The incorporation of substituted stilbenes in copolymers affects the resulting solution properties and their controlled radical polymerizations. Substituted stilbene monomers readily polymerize in an alternating fashion with acceptor comonomers such as maleic anhydride and maleimide. These sterically crowded polymer backbones are classified as semi-rigid. As this is an uncommon category of polymer backbone rigidity, examples of semi-rigid and rigid polyzwitterions in the literature were reviewed as well as stilbene-containing semi-rigid polymers. Using a deprotection strategy, anionic polyelectrolytes and polyampholytes of stilbene-maleic anhydride copolymers were synthesized and characterized by first synthesizing organic-soluble polymer precursors. Solution shear rheology and statistical segment length measurements reveal that carboxylated polyanions containing stilbene and maleic acid remain semi-rigid in aqueous solutions. It was found that these semi-rigid polyanions exhibited excellent anti-HIV activity possibly due to their more extended polymer chains. This was the first time that intrinsic polymer rigidity was introduced as a possible design parameter for microbicidal applications. Reversible addition fragmentation chain transfer (RAFT) polymerization techniques were used to copolymerize 4-diethylaminostilbene with maleic anhydride. These new semi-rigid copolymers were incorporated into double hydrophilic block copolymers (DHBCS) containing semi-rigid and flexible segments. The subsequent solutions properties of these DHBCs were evaluated with respect to pH and salt responsiveness. Notably, the DHBCs exhibited a "like-charge" attraction as ionic strength increased which was attributed to the semi-rigid character of the polyampholyte block copolymer. / Ph. D.

The advent of microfluidic technology presents many difficulties but also many opportunities for separation science. Leveraging the potential of micro- and nanofluidic geometries is not only a matter of shrinking systems. Miniaturization can shift the relative importance of physical phenomena leading to separation. Theoretical and computational studies into the consequences of miniaturization are vital. Mesoscopic, multi-particle collision dynamics simulations are performed on polyelectrolytes and hard, colloidal solutes. Multiple variations of this simulation algorithm are implemented to achieve versatility for simulating non-equilibrium flows and dispersed solutes. The algorithm is extended to simulate the effects of finite Debye layers on the electro-hydrodynamics of electrophoresing macromolecules and used to study the electrophoresis of charged oligomers, polyelectrolytes and polyampholytes in both free-solution and confined geometries. Multi-particle collision dynamics simulations of hydrodynamic chromatography and field-flow fractionation are also performed to test the predictions of the derived unified, ideal retention theory. This unified, ideal retention predicts the transitions between multiple operational modes, including Faxén-mode FFF. Simulations and the theory show that increases in drag due to hydrodynamic interactions with microfluidic channel walls perturb the retention curves from the ideal predictions at large particle sizes. Further complications to field-flow fractionation including undesirable forces perpendicular to the flow direction, slip at channel walls and rectangular channel geometries are investigated. These theoretical studies lead to the proposal of several novel fractionation techniques, namely adverse-mode FFF, slip-mode FFF and polymer/depletant HC.

Made available in DSpace on 2014-06-11T19:22:54Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-08-01Bitstream added on 2014-06-13T19:49:16Z : No. of bitstreams: 1 valle_rml_me_sjrp.pdf: 866733 bytes, checksum: 903cda2dc88f2ecf24f8cec8bd5ce702 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho utilizamos simulações de Monte Carlo para estudar as propriedades elétricas e conformacionais de polianfóteros fracos, investigando o efeito da estrutura primária, do pH da solução da valência dos contraíons. O polímero foi representado por um conjunto de esferas rígidas conectadas por um potencial harmônico (modelo bead-spring ) e os contraíons da solução, de valência 1, 2 e 3, foram tratados de maneira explícita segundo o modelo primitivo restrito. Todo o sistema foi confinado em uma célula esférica com o polímero fixado em seu centro. Dentre as análises de propriedades elétricas do polianfótero, foi observado que a fração de grupos básicos protonados se aproxima do caso ideal com o aumento da valência dos contraíons, para todas as sequências primárias estudadas. Diferentemente do que ocorre para homopolímeros carregados, nos quais os efeitos de correlação entre contraíons multivalentes provocam alta compactação da cadeia, o raio de giração de polienfóteros com contra ons trivalentes se mostrou muito próximo de cadeias (self-avoiding walk ). Em relação ao efeito da sequência primária, cadeias com baixa carga líquida apresentaram maior compactação nos casos de distribuição de monômero com menor número de blocos, assim como já previsto na literatura utilizando eletrólito implícito através da teoria de Debye-Hückel. A medida que aumentamos o valor de pH, o polinafótero ca carregado e conformações globulares não são mais observadas. Nestas condições, verificamos a formação de estruturas conhecidas como tadpoles apenas utilizando contraíons monovalente. Em nossa análise de Scaling, os valores conhecidos na literatura para o índice v da relação Rg ~ N vm foram obtidos para os casos Alternado (caso SAW) e Dibloco (caso globular) em regimes de pH nos quais a macromolécula está neutra apenas considerando diluição infinita / In this work we use the Monte Carlo simulations to study conformational and electrical properties of weak Polyampholytes and investigate the e ect of the primary structure, pH and the valency of the counterion on these conformations. The polymer was represented by a set of rigid spheres connected by a harmonic potential (bead-spring model) and the counterions of the solution of valency 1, 2 and 3 were treated explicitly according to the restricted primitive model. The system was enclosed in a spherical cell with the polymer set at its center. Among the analysis of electrical properties of the polyampholyte, it was observed that the fraction of protonated basic groups approaches the ideal case with the increase in valency of the counterion for all the primary sequence studied. Di erently from what occurs for homopolymers, in which the e ects of correlation between multivalent counterions cause high compression of the chain, the radius of gyration of polyampholytes considering trivalent counterions is very close to those obtained for Gaussian chains with excluded volume interaction (Self-Avoiding Walk ). Regarding the e ect of primary sequence, chains with low net charge showed higher compression in cases of fewer blocks monomers distribution, as already provided in previous work using implicit counterions by the Debye-H uckel theory. As the pH increased, the polyampholyte has a net charge and globular conformations are no longer observed. Accordingly, we observed the formation of structures known as tadpoles using monovalent counterions. In our analysis of Scaling, the known values for the index (in Rg N m) were obtained for Alternating case (SAW) and Diblock case (globular) in pH regimes in which the macromolecule has no net charge and only considering in nite dilution

The advent of microfluidic technology presents many difficulties but also many opportunities for separation science. Leveraging the potential of micro- and nanofluidic geometries is not only a matter of shrinking systems. Miniaturization can shift the relative importance of physical phenomena leading to separation. Theoretical and computational studies into the consequences of miniaturization are vital. Mesoscopic, multi-particle collision dynamics simulations are performed on polyelectrolytes and hard, colloidal solutes. Multiple variations of this simulation algorithm are implemented to achieve versatility for simulating non-equilibrium flows and dispersed solutes. The algorithm is extended to simulate the effects of finite Debye layers on the electro-hydrodynamics of electrophoresing macromolecules and used to study the electrophoresis of charged oligomers, polyelectrolytes and polyampholytes in both free-solution and confined geometries. Multi-particle collision dynamics simulations of hydrodynamic chromatography and field-flow fractionation are also performed to test the predictions of the derived unified, ideal retention theory. This unified, ideal retention predicts the transitions between multiple operational modes, including Faxén-mode FFF. Simulations and the theory show that increases in drag due to hydrodynamic interactions with microfluidic channel walls perturb the retention curves from the ideal predictions at large particle sizes. Further complications to field-flow fractionation including undesirable forces perpendicular to the flow direction, slip at channel walls and rectangular channel geometries are investigated. These theoretical studies lead to the proposal of several novel fractionation techniques, namely adverse-mode FFF, slip-mode FFF and polymer/depletant HC.

Orientador: Sidney Jurado de Carvalho / Banca: Antonio Caliri / Banca: Jorge Chahine / Resumo: Neste trabalho utilizamos simulações de Monte Carlo para estudar as propriedades elétricas e conformacionais de polianfóteros fracos, investigando o efeito da estrutura primária, do pH da solução da valência dos contraíons. O polímero foi representado por um conjunto de esferas rígidas conectadas por um potencial harmônico (modelo bead-spring ) e os contraíons da solução, de valência 1, 2 e 3, foram tratados de maneira explícita segundo o modelo primitivo restrito. Todo o sistema foi confinado em uma célula esférica com o polímero fixado em seu centro. Dentre as análises de propriedades elétricas do polianfótero, foi observado que a fração de grupos básicos protonados se aproxima do caso ideal com o aumento da valência dos contraíons, para todas as sequências primárias estudadas. Diferentemente do que ocorre para homopolímeros carregados, nos quais os efeitos de correlação entre contraíons multivalentes provocam alta compactação da cadeia, o raio de giração de polienfóteros com contra ons trivalentes se mostrou muito próximo de cadeias (self-avoiding walk ). Em relação ao efeito da sequência primária, cadeias com baixa carga líquida apresentaram maior compactação nos casos de distribuição de monômero com menor número de blocos, assim como já previsto na literatura utilizando eletrólito implícito através da teoria de Debye-Hückel. A medida que aumentamos o valor de pH, o polinafótero ca carregado e conformações globulares não são mais observadas. Nestas condições, verificamos a formação de estruturas conhecidas como tadpoles apenas utilizando contraíons monovalente. Em nossa análise de Scaling, os valores conhecidos na literatura para o índice v da relação Rg ~ N vm foram obtidos para os casos Alternado (caso SAW) e Dibloco (caso globular) em regimes de pH nos quais a macromolécula está neutra apenas considerando diluição infinita / Abstract: In this work we use the Monte Carlo simulations to study conformational and electrical properties of weak Polyampholytes and investigate the e ect of the primary structure, pH and the valency of the counterion on these conformations. The polymer was represented by a set of rigid spheres connected by a harmonic potential (bead-spring model) and the counterions of the solution of valency 1, 2 and 3 were treated explicitly according to the restricted primitive model. The system was enclosed in a spherical cell with the polymer set at its center. Among the analysis of electrical properties of the polyampholyte, it was observed that the fraction of protonated basic groups approaches the ideal case with the increase in valency of the counterion for all the primary sequence studied. Di erently from what occurs for homopolymers, in which the e ects of correlation between multivalent counterions cause high compression of the chain, the radius of gyration of polyampholytes considering trivalent counterions is very close to those obtained for Gaussian chains with excluded volume interaction (Self-Avoiding Walk ). Regarding the e ect of primary sequence, chains with low net charge showed higher compression in cases of fewer blocks monomers distribution, as already provided in previous work using implicit counterions by the Debye-Huckel theory. As the pH increased, the polyampholyte has a net charge and globular conformations are no longer observed. Accordingly, we observed the formation of structures known as tadpoles using monovalent counterions. In our analysis of Scaling, the known values for the index (in Rg N m) were obtained for Alternating case (SAW) and Diblock case (globular) in pH regimes in which the macromolecule has no net charge and only considering in nite dilution / Mestre