par ESI-MS (l’ionisation électrospray). Ce travail s’est articulé autour de trois axes : i) étude de la stœchiométrie et de la topologie du complexe SAGA HAT (Spt-Ada-Gcn5 Acétyltransferase, module Histone Acétyl Transferase) par pontage chimique couplé à la MS ; ii) suivi de la dimérisation des complexes formés par RAR-RXR (récepteur de l’acide rétinoïque - récepteur X des rétinoïdes) avec différents ADNs ; iii) mesure de la constante de dissociation des complexes RXR-ligand. Les méthodologies développées ont permis de repousser le potentiel de la MS et d’obtenir des informations structurales des complexes biologiques. / Elucidation of non-covalent interactions of biological complexes takes on great importance for the understanding of cellular function. The purpose of this thesis is a further development of mass spectrometry (MS) for the study of these complexes, either by MALDI-MS (matrix-assisted laser desorption-ionization) or by ESI-MS (electrospray ionization). This work was focused on three main lines: i) study of the stoichiometry and the topology of SAGA HAT (Spt-Ada-Gcn5 Acetyltransferase, Histone Acetyl Transferase module) complex by chemical cross-linking coupled to MS; ii) monitoring the dimerization of the complexes formed by RAR-RXR (retinoic acid receptor - retinoid X receptor) with different DNAs; iii) measuring the dissociation constant of RXR-ligand complexes. The developed methodologies made it possible to expand the potential of MS and get insight into structure of biological complexes.