O presente estudo demonstrou que a formação de cavidades (breath figures) em filmes de CA, CAPh, CAB e CMCAB preparados por spin-coating de soluções em tetrahidrofurano (THF) foi dependente das características moleculares dos polímeros quando preparados em ambiente com umidade relativa baixa (UR 35%), enquanto que em UR mais elevadas (55% e 75%) o balanço entre a energia superficial da água, THF e energia interfacial entre água e THF foi determinante. Por outro lado, a rápida exposição (de 3 a 6 min) desses filmes ao vapor de solvente teve um efeito plastificante tornando os filmes de CAB, CAPh e CMCAB completamente lisos, enquanto que para filmes de CA foi observado o efeito dewetting. Surfactantes biocompatíveis à base de sorbitano (Tween®) foram usados como plastificantes para filmes de ésteres de celulose obtidos por evaporação de solvente. O comportamento térmico dos filmes foi dependente do tamanho da cauda hidrofóbica do surfactante, do tipo do grupo lateral dos polímeros e da composição da mistura. Tween 20 e 40 mostraram agir como um excelente plastificante para os ésteres de celulose, exceto para o CA, no qual foi imiscível. Teores baixos de Tween favoreceram a flexibilidade das cadeias de polímeros ao passo que quantidades maiores aumentaram a mobilidade molecular dos ésteres de celulose levando a variações de Tg de até 200 °C. Filmes de nanocompósitos de CAB reforçados com nanocristais de celulose (CNC) modificados com diferentes grupos funcionais (acetato e metiladipoíla) foram preparados a partir de dispersões em acetato de etila (AE), THF e N,N-dimetilformamida (DMF). A melhor estabilidade coloidal foi verificada em DMF, devido sua alta polaridade. Suspensões em AE e THF de CNC modificados foram mais estáveis do que CNC por conta das interações entre grupos substituintes e solventes. As propriedades mecânicas dos nanocompósitos, resultantes da dispersibilidade de nanocristais na matriz de CAB mostraram forte relação com a estabilidade coloidal das dispersões. Beads de celulose foram obtidos utilizando polpa pré-tratada de eucalipto, oxidados e utilizados como suporte para incorporação de um agente bactericida QPVP-C5. Bactérias de Micrococcus luteus adsorveram sobre beads oxidados e nos beads contendo baixa quantidade de QPVP-C5 adsorvido e foi observada propriedade biocida nos beads com elevada quantidade de QPVP-C5 adsorvido. Os resultados mostram o preparo de materiais celulósicos multifuncionais de baixo custo e simples preparação para aplicações em meios aquosos com a finalidade de imobilização e ação biocida frente a bactérias Gram-positivas. / The present study demonstrated that the breath figures formation in CA, CAPh, CAB and CMCAB films spin-coated from solutions in tetrahydrofuran (THF) was dependent on the polymers molecular characteristics when prepared under low relative humidity (RH 35%), whereas under higher RH (55% and 75%), the balance among water and THF surface energy and interfacial energy between water and THF was determinant. On the other hand, the short solvent vapor exposure had a plasticizer effect, making CAB, CAPh and CMCAB films completely smooth (from 3 up to 6 min), while dewetting phenomena was observed for CA films. Biocompatible sorbitan-based surfactants (Tween®) were used as plasticizer for CA, CAPh, CAB and CMCAB casted films. The thermal behavior of films was dependent on the size of surfactant hydrophobic tail, type of polymer side group and the mixture composition. Tween 20 and 40 showed act as an excellent plasticizer for cellulose esters, except for CA, which was immiscible. Low Tween content favored polymeric chains flexibility while higher content increased the cellulose esters molecular mobility leading to Tg variations up to 200 °C. CAB-based nanocomposites casted films reinforced with cellulose nanocrystals (CNC) modified with different functional groups (acetate and methyl adipoil) were prepared from dispersions in ethyl acetate (EA), THF and N,N-dimethylformamide (DMF). The best colloidal stability was verified in DMF, due its high polarity. Suspensions in EA and THF of modified CNC where more stable than unmodified CNC, regarding the interactions among substituents groups and solvents. The mechanical properties of nanocomposites stemming from nanocrystals dispersibility in the CAB matrix showed strong relationship with the colloidal stability. Cellulose beads were obtained by using pretreated Eucalyptus pulp, oxidized and used as a support for the incorporation of a biocide agent. Micrococcus luteus bacteria adsorbed onto oxidized beads and on the beads with low content of adsorbed QPVP-C5. It was observed biocide property for the beads with high QPVP-C5 content. The results show the simple preparation of low cost multifunctional cellulosic materials for applications in aqueous media for the purpose of immobilization and biocide action against Gram-positive bacteria.

O presente estudo demonstrou que a formação de cavidades (breath figures) em filmes de CA, CAPh, CAB e CMCAB preparados por spin-coating de soluções em tetrahidrofurano (THF) foi dependente das características moleculares dos polímeros quando preparados em ambiente com umidade relativa baixa (UR 35%), enquanto que em UR mais elevadas (55% e 75%) o balanço entre a energia superficial da água, THF e energia interfacial entre água e THF foi determinante. Por outro lado, a rápida exposição (de 3 a 6 min) desses filmes ao vapor de solvente teve um efeito plastificante tornando os filmes de CAB, CAPh e CMCAB completamente lisos, enquanto que para filmes de CA foi observado o efeito dewetting. Surfactantes biocompatíveis à base de sorbitano (Tween®) foram usados como plastificantes para filmes de ésteres de celulose obtidos por evaporação de solvente. O comportamento térmico dos filmes foi dependente do tamanho da cauda hidrofóbica do surfactante, do tipo do grupo lateral dos polímeros e da composição da mistura. Tween 20 e 40 mostraram agir como um excelente plastificante para os ésteres de celulose, exceto para o CA, no qual foi imiscível. Teores baixos de Tween favoreceram a flexibilidade das cadeias de polímeros ao passo que quantidades maiores aumentaram a mobilidade molecular dos ésteres de celulose levando a variações de Tg de até 200 °C. Filmes de nanocompósitos de CAB reforçados com nanocristais de celulose (CNC) modificados com diferentes grupos funcionais (acetato e metiladipoíla) foram preparados a partir de dispersões em acetato de etila (AE), THF e N,N-dimetilformamida (DMF). A melhor estabilidade coloidal foi verificada em DMF, devido sua alta polaridade. Suspensões em AE e THF de CNC modificados foram mais estáveis do que CNC por conta das interações entre grupos substituintes e solventes. As propriedades mecânicas dos nanocompósitos, resultantes da dispersibilidade de nanocristais na matriz de CAB mostraram forte relação com a estabilidade coloidal das dispersões. Beads de celulose foram obtidos utilizando polpa pré-tratada de eucalipto, oxidados e utilizados como suporte para incorporação de um agente bactericida QPVP-C5. Bactérias de Micrococcus luteus adsorveram sobre beads oxidados e nos beads contendo baixa quantidade de QPVP-C5 adsorvido e foi observada propriedade biocida nos beads com elevada quantidade de QPVP-C5 adsorvido. Os resultados mostram o preparo de materiais celulósicos multifuncionais de baixo custo e simples preparação para aplicações em meios aquosos com a finalidade de imobilização e ação biocida frente a bactérias Gram-positivas. / The present study demonstrated that the breath figures formation in CA, CAPh, CAB and CMCAB films spin-coated from solutions in tetrahydrofuran (THF) was dependent on the polymers molecular characteristics when prepared under low relative humidity (RH 35%), whereas under higher RH (55% and 75%), the balance among water and THF surface energy and interfacial energy between water and THF was determinant. On the other hand, the short solvent vapor exposure had a plasticizer effect, making CAB, CAPh and CMCAB films completely smooth (from 3 up to 6 min), while dewetting phenomena was observed for CA films. Biocompatible sorbitan-based surfactants (Tween®) were used as plasticizer for CA, CAPh, CAB and CMCAB casted films. The thermal behavior of films was dependent on the size of surfactant hydrophobic tail, type of polymer side group and the mixture composition. Tween 20 and 40 showed act as an excellent plasticizer for cellulose esters, except for CA, which was immiscible. Low Tween content favored polymeric chains flexibility while higher content increased the cellulose esters molecular mobility leading to Tg variations up to 200 °C. CAB-based nanocomposites casted films reinforced with cellulose nanocrystals (CNC) modified with different functional groups (acetate and methyl adipoil) were prepared from dispersions in ethyl acetate (EA), THF and N,N-dimethylformamide (DMF). The best colloidal stability was verified in DMF, due its high polarity. Suspensions in EA and THF of modified CNC where more stable than unmodified CNC, regarding the interactions among substituents groups and solvents. The mechanical properties of nanocomposites stemming from nanocrystals dispersibility in the CAB matrix showed strong relationship with the colloidal stability. Cellulose beads were obtained by using pretreated Eucalyptus pulp, oxidized and used as a support for the incorporation of a biocide agent. Micrococcus luteus bacteria adsorbed onto oxidized beads and on the beads with low content of adsorbed QPVP-C5. It was observed biocide property for the beads with high QPVP-C5 content. The results show the simple preparation of low cost multifunctional cellulosic materials for applications in aqueous media for the purpose of immobilization and biocide action against Gram-positive bacteria.

Perlcellulose stellt ein interessantes Material für den Einsatz in der wässrigen Größenausschlusschromatgraphie (SEC) dar. Sie ist aufgrund ihrer guten Modifizierbarkeit zudem ein perfektes Ausgangsmaterial für Protein-Aggregationsuntersuchungen. Ein Protein von besonderem praktischem Interesse ist Insulin. Dessen Fehlfaltung und Aggregation verursacht eine Reihe von schwerwiegenden Problemen (z.B. in Drug-Delivery-Systemen). Hierbei erfolgt eine Umwandlung von alpha-Helix- in beta-Faltblatt-Strukturen wobei sich unlösliche Fibrillen bilden. Deren Rückfaltung mit Hilfe fluorierter Alkohole sowie mit fluorierten Nanopartikeln wurde in der Literatur beschrieben. Der Ansatzpunkt dieser Arbeit war es zu untersuchen, ob Fluor auf Oberflächen mit hohem Anteil von Hydroxygruppen eine Rückfaltung von Proteinen wie Insulin bewirken kann. Das Ziel war es, schaltbare stationäre Phasen zu erhalten, mit denen sowohl eine Rückfaltung als auch die Trennung von Proteinen durchgeführt werden können. Zunächst erfolgte die Charakterisierung geeigneter Perlcellulosen, wobei erstmals eine Kombination der „klassischen“ Porosimetrie (Hg-Intrusion, N2-Sorption) mit SAXS und Inverser SEC zur Untersuchung der Porenstruktur von Cellulose angewandt wurde. Es konnte die reversible Schrumpfung der Poren während der Trockungsprozesse beschrieben werden. Die Immobilisierung von Fluor auf der Oberfläche von Cellulosepartikeln erfolgte u.a. durch Pfropfung von fluorierten Acrylaten mittels Cer(IV)-Redoxinitiierung. Es gelang eine homopolymerfreie Pfropfung, wobei es zu keiner Veränderung der Porenstruktur kam. Die Kontrolle der Proteinadsorption auf der modifizierten Oberfläche mittels chemischer Stimuli konnte beschrieben werden. Aggregationsuntersuchungen mittels SEC, DLS und SAXS ergaben, dass fluormodifizierte Perlcellulose keine Verzögerung der Insulinaggregation bewirkt. Jedoch zeigte sich, dass unmodifizierte Perlcellulose eine signifikante Verzögerung der Aggregation bewirken kann. / Porous bead cellulose is an interesting material for the application in aqueous size exclusion chromatography (SEC). Its good modifiability makes it furthermore to a perfect starting material for protein aggregation studies. A protein with huge practical importance is insulin. Misfolding and aggregation of insulin creates serious problems e.g. in drug delivery systems. Thereby it undergoes a change from alpha-helix to beta-sheet structure and forms insoluble fibrils. A back-folding with (toxic) fluorinated alcohols and fluorinated nanoparticles was already shown in literature. The approach for this work was that fluorine (CF3-) on a surface with high hydroxyl-content can induce the back folding of proteins like insulin. The purpose was to get stationary phases that can induce back folding and separation of proteins on a single column. At first a characterization of suitable cellulose beads with focus on different porosimetry methods was done. For the first time a combination of “classical” porosimetry methods (Hg-Intrusion; N2-Sorption) with SAXS and inverse SEC was applied for porous cellulose particles. A reversible shrinking of pores during drying process was shown. Immobilization of fluorine on the surface of cellulose beads was done by grafting of fluorinated acrylates via cer(IV)-redox-initiation and by polymer analogous reaction with fluorinated iodo alkanes. Homopolymer free graft-copolymerization was achieved, whereas no effect on pore structure was observed. The control of protein adsorption on surface by chemical stimuli was shown. Aggregation studies using SEC, DLS and SAXS showed that fluoro-modified cellulose beads do not delay insulin-aggregation due to strong adsorption effects. Though a significant aggregation delay for insulin with unmodified cellulose beads was discovered.