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.

Yes / This paper outlined our method for developing polymer-linked contact lens type materials for rapid detection and differentiation of Gram-positive, Gram-negative bacteria and fungi in infected corneas. It can be applied to both model synthetic or ex-vivo corneal models and has been successfully trialed in an initial efficacy tested animal study. First a hydrogel substrate for the swab material is selected, we have demonstrated selective swabs using a glycerol monomethacrylate hydrogel. Alternatively any commercial material with carboxylic acid functional groups is suitable but risks nonspecific adhesion. This is then functionalised via use of N-hydroxysuccinimide reaction with amine groups on the specified highly branched polymer ligand (either individually gram negative, gram positive or fungal binding polymers or a combination of all three can be employed for desired sensing application). The hydrogel is then cut into swabs suitable for sampling, used, and then the presence of gram positive, game negative and fungi are disclosed by the sequential addition of dyes (fluorescent vancomycin, fluorescein isothiocyanate and calcofluor white). In summary this method presents: Method to produce glycerol monomethacrylate hydrogels to minimize nonspecific binding Methods of attaching pathogen binding highly branched polymers to produce selective hydrogel swabs Method for disclosing bound pathogens to this swab using sequential dye addition

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Die Charakterisierung von verzweigten Polymeren stellt eine große Herausforderung dar. In dieser Arbeit wurden zum einen die Asymmetrische Fluss-Feldflussfraktionierung (AF4) als Alternative zur Größenausschlusschromatographie angewandt, um dendritische Polymere zu charakterisieren. Dabei wurden erstmals auch Komplexierungs-und Aggregationsstudien von dendritischen Glykopolymeren durchgeführt. Weiterhin ist es mittels Adaption der Phasenverteilungschromatographie gelungen, in Abhängigkeit des Verzweigungscharakters aufzutrennen. Hierbei konnten lineare und sternförmige Polystyrenproben separiert werden.

Die Charakterisierung von verzweigten Polymeren stellt eine große Herausforderung dar. In dieser Arbeit wurden zum einen die Asymmetrische Fluss-Feldflussfraktionierung (AF4) als Alternative zur Größenausschlusschromatographie angewandt, um dendritische Polymere zu charakterisieren. Dabei wurden erstmals auch Komplexierungs-und Aggregationsstudien von dendritischen Glykopolymeren durchgeführt. Weiterhin ist es mittels Adaption der Phasenverteilungschromatographie gelungen, in Abhängigkeit des Verzweigungscharakters aufzutrennen. Hierbei konnten lineare und sternförmige Polystyrenproben separiert werden.

Title: The study of the association behaviour of the amphiphilic copolymers in solutions containing low molar compounds by means of computer simulations. Author: Mgr. Karel Šindelka Department: Faculty of Science, Charles University Supervisor: Doc. Ing. Zuzana Limpouchová, Csc. Abstract This doctoral thesis focuses on the study of electrostatic self- and co-assembly in complex polymer solutions containing polyelectrolyte (PE) block copolymers together with surfactants, neutral homopolymers, or oppositely charged PEs using the dissipative particle dynamics (DPD). It was shown that the electro- static self-assembly depends not only on the cooperative interactions of oppo- sitely charged PE chains, but also on the amphiphilicity of PE species or on the polymer block compatibility, among other properties. PEs with incompatible blocks create well-defined core-shell structures, while large ill-defined crew-cut aggregates form from PEs with compatible blocks In non-stoichiometric mixtures of PEs with incompatible blocks, co-assembled nanoparticles are smaller than in stoichiometric mixtures and are charged. The destabilization of larger aggregates depends on how the PE charge surplus is introduced: the effect is strongest when the density of the surplus PE charge on the PE chains is increased and weakest when the...

Estudamos o diagrama de fases e o ponto tricrítico da transição de colapso em um modelo de animais na rede quadrada, a partir da expansão em série da compressibilidade isotérmica KT do sistema. Como função das variáveis x (fugacidade) e y = e1/T (T é a temperatura reduzida), a serie KT é analisada utilizando-se a técnica dos aproximantes diferenciais parciais. Determinamos o padrão de fluxo das trajetórias características de um típico aproximante diferencial parcial com ponto fixo estável. Obtemos estimativas satisfatórias para a fugacidade tricrítica Xt = 0.024 &#177 0.005 e a temperatura tricritica Tt = 0.54 &#177 0.04. Considerando somente campos de escala lineares, obtemos também o expoente de escala &#947 = 1.4 &#177 0.2 e o expoente \"crossover\" &#934 = 0.66 &#177 0.08. Nossos resultados estão em boa concordância com estimativas prévias obtidas por outros métodos. Também estudamos um processo de polimerização ramifIcada através de simulações computacionais na rede quadrada baseadas em um modelo de crescimento cinético generalizado para se incorporar ramifIcações e impurezas. A configuração do polímero e identificada com uma árvore-ligação (\"bond tree\") a fim de se examinar os aspectos topológicos. As dimensões fractais dos aglomerados (\"clusters\") são obtidas na criticalidade. As simulações também permitem o estudo da evolução temporal dos aglomerados bem como a determinação das auto-correlações temporais e expoentes críticos dinâmicos. Com relação aos efeitos de tamanho finito, uma técnica de cumulantes de quarta ordem e empregada para se estimar a probabilidade de ramificação critica bc e os expoentes críticos v e &#946. Na ausência de impurezas, a rugosidade da superfície e descrita em termos dos expoentes de Hurst. Finalmente, simulamos este modelo de crescimento cinético na rede quadrada utilizando um método de Monte Carlo para estudar a polimerização ramificada com interações atrativas de curto alcance entre os monômeros. O diagrama de fases que separa os regimes de crescimento finito e infinito e obtido no plano (T,b) (T é a temperatura reduzida e b é a probabilidade de ramificação). No limite termodinâmico, extrapolamos a temperatura T&#8727 = 0.102 &#177 0.005 abaixo da qual a fase e sempre infinita. Observamos também a ocorrência de uma transição de rugosidade na superfície do polímero. / The phase diagram and the tricritical point of a collapsing lattice animal are studied through an extended series expansion of the isothermal compressibility KT on a square lattice. As a function of the variables x (fugacity) and y = e1/T (T is the reduced temperature), this series KT is investigated using the partial differential approximants technique. The characteristic flow pattern of partial differential approximant trajectories is determined for a typical stable fixed point. We obtain satisfactory estimates for the tricritical fugacity Xt = 0.024 &#177 0.005and temperature Tt = 0.54 &#177 0.04.Taking into account only linear scaling fields we are also able to get the scaling exponent &#947 = 1.4 &#177 0.2 and the crossover exponent &#934 = 0.66 &#177 0.08. Our results are in good agreement with previous estimates from other methods. We also study ramified polymerization through computational simulations on the square lattice of a kinetic growth model generalized to incorporate branching and impurities. The polymer configuration is identified with a bond tree in order to examine its topology. The fractal dimensions of clusters are obtained at criticality. Simulations also allow the study of time evolution of clusters as well as the determination of time autocorrelations and dynamical critical exponents. In regard to finite size effects, a fourth-order cumulant technique is employed to estimate the critical branching probability be and the critical exponents v and &#946. In the absence of impurities, the surface roughness is described in terms of the Hurst exponents. Finally we simulate this kinetic growth model on the square lattice using a Monte Carlo approach in order to study ramified polymerization with short distance attractive interactions between monomers. The phase boundary separating finite from infinite growth regimes is obtained in the (T,b) space (T is the reduced temperature and b is the branching probability). In the thermodynamic limit, we extrapolate the temperature T = 0.102 &#177 0.005 below which the phase is found to be always infinite. We also observe the occurrence of a roughening transition at the polymer surface.

Estudamos o diagrama de fases e o ponto tricrítico da transição de colapso em um modelo de animais na rede quadrada, a partir da expansão em série da compressibilidade isotérmica KT do sistema. Como função das variáveis x (fugacidade) e y = e1/T (T é a temperatura reduzida), a serie KT é analisada utilizando-se a técnica dos aproximantes diferenciais parciais. Determinamos o padrão de fluxo das trajetórias características de um típico aproximante diferencial parcial com ponto fixo estável. Obtemos estimativas satisfatórias para a fugacidade tricrítica Xt = 0.024 &#177 0.005 e a temperatura tricritica Tt = 0.54 &#177 0.04. Considerando somente campos de escala lineares, obtemos também o expoente de escala &#947 = 1.4 &#177 0.2 e o expoente \"crossover\" &#934 = 0.66 &#177 0.08. Nossos resultados estão em boa concordância com estimativas prévias obtidas por outros métodos. Também estudamos um processo de polimerização ramifIcada através de simulações computacionais na rede quadrada baseadas em um modelo de crescimento cinético generalizado para se incorporar ramifIcações e impurezas. A configuração do polímero e identificada com uma árvore-ligação (\"bond tree\") a fim de se examinar os aspectos topológicos. As dimensões fractais dos aglomerados (\"clusters\") são obtidas na criticalidade. As simulações também permitem o estudo da evolução temporal dos aglomerados bem como a determinação das auto-correlações temporais e expoentes críticos dinâmicos. Com relação aos efeitos de tamanho finito, uma técnica de cumulantes de quarta ordem e empregada para se estimar a probabilidade de ramificação critica bc e os expoentes críticos v e &#946. Na ausência de impurezas, a rugosidade da superfície e descrita em termos dos expoentes de Hurst. Finalmente, simulamos este modelo de crescimento cinético na rede quadrada utilizando um método de Monte Carlo para estudar a polimerização ramificada com interações atrativas de curto alcance entre os monômeros. O diagrama de fases que separa os regimes de crescimento finito e infinito e obtido no plano (T,b) (T é a temperatura reduzida e b é a probabilidade de ramificação). No limite termodinâmico, extrapolamos a temperatura T&#8727 = 0.102 &#177 0.005 abaixo da qual a fase e sempre infinita. Observamos também a ocorrência de uma transição de rugosidade na superfície do polímero. / The phase diagram and the tricritical point of a collapsing lattice animal are studied through an extended series expansion of the isothermal compressibility KT on a square lattice. As a function of the variables x (fugacity) and y = e1/T (T is the reduced temperature), this series KT is investigated using the partial differential approximants technique. The characteristic flow pattern of partial differential approximant trajectories is determined for a typical stable fixed point. We obtain satisfactory estimates for the tricritical fugacity Xt = 0.024 &#177 0.005and temperature Tt = 0.54 &#177 0.04.Taking into account only linear scaling fields we are also able to get the scaling exponent &#947 = 1.4 &#177 0.2 and the crossover exponent &#934 = 0.66 &#177 0.08. Our results are in good agreement with previous estimates from other methods. We also study ramified polymerization through computational simulations on the square lattice of a kinetic growth model generalized to incorporate branching and impurities. The polymer configuration is identified with a bond tree in order to examine its topology. The fractal dimensions of clusters are obtained at criticality. Simulations also allow the study of time evolution of clusters as well as the determination of time autocorrelations and dynamical critical exponents. In regard to finite size effects, a fourth-order cumulant technique is employed to estimate the critical branching probability be and the critical exponents v and &#946. In the absence of impurities, the surface roughness is described in terms of the Hurst exponents. Finally we simulate this kinetic growth model on the square lattice using a Monte Carlo approach in order to study ramified polymerization with short distance attractive interactions between monomers. The phase boundary separating finite from infinite growth regimes is obtained in the (T,b) space (T is the reduced temperature and b is the branching probability). In the thermodynamic limit, we extrapolate the temperature T = 0.102 &#177 0.005 below which the phase is found to be always infinite. We also observe the occurrence of a roughening transition at the polymer surface.