.

The biological function of a protein is determined by its amino acid sequence, structure, and internal dynamics. In turn the prediction of a protein structure from its folding pathway involves the characterization of the dynamics of the polypeptide backbone. This study addresses how the internal dynamics of arborescent polypeptides are affected by increased crowding of the interior of these branched polymer molecules. Linear, comb-branched, and arborescent poly(L-glutamic acid) (PGA) samples were analyzed by 1H NMR spectroscopy to determine their chain conformation. The PGA chains of these constructs were shown to adopt α-helical and random coil conformations in N,N-dimethylformamide (DMF) and in dimethyl sulfoxide (DMSO), respectively. The hydrodynamic diameter (Dh) of the arborescent PGAs, determined using dynamic light scattering measurements, increased with increasing generation number and when the side-chains adopted random coil instead of α-helical conformations. The PGA samples were labelled with 1-pyrenemethylamine to determine how their structure affected the internal dynamics of the arborescent polymers in solution, from the analysis of their fluorescence spectra and decays. For each pyrene-labelled polymeric construct excimer formation increased with increasing pyrene content, and the efficiency of excimer formation increased with the generation number due to the increased density of the macromolecules. Comparison of the time-resolved fluorescence results acquired in DMF and in DMSO demonstrated that the helical conformation led to slower chain dynamics in DMF and that despite the higher viscosity of DMSO, the polypeptide side-chains were more mobile as a consequence of the random coil conformation of the linear PGA segments. These results suggest that the formation of structural motives inside a polypeptide slows down its internal dynamics.

The research presented focused on the synthesis and the characterization of graft polymers, of interest either as model systems or for large-scale applications. The materials selected as substrates for grafting reactions were carbosilane dendrimers, linear and branched polystyrenes, and cross-linked polystyrene latex particles. The synthesis of dendrimer-arborescent polymer hybrids was thus achieved by derivatization of the carbosilane dendrimers with dichlorosilane moieties and coupling with 1,4-polybutadiene side chains with Mn ≈ 1000. A second derivatization and coupling reaction with Mn ≈ 1500, 5000, or 30000 side chains yielded hybrid polymers with narrow molecular weight distributions (Mw/Mn ≤ 1.16). In the second part of the thesis, a procedure for the large-scale (100-g) synthesis of arborescent styrene homopolymers and copolymers incorporating poly(2-vinylpyridine) segments is presented. End-capping of the polystyryllithium chains with 1,1-diphenylethylene in the presence of LiCl, followed by the addition of 3 – 6 equivalents of 2-vinylpyridine per side chain, eliminated side reactions and led to grafting yields of up to 95 %. A systematic investigation of the solution properties of polyelectrolytes obtained by protonation of the poly(2-vinylpyridine) arborescent copolymers with a strong acid (trifluoroacetic acid) is also presented. The relative importance of the electrostatic repulsion and the elastic deformation forces on molecular expansion was investigated by examining the solution properties of the copolymers as a function of structure, protonation level, and the presence of salts in polar solvents (methanol, DMF, H2O). The viscosity of the arborescent copolymer solutions was also found to be much lower than for linear P2VP samples under the same conditions. In the last part of the thesis, the synthesis of model filler particles was achieved by grafting polyisoprene chains onto cross-linked polystyrene latex particles derivatized with acetyl coupling sites. These substrates, which can be viewed as an extreme case of a dense (hard-sphere) arborescent polymer structure, were used to investigate the influence of filler-matrix polymer interactions on the rheological behavior of filled polyisoprene samples. The influence of the filler structure on the rheological behavior of the blends was examined by dynamic mechanical analysis in terms of frequency-dependent complex viscosity, storage modulus, and damping factor. All the blends exhibited enhanced complex viscosity, storage modulus, and decreased damping factor values relative to the matrix polymer.

The research presented focused on the synthesis and the characterization of graft polymers, of interest either as model systems or for large-scale applications. The materials selected as substrates for grafting reactions were carbosilane dendrimers, linear and branched polystyrenes, and cross-linked polystyrene latex particles. The synthesis of dendrimer-arborescent polymer hybrids was thus achieved by derivatization of the carbosilane dendrimers with dichlorosilane moieties and coupling with 1,4-polybutadiene side chains with Mn ≈ 1000. A second derivatization and coupling reaction with Mn ≈ 1500, 5000, or 30000 side chains yielded hybrid polymers with narrow molecular weight distributions (Mw/Mn ≤ 1.16). In the second part of the thesis, a procedure for the large-scale (100-g) synthesis of arborescent styrene homopolymers and copolymers incorporating poly(2-vinylpyridine) segments is presented. End-capping of the polystyryllithium chains with 1,1-diphenylethylene in the presence of LiCl, followed by the addition of 3 – 6 equivalents of 2-vinylpyridine per side chain, eliminated side reactions and led to grafting yields of up to 95 %. A systematic investigation of the solution properties of polyelectrolytes obtained by protonation of the poly(2-vinylpyridine) arborescent copolymers with a strong acid (trifluoroacetic acid) is also presented. The relative importance of the electrostatic repulsion and the elastic deformation forces on molecular expansion was investigated by examining the solution properties of the copolymers as a function of structure, protonation level, and the presence of salts in polar solvents (methanol, DMF, H2O). The viscosity of the arborescent copolymer solutions was also found to be much lower than for linear P2VP samples under the same conditions. In the last part of the thesis, the synthesis of model filler particles was achieved by grafting polyisoprene chains onto cross-linked polystyrene latex particles derivatized with acetyl coupling sites. These substrates, which can be viewed as an extreme case of a dense (hard-sphere) arborescent polymer structure, were used to investigate the influence of filler-matrix polymer interactions on the rheological behavior of filled polyisoprene samples. The influence of the filler structure on the rheological behavior of the blends was examined by dynamic mechanical analysis in terms of frequency-dependent complex viscosity, storage modulus, and damping factor. All the blends exhibited enhanced complex viscosity, storage modulus, and decreased damping factor values relative to the matrix polymer.

The biological function of a protein is determined by its amino acid sequence, structure, and internal dynamics. In turn the prediction of a protein structure from its folding pathway involves the characterization of the dynamics of the polypeptide backbone. This study addresses how the internal dynamics of arborescent polypeptides are affected by increased crowding of the interior of these branched polymer molecules. Linear, comb-branched, and arborescent poly(L-glutamic acid) (PGA) samples were analyzed by 1H NMR spectroscopy to determine their chain conformation. The PGA chains of these constructs were shown to adopt α-helical and random coil conformations in N,N-dimethylformamide (DMF) and in dimethyl sulfoxide (DMSO), respectively. The hydrodynamic diameter (Dh) of the arborescent PGAs, determined using dynamic light scattering measurements, increased with increasing generation number and when the side-chains adopted random coil instead of α-helical conformations. The PGA samples were labelled with 1-pyrenemethylamine to determine how their structure affected the internal dynamics of the arborescent polymers in solution, from the analysis of their fluorescence spectra and decays. For each pyrene-labelled polymeric construct excimer formation increased with increasing pyrene content, and the efficiency of excimer formation increased with the generation number due to the increased density of the macromolecules. Comparison of the time-resolved fluorescence results acquired in DMF and in DMSO demonstrated that the helical conformation led to slower chain dynamics in DMF and that despite the higher viscosity of DMSO, the polypeptide side-chains were more mobile as a consequence of the random coil conformation of the linear PGA segments. These results suggest that the formation of structural motives inside a polypeptide slows down its internal dynamics.

No description available.

La version intégrale de cette thèse est disponible uniquement pour consultation individuelle à la Bibliothèque de musique de l’Université de Montréal (http://www.bib.umontreal.ca/MU). / Cette thèse de doctorat comprend l’analyse, les partitions et les enregistrements sonores de plusieurs compositions musicales écrites et improvisées qui furent enregistrées au cours des années 2009 et 2010. Elle vise le développement des éléments de détermination d’un langage musical personnel. Pour ce faire, divers outils furent mis en place, tels que le développement d’un système mélodico harmonique flexible et l’expansion de la palette sonore du vibraphone, grâce à la maîtrise du bending tone. Le corps de cet ouvrage se divise donc en deux parties consacrées à l’élaboration du système de superposition arborescente et à l’aspect soliste recherchant la flexibilité, la virtuosité et l’élargissement des possibilités liées au son de cet instrument de musique. Les concepts élaborés sont appuyés par des illustrations, des références aux partitions et des exemples musicaux ciblés de type jazz et de type classique occidental. / This doctoral thesis involves the analysis, scores and sound recordings of several composed and improvised musical compositions recorded during the years 2009 – 2010. Its main objective is the development of elements determining a personal musical language. To achieve this objective, different tools were put in place such as the development of a flexible harmonic and melodic system and the expansion of the multitude of sound effects of the vibraphone, both achieved by mastering the “bending tone”. The body of this document is divided in two parts devoted to the elaboration of a system of superposition of the different changes that can be brought to the core element and the aspect of the soloist searching for flexibility, virtuosity and the diversity of sounds linked to this particular instrument. The concepts elaborated are supported by illustrations, score references and targeted musical examples including jazz and western classical styles.

Graft copolymers with a dendritic (arborescent) architecture and unimolecular micelle properties have been synthesized and examined for their solution properties as well as their ability to serve as templates for the preparation of metallic nanoparticles. The research focused on two types of arborescent copolymers, namely core-shell (CS) and core-shell-corona (CSC) architectures. Copolymer amphipolarity was provided by a hydrophobic polystyrene (PS) component and a polar poly(2-vinylpyridine), P2VP, phase. The CS copolymers were obtained by grafting P2VP onto linear or branched PS substrates to yield PS-g-P2VP unimolecular micelles. These copolymers exhibited solubility with limited aggregation in aqueous environments after protonation with HCl. Coordination of the coronal P2VP phase with HAuCl4 was achieved, and the resulting polymer-stabilized metallic nanoparticles had a spherical morphology. The tri-layered copolymers were synthesized in similar fashion, by grafting PS-b-P2VP block copolymers onto linear or branched PS substrates to afford a CSC morphology with a PS core, a P2VP inner shell, and a PS corona. While the grafting reaction proceeded with lower than expected grafting yields as compared to grafting reactions of homopolymer side-chains, significant P2VP content and molecular weight increases were achieved. It was determined that aggregation of the block copolymer side-chains hindered the coupling reaction of the reactive centers with the substrate. After purification of the PS-g-(P2VP-b-PS) arborescent copolymers, in part by developing a cloud-point centrifugation purification technique, the spherical copolymers were successfully loaded with various metallic compounds. The uptake of compounds such as HAuCl4 by the P2VP phase of the copolymers induced intramolecular phase segregation for copolymers of generations (G) 2 and above. Phase segregation produced some unique and intricate morphologies different from the ones observed previously for other unimolecular metal scaffolds. Intramolecular toroidal, nodular, and cylindrical morphologies were observed for the G2, G3, and G4 arborescent copolymers, respectively. Templates of generations 0 and 1 displayed a spherical morphology similar to their PS-b-P2VP intermolecular micelle analogues when loaded with metals. Phase segregation is believed to be mediated mainly by the characteristics of the PS core, the length of the P2VP segments having less influence on the morphologies obtained. Reduction of the metallic salts was performed using various agents and protocols. Stronger reducing agents yielded smaller and more narrowly distributed gold nanoparticles, while other reduction methods also removing the polymer scaffold resulted in larger nanoparticles.

Graft copolymers with a dendritic (arborescent) architecture and unimolecular micelle properties have been synthesized and examined for their solution properties as well as their ability to serve as templates for the preparation of metallic nanoparticles. The research focused on two types of arborescent copolymers, namely core-shell (CS) and core-shell-corona (CSC) architectures. Copolymer amphipolarity was provided by a hydrophobic polystyrene (PS) component and a polar poly(2-vinylpyridine), P2VP, phase. The CS copolymers were obtained by grafting P2VP onto linear or branched PS substrates to yield PS-g-P2VP unimolecular micelles. These copolymers exhibited solubility with limited aggregation in aqueous environments after protonation with HCl. Coordination of the coronal P2VP phase with HAuCl4 was achieved, and the resulting polymer-stabilized metallic nanoparticles had a spherical morphology. The tri-layered copolymers were synthesized in similar fashion, by grafting PS-b-P2VP block copolymers onto linear or branched PS substrates to afford a CSC morphology with a PS core, a P2VP inner shell, and a PS corona. While the grafting reaction proceeded with lower than expected grafting yields as compared to grafting reactions of homopolymer side-chains, significant P2VP content and molecular weight increases were achieved. It was determined that aggregation of the block copolymer side-chains hindered the coupling reaction of the reactive centers with the substrate. After purification of the PS-g-(P2VP-b-PS) arborescent copolymers, in part by developing a cloud-point centrifugation purification technique, the spherical copolymers were successfully loaded with various metallic compounds. The uptake of compounds such as HAuCl4 by the P2VP phase of the copolymers induced intramolecular phase segregation for copolymers of generations (G) 2 and above. Phase segregation produced some unique and intricate morphologies different from the ones observed previously for other unimolecular metal scaffolds. Intramolecular toroidal, nodular, and cylindrical morphologies were observed for the G2, G3, and G4 arborescent copolymers, respectively. Templates of generations 0 and 1 displayed a spherical morphology similar to their PS-b-P2VP intermolecular micelle analogues when loaded with metals. Phase segregation is believed to be mediated mainly by the characteristics of the PS core, the length of the P2VP segments having less influence on the morphologies obtained. Reduction of the metallic salts was performed using various agents and protocols. Stronger reducing agents yielded smaller and more narrowly distributed gold nanoparticles, while other reduction methods also removing the polymer scaffold resulted in larger nanoparticles.

No description available.