Structure and functional study of glycans are highly challenging due to the difficulties in analyzing glycans and limited availability of samples for study. These limitations could be resolved by attaching DNA barcode to the glycan, which virtually represent glycan in further application, by increasing the sensitivity of detection by polymerase chain reaction (PCR), requiring minimal samples for analysis. Assuming bigger arena of DNA Encoded Glycan Libraries (DEGL) in future, we propose here a method for uniquely coding all glycans using computer program that can convert the structural information of glycans to DNA barcode. A unique and universal coding for glycans will benefit both synthesis and analysis of DEGLs. As a proof of principle study, a small DNA Encoded Glycan Library (DEGL) of blood and globo series glycan antigen and its application was demonstrated in detecting blood group and breast cancer from plasma.

Ce travail avait pour but de synthétiser et caractériser des copolymères amphiphiles à base de poly(éthylène glycol) (PEG) et de poly(acide lactique) (PLA) pour la confection de systèmes de délivrance de principes actifs (PA). Les polymères ont été choisis pour leur biocompatibilité et de leur biorésorbabilité. Plusieurs architectures de copolymères amphiphiles ont été créées et leur comportement auto-associatif en milieu aqueux ainsi que leur capacité à encapsuler des principes actifs ont été étudiés. Tout d'abord, un copolymère greffé a été synthétisé par copolymérisation d'un monomère fonctionnel, le glycolide monopropargylé, avec du L-lactide pour obtenir un squelette polyester fonctionnel sur lequel des branches hydrophiles de PEG ont été greffés avec plusieurs degrés de substitution. Ensuite, un copolymère peigne tribloc a été synthétisé à partir d'un bloc central PLA dont les extrémités de chaînes ont été modifiées pour permettre l'amorçage de la polymérisation de méthacrylate d'oligo(éthylène glycol) avec des taux de substitution variables. L'étude de l'auto-assemblage et de la capacité à encapsuler des PA a révélé que l'architecture et la balance hydrophile/hydrophobe sont des facteurs déterminants pour la nature des objets formés et leur potentiel d'encapsulation. Enfin, des stratégies de fonctionnalisation ont été mises en place afin d'augmenter et de moduler l'efficacité des PA encapsulés. Ceci est illustré par le couplage d'une molécule fluorescente modèle et, dans le cadre d'une collaboration, par la conjugaison d'un peptide immunostimulateur sur un système dibloc amphiphile. La comparaison à d'autres formulations a montré que le conjugué permettait de moduler et renforcer l'efficacité du PA utilisé. / The objective of this work was to synthesize and characterize amphiphilic copolymers based on poly(ethylene glycol) (PEG) and poly(lactic acid) (PLA) intended for drug delivery applications. The polymers were chosen regarding to their biocompatibility and bioresorbability. Different architectures of amphiphilic copolymers were prepared, and their behavior in aqueous media, as well as their abilities to encapsulate drugs were studied. First, a graft copolymer was synthesized through copolymerization of a functional monomer, monopropargylated glycolide, with L-lactide to yield a functionalized polyester backbone. The latter was then grafted with different densities of hydrophilic branches of PEG. Then, a brush-like triblock copolymer was synthesized through ROP and ATRP. To this end, chain ends of a telechelic block of PLA were modified to yield a macroinitiator able to initiate oligo(ethylene glycol) methacrylate polymerization with variable substitution degrees. Self-assembly and drug loading studies revealed that architecture and hydrophobic/hydrophilic balance played a major role on the nature of the formed objects and on their encapsulation potential. Finally, to modulate and increase the efficacy of encapsulated drugs, functionalization strategies were realized. This is illustrated by the linking of a fluorescent model molecule on a triblock brush-like copolymer and, in a collaboration project, the linking of an immunostimulant peptide on an amphiphilic diblock system. Comparison with other formulations revealed that the conjugate allowed modulating and reinforcing the drug's efficacy.

Pay per click (PPC) advertising over the past few years has gained importance and companies invest larger amounts of money into it. There are more PPC systems in the market from which to choose for advertising. Which PPC system is appropriate to use for a specific campaign? This thesis consists of four chapters (excluding introduction and conclusion). The first chapter clarifies terms, talks about the basic characteristics of the subject and gives an idea of the importance of the topic (position of pay per click in the market of internet advertising). The second chapter characterizes three PPC systems (and their principles) which the author considers to be the most important in the Slovak market. The third chapter is important for the characterisation of different types of PPC campaigns. In it the author used his own classification of PPC campaigns. Two case studies are analysed in the fourth chapter. According to them an evaluation of the suitability of selected PPC systems is made (using induction method). The first three chapters are based on an analysis of available literature, the fourth part on the author's own experiences.

L'objectif de ces travaux était d'utiliser certains aspects de l'activité chimique et photochimique de télomères fluorés porteurs de fonctions azides, dans le but de promouvoir les synthèses de polymères thermostables et de nouveaux matériaux photoréticulés. En premier lieu, nous avons développé et caractérisé une nouvelle classe de poly(alkyl-aryl) éthers par une promotion de la compétition de la réaction de « Click » et de couplage de Hay. Par la suite, l'activité photochimique de ces composés fluorés a été étudiée et utilisée pour élaborer des matériaux photoréticulés. Les énergies libres des surfaces des films obtenus ont été calculées en utilisant le modèle d'Owens et Wendt. Les rugosités et les compositions de ces surfaces présentant des mouillabilités singulières ont été investiguées par le biais d'analyses par profilométrie, AFM et EDX. En dernier lieu, les synthèses et caractérisations de réseaux photoréticulés sont abordées. La post sulfonation de ces matériaux a conduit à la préparation de nouveaux électrolytes pour l'application pile à combustible dont les microstructures et propriétés physico-chimiques ont été étudiées. / This work aims at using both chemical and photochemical activities of fluorinated telomers bearing azido end groups, to promote the synthesis of thermostable macromolecules and original photocrosslinked networks. In a first part, we have prepared and characterized a novel class of linear poly(alkyl aryl) ethers by the promotion of competitive “Click” reaction and Hay coupling. Then, the photolysis under UV irradiation of these fluorinated polymers was studied and used to generate photocrosslinked materials. The surface free energies of the resulting films were established using the Owens-Wendt model. The roughness and composition of the surfaces were investigated by profilometry, AFM and EDX analysis. Finally, the preparation under UV irradiation of original polymer networks was performed. The post-sulfonation of these materials allowed to prepare new proton exchange membranes for fuel cells application. The microstructures, physical and chemical properties of these electrolytes were investigated.

Natural compounds have been the primary resource used to produce polymeric materials by humankind since the mid-1900s. Yet, progress in bio-based polymers from renewable feedstock has encountered some obstacles, mainly due to the low prices of petroleum-based monomers, compared to natural and sustainable materials. However, most commodity plastics are non-degradable materials, and solid plastic waste accumulation adversely affects the environment. As the world population is growing and demanding chemicals, energy, and plastics materials, polymer research is focusing on synthesizing bio-based and degradable polymers. Thus, biomass, a sustainable and inexpensive feedstock, is highly appropriate for designing alternative thermoplastics that are degradable to reduce the current environmental issues. In this dissertation, three different approaches were used to afford alternative thermoplastics to petroleum‐based commodities: bio-based poly(ether-amide)s, random aromatic copolyesters, and copoly(acetal triazole)s. In our first approach, two new lignin‐derived poly(ether‐amide)s (PEA)s were prepared. Their thermal properties showed high degradation temperature (Td) ranging from 330 °C to 380 °C, and glass transition temperature (Tg) between 100 °C and 120 °C. The chemical degradation studies revealed that the PEAs were degradable in 4 M H2SO4, HNO3, and TFA in 3 days. The second polymer group synthesized were semicrystalline bio-based aromatic copolyesters with tunable thermal properties. The thermal analysis of these copolyesters revealed high Td (413 °C to 446 °C) and Tg and Tm ranging from –36 °C to 67 °C and 60 °C to 267 °C, respectively. Their crystallization behavior showed a dependence on the comonomer composition, exhibiting a pseudo-eutectic region. Finally, furfural- and benzaldehyde-based copoly(acetal triazole)s (Td range 280–340 °C) were prepared by click polymerization at room temperature. Preliminary results showed that furfural-based copoly(acetal triazole)s were susceptible to hydrolytic degradation under neutral conditions after only 8 days at 40 °C. Overall, degradable and bio-based polymers were successfully synthesized as a potential thermoplastic alternative for packaging applications.

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Oligosaccharides play very crucial biological roles in the human body. They are structurally diverse and very challenging to analyze. In an attempt to contribute towards the analysis of oligosaccharides in the growing filed of 'Glycomics', we explored different ways to make novel efficient oligosaccharide tags to label N -linked oligosaccharides from glycoproteins. We synthesized and characterized various oligosaccharide tags which are useful to analyze the oligosaccharide by mass spectrometry, HPLC, and bioaffinity. In these tags we incorporated ar UV/fluorescent core, a biotin moiety and an amino/azido/alkyne terminus. We varied the structures of the tags for improved solubility in common organic solvents. These tags were used to label standard oligosaccharides, and the labeling efficiency was evaluated.

I performed the role of Brick Pollitt at Lake Mirror Theatre in Lakeland, Florida from April 20- April 30 2006. The role of Brick Pollitt provided me with several acting challenges as well as multiple subjects to research. The most challenging aspects of portraying the character of Brick Pollitt are his alcoholism, issues of sexuality, and tormented familial relationships. Brick Pollitt journeys in the period of one day through major challenges in two key relationships. He moves from dominance in his relationship with Maggie to capitulation and from isolation in his relationship with Big Daddy to mutual understanding. Brick's relationships are further complicated by questions surrounding his recently deceased best friend Skipper and drives (alcoholism) that may be perceived as self destructive. My preliminary work has led me to believe Brick is in search of peace ('the click') in a tormented life (Williams, Cat 2.47). The nature of the torment needs further research for definition. Some critics argue Brick's sexuality is ambivalent, and he is repressing homosexual drives. Equally possible is arguing the homosexuality was restricted to Skipper. Making a decision about the definition of this relationship is key to making choices within the play because the friendship was so important to Brick's perception of himself. Brick believed his relationship was the "one true and pure thing" in a life filled with "mendacity" (Williams, Cat 2.50). 'Mendacity' is Bricks reference to his disgust with "lyin' an' liars' (Williams, Cat 2.50-51). He is lost without this anchor for his life and it has impacted his ability to interact with the world around him. Determining Brick's sexuality in my portrayal will be central to my process while I also embrace research into related areas of behavior. To supplement my research of alcoholism and Brick's sexuality, the following topics: -A Psycho-Analytical study of the character Brick Pollitt and his "archetypal" relationships with Maggie, Big Daddy, Skipper, Gooper, and his place in society. -The evolution of the character Brick Pollitt through various scripts and screenplays. From Williams's first script through to dealing with the Hays Code. A study of Tennessee Williams life history and the influence on the play. -The history of Cat on a Hot Tin Roof from its Morosco Theatre Broadway debut in New York City on March 24, 1955, followed by its film release in 1955 starring Paul Newman, Burl Ives, and Elizabeth Taylor. Any successful portrayal of Brick Pollitt in Cat on a Hot Tin Roof demands intense focus to individual relationships within the ensemble. The central theme of the play is 'mendacity' (deceit) (Williams, Cat 2.50). Brick uses this word to describe his disgust, but the 'mendacity' of his human relations in the aging and decaying Southern society is what troubles him (Williams, Cat 2.50). Discovering the ties between family, 'mendacity', and society are relevant to the execution of the play (Williams, Cat 2.50). I believe depiction of Brick Pollitt in this Pulitzer Prize winning American Classic will best present my abilities achieved in the Master of Fine Arts Program

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