Proteins can often adsorb irreversibly at fluid/fluid interfaces; the understanding of the adsorption mechanism has relevance across a variety of industrial (e.g. the creation of stable emulsions) and biological (e.g. biofilm formation) processes. I performed molecular dynamics simulations of two surfactant proteins as they interact with air/water and oil/water interfaces, describing the origin of the surface activity, the adsorption dynamics and the conformational changes that these proteins undergo at the interface. BslA is an amphiphilic protein that forms a highly hydrophobic coat around B. subtilis biofilms, shielding the bacterial community from an external aqueous solution. By investigating the behaviour of BslA variants at oil/water interfaces via coarse-grained molecular dynamics, I show that BslA represents a biological example of an ellipsoidal Janus nanoparticle, whose surface interactions are controlled by a local conformational change. All-atom molecular dynamics simulations then reveal the details of the conformational change of the protein upon adsorption, and the self-assembly into a two-dimensional interfacial crystal. Ranaspumin-2 is one of the main components of the tungara frog foam nest. Contrary to most surfactant proteins, its structure lacks any sign of amphiphilicity. All-atom simulations show that the adsorption proceeds via a two-step mechanism where firstly the protein binds to the interface through its flexible N-terminal tail and then it undergoes a large conformational change in which the hydrophobic core becomes exposed to the oil phase. I then developed a simple structure-based coarse-grained model that highlights the same adsorption mechanism observed in all-atom simulations, and I used it to compare the dynamics of adsorption and the underlying free energy landscape of several mutants. These results agree with and are used to rationalise the observations from Langmuir trough and pendant drop experiments. Colloids can often be considered simpler versions of proteins that lack conformational changes. I performed coarse-grained simulations of the compression of interfacial monolayers formed by rod-like particles. These simulations show a rich behaviour characterised by the flipping of adsorbed rods, nematic ordering and bilayer formation. I report the series of transitions that take place as the rod aspect ratio is increased from 3 to 15.

Pressure-sensitive adhesives (PSAs) are complex macromolecular-based blend formulations that, in dry form will adhere permanently to diverse surfaces with the application of mere finger pressure. This thesis addresses the bonding and debonding mechanisms of coated films of different commercially available PSAs by systemically investigating the film characteristics on multiple levels. The methods implemented involve a novel procedure in investigating viscoelastic properties with Dynamic Mechanical Analysis, film surface chemistry with Time-of-flight Secondary Ion Mass Spectrometry and film morphology, modulus and bonding characteristics with Atomic Force Microscope. The theoretical aspect invoked rubber elasticity, viscoelasticity and thermodynamic concepts in representation of film morphology with corresponding adhesion nature. The results indicate that the bonding and debonding behaviour of PSA films are of a viscoelastic nature, dictated mainly by two fundamental morphological elements. These elements are; (1) the formation of phase-separated self-assembly of polystyrene-richcopolymer nano-domains within the adhesive matrix and (2) the inter-linking of the nanodomains by elastically active elastomer segments into a physical crosslinked network system that is highly efficient in dissipating large strain energy. These morphological factors are manifested through a profound contribution to the peel strength of the adhesive films when either coated at high temperatures or annealed. Increasing the content of the polystyrene endblock-tackifier in the adhesive blend formulation increased the PSA’s performance sensitivity to the film coating temperature. Meanwhile increasing the cis-C=C bond concentration in the formulation reduced the film’s performance sensitivity to coating temperature, as polydienes are premised to promote the entropy-elasticity of the film matrix by contributing to the nano-domain interconnections. This thesis generates many qualitative similarities, despite the significantly different adhesive blends investigated and hopefully the results reported here are more universal than one might expect.

Highly crosslinked epoxy resin systems are essential in aerospace applications due to the high operating temperatures. Although highly crosslinked epoxy resins have the required glass transition temperature (Tg) for the application, they are inherently brittle and matrix toughness is improved by incorporation of a second phase. Previous studies have focused mostly on toughening of lightly crosslinked epoxy systems, whereas this study investigates toughening of a highly crosslinked epoxy resin system using thermoplastic toughners poly(ether sulfone) (PES) and a poly(methyl methacrylate)-b- poly(butyl acrylate)-b-poly(methyl methacrylate) (MAM) block copolymer (BCP).

Innerhalb des Forschungsprojekts “InduRex” sollen u.a. dünnwandige Graphit-Polymer Bipolarplatten (BPP) für Brennstoffzellen (BZ) entwickelt werden. Der Fokus liegt dabei auf hochgefüllten Compoundmaterialien und Prozesstechniken zur kontinuierlichen Herstellung dünnwandiger Folien. Dabei wird die gesamte Prozesskette, beginnend von der Auswahl der verwendeten Rohstoffe, über die Folienherstellung bis hin zur Einbringung der erforderlichen Strukturen betrachtet. Die vom „Department of Energy“ festgelegten physikalischen und chemischen Zielwerte werden auch für die Folien als Zielvorgabe gesetzt. Der Schwerpunkt der wissenschaftlichen Arbeit liegt auf einem grundlegenden Verständnis der Materialzusammensetzung und deren Zusammenhang mit den endgültigen Eigenschaften der strukturierten Bipolarplatten, sowie deren Leistung in einem Brennstoffzellenstapel. Die hergestellten Bipolarplattenfolien wurden vor einem Zelltest umfassend hinsichtlich elektrischer Widerstände, H2-Permeation, Warmformbeständigkeit u.a. charakterisiert, um den Einfluss des Produktionsprozesses auf ihre Qualität zu bewerten. / Within the research project 'InduRex', thin-walled graphite-polymer bipolar plates (BPP) for fuel cells (FC) are to be developed, among other things. The focus is on highly filled compound materials and process technologies for the continuous production of thin-walled foils. The entire process chain, starting with the selection of the raw materials used, through film production, to the insertion of the required structures, will be considered. The physical and chemical target values defined by the 'Department of Energy' are also set as targets for the films. The focus of the scientific work is on a fundamental understanding of the material composition and its relationship to the final properties of the patterned bipolar plates, as well as their performance in a fuel cell stack. The fabricated bipolar plate films were extensively characterized in terms of electrical resistances, H2 permeation, heat deflection temperature, and others prior to a cell test to evaluate the impact of the production process on their quality.

Notre étude se veut une analyse qui traverse la sémiotique du sensible et la littérature africaine d’expression française. L’étude part, en effet, des sources orales épiques pour aboutir à l’analyse du sujet tensif par la circulation de l’objet valeur. C'est dire que notre analyse révèle la manière dont les valeurs associées aux pratiques et aux genres de l'oralité interfèrent dans les processus de communication et de perception des objets valeurs, et infléchissent leur réception et leur interprétation.Notre approche part de l’hypothèse que les formes de communications traditionnelles relèvent du sensible. L'analyse sémiotique s’attache à montrer la perception du sensible par la circulation de la valeur que manifeste l’oralité traditionnelle, en prenant en compte les données sémio-linguistiques, mais d’une manière englobant et articulée, quelques éléments de la phénoménologie, concourant à la construction de la signification. En fait, l'étude part d’un renouvellement esthétique qui caractérise l’écriture africaine comme étant liée au sens conféré par l’intégration de l’oralité. Ce qui revient à dire que, dans la prose romanesque africaine, une saisie du sensible s’est avérée possible grâce à l’innovation littéraire, à la présence énonciative et corporelle apte à manifester le sens, sur trois points de vue complémentaires : i) une appréhension de la valeur, à travers le sensible autour du corps, formée par les notions de perception, d’émotion-passions et de langage entendue comme « processus de pensée », ii) sur des parcours sémiotiques de l’énonciation permettant de décrire des états thymiques, comme si, l’analyse du discours en acte du sujet-locuteur, suscite l’affect de la chair et iii) sur ces états affectifs, comme processus des dispositions passionnelles relevant par le dynamisme d’un déploiement passionnelle (des dispositions modaux et tensifs), qui met en évidence des étants. Par voie de conséquence, ces phénomènes passionnels ont autorisé à atteindre une stratégie argumentative manifestée comme une passion intégrée dans la culture orale africaine, comme forme de vie. / Our research is an analysis that crosses the semiotics of the sensible and the african french-speaking literature. The study by, in fact, epic oral sources to achieve the analysis of the tensive subject by the flow of value.This means that our analysis shows how the values associated with the practices and genres of oral interfere in the processes of communication and perception of values object and inflect their reception and their interpretation.Our thesis assumes that the forms of traditional communications fall within the sensitive. The study attempts to show the perception of the sensitive circulation of value that manifests the traditional orality, taking into account the semiotic - linguistic data, but in a way encompassing and articulated some elements of phenomenology, contributing to the construction of the meaning. The study from an aesthetic renewal that characterizes the African writing as being related to the meaning given by the integration of orality. That is to say that in African fiction prose seizure sensitive proved possible with the literary innovation, indicative and bodily presence able to express the meaning, on three complementary views : i) apprehension of value, through the sensitive around the body, formed by notions of perception , emotion-passions and language understood as “thought process”, ii) on semiotic course the saying to describe states of mood , as if the analysis of the speech act of the subject - speaker raises the affect of the flesh.iii) these emotional states, such as process passionate provisions within the dynamism of a passionate deployment ( disposition modals and tensifs ), which highlights beings. Consequently, these phenomena have passion allowed to reach an argumentative strategy manifested as an integrated passion in african oral culture, as a form of life.

In this study, optimization of a transformation and regeneration system via indirect and direct organogenesis in cotyledon, hypocotyl, petiole, leaf and shoot base tissues of sugar beet (Beta vulgaris L. cv. ELK 345 and 1195) was investigated. Two different germination, three different callus induction and shoot induction medium was used for indirect organogenesis of sugar beet cultivar ELK 345. Except cotyledon, other explants (hypocotyl, petiole and leaf) produced callus. However no shoot development was observed from callus of these explants. Shoot base tissue of sugar beet cultivar 1195 was employed for direct organogenesis. Shoot development was achieved via direct organogenesis using 0.1 mg/L IBA and 0.25 mg/L BA. Root development and high acclimatization rate were accomplished from shoot base tissue. Different concentrations of kanamycin and PPT were applied to leaf blade explants to find out optimum dose for selection of transformants. Kanamycin at 150 mg/L and PPT at 3 mg/L totally inhibited shoot development from leaf blades. Moreover, an Agrobacterium mediated transformation procedure for leaf explants of ELK 345 was also optimized by monitoring transient uidA expression 3rd days after transformation. Effects of different parameters (vacuum infiltration, bacterial growth medium, inoculation time with bacteria, Agrobacterium strains and L-cysteine application in co-cultivation medium) were investigated to improve transformation procedure. Vacuum infiltration and Agrobacterium strains were significantly improved transformation procedure. Percentage of GUS expressing areas on leaves increased three folds from the beginning of the study.

A review of the chemistry of poly(lactic acid) was carried out with a focus on techniques and applications of PLA polymer and copolymers with reference to some of the work that has been accomplished over the last 20 years or so. A review of the characterisation techniques used to analyse PLA polymers and copolymers was also carried out giving reference to the equipment and methods used herein. An investigation into the potential of PLA as the hydrophilic portion of a polymeric surfactant was carried out. To develop PLA based surfactants, the ring opening polymerisation of lactide was carried out in a melt in the presence of a long chain alcohol (C₇ to C₂₀) or diol (C₄ & C₆) to produce AB or ABA type polymers that follow the traditional surfactant template. Stannous octanoate and 4-dimethylaminopyridine were typically used as catalysts due to their high activity and relative cheapness. PLA only shows good hydrophilicity with up to 12 lactic acid units in the chain. Above this the electrostatic interactions between polymer chains reduced water solubility. It was also noted that D,L-lactide produced more water soluble polymers (syndiotactic) than the enantiomerically pure L-lactide (isotactic polymer chains). An investigation of the hydrophobic properties of PLA was carried out to evaluate their usefulness for other biodegradable surfactant applications. To this end an investigation of sugars as the hydrophilic portion of the molecule was carried out. Due to problems with solubilising sugars, they were deemed unsuitable for use as initiatiors within the scope of this research. Choline chloride was then investigated as a potential hydrophilic initiator and indeed has produced some of the most water soluble of PLA polymers. Choline chloride presented several challenges as an initiator, its high melting point resulted in polar solvents such as t-butanol being employed. Alternatively, more success was achieved by preparation of a choline chloride eutectic mixture prior to the polymerisation. It was discovered that a choline chloride/urea eutectic mixture was capable of self initiation, thus required no further addition of catalyst, this result shows a potential step forward in PLA green chemistry. A final investigation into producing surface-active PLA in a one-pot process that required only a hydroxycarboxylate initiator was carried out. The production of PLA sodium or potassium salts was carried out in a melt polymerisation and the results show some promise. Initiators that have been employed include a range of a, b and g-hydroxycarboxylic acids. These work through tautomerisation to the alkoxide, which then initiates a living type polymerisation of lactide to produce surface-active polymers. As well as the synthesis of these polymers some analysis of the physical and aqueous properties of these materials was carried out. PLA sodium salts were shown to have reasonable surfactant ability (~45 mNm⁻¹) and low CMC values of around 5x10⁻⁹ mol cm⁻³. They were also shown to have some properties as emulsifiers, and in some cases showed non-Newtonian fluid behaviour such as shear-thinning (thixotropy) and shear-thickening (dilatant). The thermal characteristics of the polymers such as T[subscript]g and stability were assessed as well as their ability to retain water.

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La première synthèse d'un carbène N-hétérocylique borane (NHC-borane) stable a été réalisée en 1993. Pourtant la découverte de leur vaste potentiel en chimie n'a réellement débuté qu'à partir de 2007. Les domaines d'application de ces composés du bore, stables et facile d'accès, s'étendent de la synthèse d'organique (réduction d'imine, hydroboration de liaisons multiples, médiateurs radicalaires) à la chimie organométallique (couplage de Suzuki-Miyaura) en passant par la chimie des polymères (amorceurs ou co-amorceurs de photopolymérisation). L'objectif de ce projet aura été d'étendre l'application des NHC-boranes dans deux différents systèmes de photopolymérisation. Le premier système étudié a permis l'obtention de matériaux acrylates contenant des nanoparticules métalliques à partir d'un seul composé dans un processus monotope. Le second système visait l'amorçage de réactions de polymérisation en émulsion sous irradiation visible. Nous avons utilisé le pouvoir réducteur des NHC-boranes pour former des nanoparticules d'or ou d'argent directement dans des monomères acrylates. Puis, la formation par le NHC-borane de la matrice polymère contenant les nanoparticules est déclenchée par une irradiation UV. L'analyse par HRTEM a mis en évidence des petites nanoparticules (ca. 10 nm) emprisonnées dans la matrice. Cette méthode présente une approche encore plus directe pour obtenir ce type de matériau plutôt que les procédés multi-étapes déjà existants. Le second système étudié utilise pour la première fois un NHC-borane comme co-amorceur de la polymérisation du styrène ou du méthacrylate de méthyle en émulsion sous irradiation visible. Il en résulte des latex stables, composés de particules de tailles moyennes contrôlées formés à partir de quantités de tensioactifs inférieures à celles utilisées dans des systèmes photoamorcés déjà décrits. Ces systèmes amorcés par une irradiation visibles pourraient être intéressants pour réduire les coûts énergétiques des synthèses et éviter la dégradation de composés thermo- ou UV- fragiles / Despite the first synthesis of stable N-heterocyclic carbene (NHC)-boranes occurring as early as 1993, the widespread exploration of their potential in chemistry truly began only in 2007. The versatility of these stable and easily accessible boron compounds has led to their application in organic reactions (imine reduction, multiple bond hydroboration, radical reductions), organometallic reactions (Suzuki- Miyaura cross coupling) and polymerization (initiation or co-initiation of polymerization). The aim of my project was to extend the applicability of NHC-boranes to two different photopolymerization systems. The first aimed to synthesize polymer matrices containing metal nanoparticles in a one pot, one reactant process. The second aimed to perform emulsion polymerizations initiated by visible light. In the first system, the reductive capacity of NHC-boranes was used to generate gold or silver nanoparticles directly in acrylate monomers. Then, the initiating ability of NHC-boranes was triggered by UV light to form the polymer matrix containing embedded nanoparticles. Characterization by HRTEM showed small nanoparticles (ca. 10 nm) successfully contained within the matrix. This method represents a more straightforward approach than obtaining such materials through the multistep processes already reported in literature. In the second system, NHC-boranes were employed for the first time as co-initiators in visible light initiated emulsion polymerization styrene and methyl methacrylate. Stable latexes were generated with controllable particle sizes at lower surfactant concentrations than those used in related light-initiated systems. Such visible light-triggered initiation systems are interesting for reducing energy consumption and avoiding degradation of heat- or UV-sensitive materials

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