Thesis (Ph. D.)--Drexel University, 2004. / Includes abstract and vita. Includes bibliographical references.

The conformational dynamics of an unfolded biopolymer such as a polypeptide or DNA has attracted a significant amount of attention in the context of protein folding and the design of biomimetic technologies. To this end, recent advances in single-molecule experiments have allowed for biomolecules to be probed with an unprecedented level of detail, shedding light on their dynamics. Motivated by the need to interpret experimental data and to help guide future studies, we use concepts from polymer physics, computer simulations, and experimental data to study the timescales in which an unfolded biopolymer undergoes conformational rearrangement. First, we examine the end-to-end loop formation time in the experimentally relevant scenario where the dynamics are probed using a fluorescence probe and quencher. We show that the loop formation time in the experimentally relevant case is quantitatively dissimilar from the predictions of previous theoretical studies that neglect the quenching kinetics, which are often used to interpret experimental data. We additionally find that the loop formation times can be re-casted in a simple, universal dependence that is characteristic of random-coils. Furthermore, deviations from this universal dependence can be used as a sensitive tool for detecting structural order in unfolded biopolymers. We also consider a surface-tethered polymer chain and investigate the rate of a reaction between the free end and the surface. We explore this rate in the reaction-controlled limit and the diffusion-controlled limit, providing evidence for near-universal dependences of the rate in the respective limits. Next, we examine the transit time of end-to-end loop formation in a case study. We find that approximating the end-to-end dynamics as diffusion in a 1D potential of mean force fails dramatically to describe the transit time. Furthermore, we find that the transit time is uninfluenced by the average entropic force imposed by the polymer chain and is well described by a simple free-diffusion model. Finally, we explore the role of internal friction in the dynamics of an unfolded protein. Using simple polymer models that incorporate internal friction as an adjustable free parameter, we mimic typical single-molecule experiments that probe the unfolded state dynamics and make several experimentally verifiable predictions. / text

In this work, thermosensitive hydrogels having tunable thermo-mechanical properties were synthesized. Generally the thermal transition of thermosensitive hydrogels is based on either a lower critical solution temperature (LCST) or critical micelle concentration/ temperature (CMC/ CMT). The temperature dependent transition from sol to gel with large volume change may be seen in the former type of thermosensitive hydrogels and is negligible in CMC/ CMT dependent systems. The change in volume leads to exclusion of water molecules, resulting in shrinking and stiffening of system above the transition temperature. The volume change can be undesired when cells are to be incorporated in the system. The gelation in the latter case is mainly driven by micelle formation above the transition temperature and further colloidal packing of micelles around the gelation temperature. As the gelation mainly depends on concentration of polymer, such a system could undergo fast dissolution upon addition of solvent. Here, it was envisioned to realize a thermosensitive gel based on two components, one responsible for a change in mechanical properties by formation of reversible netpoints upon heating without volume change, and second component conferring degradability on demand. As first component, an ABA triblockcopolymer (here: Poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (PEPE) with thermosensitive properties, whose sol-gel transition on the molecular level is based on micellization and colloidal jamming of the formed micelles was chosen, while for the additional macromolecular component crosslinking the formed micelles biopolymers were employed. The synthesis of the hydrogels was performed in two ways, either by physical mixing of compounds showing electrostatic interactions, or by covalent coupling of the components. Biopolymers (here: the polysaccharides hyaluronic acid, chondroitin sulphate, or pectin, as well as the protein gelatin) were employed as additional macromolecular crosslinker to simultaneously incorporate an enzyme responsiveness into the systems. In order to have strong ionic/electrostatic interactions between PEPE and polysaccharides, PEPE was aminated to yield predominantly mono- or di-substituted PEPEs. The systems based on aminated PEPE physically mixed with HA showed an enhancement in the mechanical properties such as, elastic modulus (G′) and viscous modulus (G′′) and a decrease of the gelation temperature (Tgel) compared to the PEPE at same concentration. Furthermore, by varying the amount of aminated PEPE in the composition, the Tgel of the system could be tailored to 27-36 °C. The physical mixtures of HA with di-amino PEPE (HA·di-PEPE) showed higher elastic moduli G′ and stability towards dissolution compared to the physical mixtures of HA with mono-amino PEPE (HA·mono-PEPE). This indicates a strong influence of electrostatic interaction between –COOH groups of HA and –NH2 groups of PEPE. The physical properties of HA with di-amino PEPE (HA·di-PEPE) compare beneficially with the physical properties of the human vitreous body, the systems are highly transparent, and have a comparable refractive index and viscosity. Therefore,this material was tested for a potential biological application and was shown to be non-cytotoxic in eluate and direct contact tests. The materials will in the future be investigated in further studies as vitreous body substitutes. In addition, enzymatic degradation of these hydrogels was performed using hyaluronidase to specifically degrade the HA. During the degradation of these hydrogels, increase in the Tgel was observed along with decrease in the mechanical properties. The aminated PEPE were further utilised in the covalent coupling to Pectin and chondroitin sulphate by using EDC as a coupling agent. Here, it was possible to adjust the Tgel (28-33 °C) by varying the grafting density of PEPE to the biopolymer. The grafting of PEPE to Pectin enhanced the thermal stability of the hydrogel. The Pec-g-PEPE hydrogels were degradable by enzymes with slight increase in Tgel and decrease in G′ during the degradation time. The covalent coupling of aminated PEPE to HA was performed by DMTMM as a coupling agent. This method of coupling was observed to be more efficient compared to EDC mediated coupling. Moreover, the purification of the final product was performed by ultrafiltration technique, which efficiently removed the unreacted PEPE from the final product, which was not sufficiently achieved by dialysis. Interestingly, the final products of these reaction were in a gel state and showed enhancement in the mechanical properties at very low concentrations (2.5 wt%) near body temperature. In these hydrogels the resulting increase in mechanical properties was due to the combined effect of micelle packing (physical interactions) by PEPE and covalent netpoints between PEPE and HA. PEPE alone or the physical mixtures of the same components were not able to show thermosensitive behavior at concentrations below 16 wt%. These thermosensitive hydrogels also showed on demand solubilisation by enzymatic degradation. The concept of thermosensitivity was introduced to 3D architectured porous hydrogels, by covalently grafting the PEPE to gelatin and crosslinking with LDI as a crosslinker. Here, the grafted PEPE resulted in a decrease in the helix formation in gelatin chains and after fixing the gelatin chains by crosslinking, the system showed an enhancement in the mechanical properties upon heating (34-42 °C) which was reversible upon cooling. A possible explanation of the reversible changes in mechanical properties is the strong physical interactions between micelles formed by PEPE being covalently linked to gelatin. Above the transition temperature, the local properties were evaluated by AFM indentation of pore walls in which an increase in elastic modulus (E) at higher temperature (37 °C) was observed. The water uptake of these thermosensitive architectured porous hydrogels was also influenced by PEPE and temperature (25 °C and 37 °C), showing lower water up take at higher temperature and vice versa. In addition, due to the lower water uptake at high temperature, the rate of hydrolytic degradation of these systems was found to be decreased when compared to pure gelatin architectured porous hydrogels. Such temperature sensitive architectured porous hydrogels could be important for e.g. stem cell culturing, cell differentiation and guided cell migration, etc. Altogether, it was possible to demonstrate that the crosslinking of micelles by a macromolecular crosslinker increased the shear moduli, viscosity, and stability towards dissolution of CMC-based gels. This effect could be likewise be realized by covalent or non-covalent mechanisms such as, micelle interactions, physical interactions of gelatin chains and physical interactions between gelatin chains and micelles. Moreover, the covalent grafting of PEPE will create additional net-points which also influence the mechanical properties of thermosensitive architectured porous hydrogels. Overall, the physical and chemical interactions and reversible physical interactions in such thermosensitive architectured porous hydrogels gave a control over the mechanical properties of such complex system. The hydrogels showing change of mechanical properties without a sol-gel transition or volume change are especially interesting for further study with cell proliferation and differentiation. / In der vorliegenden Arbeit wurden thermosensitive Hydrogele mit einstellbaren thermo-mechanischen Eigenschaften synthetisiert. Im Allgemeinen basiert der thermische Übergang thermosensitiver Gele auf einer niedrigsten kritischen Löslichkeitstemperatur (LCST) oder kritischer Mizellkonzentration bzw. –temperatur(CMC/ CMT). Der temperaturabhängige Übergang von Sol zu Gel mit großer Volumenänderung wurde im ersten Fall bei thermosensitiven Hydrogelen beobachtet und ist vernachlässigbar für CMC/ CMT abhängige Systeme. Die Änderung des Volumens führt zum Ausschluss von Wassermolekülen, was zum Schrumpfen und Versteifen des Systems oberhalb der Übergangstemperatur führt. Die Volumenänderung kann unerwünscht sein, wenn Zellen in das Gel eingeschlossen werden sollen. Die Gelierung im zweiten Fall beruht hauptsächlich auf der Mizellbildung oberhalb der Übergangstemperatur und weiterem kolloidalem Packen von Mizellen im Bereich der Gelierungstemperatur. Weil die Gelierung hauptsächlich von der Polymerkonzentration abhängt, kann sich das Gel bei Zugabe von Lösungsmittel leicht wieder lösen. Hier sollten thermosensitive Gele entwickelt werden, die auf zwei Komponenten beruhen. Eine Komponente sollte aus einem ABA-Triblockcopolymer mit thermosensitiven Eigenschaften bestehen, dem Poly(ethylen glycol)-b-Poly(propylenglycol)-b-Poly(ethylen glycol) (PEPE), dessen Sol-Gel-Übergang auf Mizellierung und kolloidalem Jamming der gebildeten Mizellen basiert, und einer weiteren makromolekularen Komponente, einem Biopolymer, dass die Mizellen vernetzt. Auf diese Weise sollten thermosensitive Gele realisiert werden, die keine oder nur eine kleine Volumenänderung während der Änderung der mechanischen Eigenschaften zeigen, die stabiler gegenüber Verdünnung sein sollten als klassische Hydrogele mit einem CMC-basierten Übergang und die jedoch gezielt abgebaut werden können. Die Hydrogele wurden auf zwei Arten vernetzt, entweder durch physikalisches Vermischen, bei dem die Vernetzung durch elektrostatische Wechselwirkungen erfolgte, oder durch kovalente Kopplung der beiden Komponenten. Als makromolekulare Komponente zur Vernetzung der Mizellen wurden Biopolymere (hier: die Polysaccharide Hyaluronsäure (HA), Chondroitinsulfat oder Pektin oder das Protein Gelatin) verwendet, um die Hydrogele enzymatisch abbaubar zu gestalten. Um eine starke ionische/elektrostatische Wechselwirkung zwischen dem PEPE und den Polysachariden zu erzielen, wurde PEPE aminiert, um hauptsächlich monoaminiertes bzw. diaminiertes PEPE einsetzen zu können. Die Gele, die auf der physikalischen Mischung von aminierten PEPE mit HA bestehen, zeigten im Vergleich zu PEPE bei gleicher Konzentration eine Zunahme der mechanischen Eigenschaften, wie beispielsweise dem elastischem Modulus (G′) und dem Viskositätsmodulus (G′′) bei gleichzeitiger Abnahme der Gelierungstemperatur (Tgel). Durch Variation des Gehalts an aminierten PEPE-, konnte die Tgel in einem Bereich von 27-36 °C eingestellt werden. Interessanterweise zeigten die physikalischen Mischungen mit diaminierten PEPE (HA·di-PEPE) höhere mechanische Eigenschaften (elastischer Modulus G′) und eine höhere Stabilität gegenüber Verdünnungseffekten als Mischungen mit monoaminiertem PEPE (HA·mono-PEPE). Dies zeigt den starken Einfluss der elektrostatischen Wechselwirkungen zwischen der Carboxylgruppe der HA und der Amingruppe von PEPE. Die physikalischen Eigenschaften HA·di-PEPE sind vergleichbar mit den physikalischen Eigenschaften des Glaskörpers im Auge hinsichtlich Transparenz, Brechungsindex und Viskosität. Deswegen wurde das Material hinsichtlich seiner biologischen Anwendung getestet und zeigte sich sowohl im Überstand als auch im direkten Kontakt als nichtzytotoxisch. Zukünftig wird dieses Material in weiteren Untersuchungen bezüglich seiner Eignung als Glaskörperersatz geprüft werden. Zusätzlich konnte der enzymatische Abbau der Hydrogele mit Hyaluronidase gezeigt werden, die spezifisch HA abbaut. Beim Abbau der Hydrogele stieg Tgel bei gleichzeitiger Abnahme der mechanischen Eigenschaften. Aminiertes PEPE wurde zusätzlich zur kovalenten Bindung unter Verwendung von EDC als Aktivator an Pektin und Chondroitinsulfat eingesetzt. Tgel konnte auf 28 – 33 °C eingestellt werden durch Variation der Pfropfungsdichte am Biopolymer bei gleichzeitiger Zunahme der thermischen Stabilität. Die Pec-g-PEPE Hydrogele waren enzymatisch abbaubar, was zu einer leichten Erhöhung von Tgel und zu einer Abnahme von G′ führte. Die kovalente Bindung der aminierten PEPE an HA erfolgte unter Verwendung von DMTMM als Aktivator, der sich in diesem Fall als effektiver als EDC herausstellte. Die Reinigung mittels Ultrafiltration führte zu einer deutlich besseren Aufreinigung des Produkts als mittels Dialyse. Die gegrafteten Systeme waren in Nähe der Körpertemperatur bereits im Gelstadium und zeigten eine Erhöhung der mechanischen Eigenschaften bereits bei sehr geringen Konzentrationen von 2.5Gew.%. Die höheren mechanischen Eigenschaften dieser Hydrogele erklären sich durch die Kombination der Mizellbildung (physikalische Wechselwirkung) des PEPE und der Bildung kovalenter Netzpunkte zwischen PEPE und HA. PEPE bzw. entsprechende physikalische Mischungen derselben Komponenten zeigten kein thermosensitives Verhalten bei einer Konzentration unterhalb von 16 Gew%. Diese thermosensitiven Hydrogele zeigten auch eine Löslichkeit auf Abruf durch enzymatischen Abbau. Das Konzept der Thermosensitivität wurde in 3D strukturierte, poröse Hydrogele (TArcGel)eingeführt, bei dem PEPE kovalent an Gelatin gebunden wurde und mit LDI vernetzt wurde. Das gepfropfte PEPE führte zu einer Erniedrigung der Helixbildung der Gelatinketten. Nach Fixierung der Gelatinketten durch Vernetzung zeigte das System eine Erhöhung der mechanischen Eigenschaften bei Erwärmung (34-42 °C). Dieses Phänomen war reversibel beim Abkühlen. Eine mögliche Erklärung der reversiblen Änderungen bezüglich der mechanischen Eigenschaften sind die starken physikalischen Wechselwirkungen zwischen den Mizellen des PEPE, die kovalent an Gelatin gebunden wurden. Ferner wurde durch AFM Untersuchungen festgestellt, dass bei Temperaturerhöhung (37 °C) die örtlichen elastischen Moduli (E) der Zellwände zugenommen haben. Zusätzlich wurde die Wasseraufnahme der TArcGele durch PEPE und die Temperatur (25 °C und 37 °C) beeinflusst und zeigte eine niedrigere Wasseraufnahme bei höherer Temperatur und umgekehrt. Durch die niedrigere Wasseraufnahme bei hohen Temperaturen erniedrigte sich die Geschwindigkeit des hydrolytischen Abbaus im Vergleich zu dem strukturierten Hydrogel aus reiner Gelatin. Diese temperatursensitiven ArcGele könnten bedeutsam sein für Anwendungen im Bereich Stammzellkultivierung, Zelldifferenzierung und gerichteter Zellmigration. Zusammenfassend konnte bei den thermosensitiven Hydrogelen gezeigt werden, dass die Vernetzung von Mizellen mit einem makromolekularen Vernetzer die Schermoduli, Viskosität und Löslichkeitsstabilität im Vergleich zu reinen ABATriblockcopolymeren mit CMC-Übergang erhöht. Dieser Effekt konnte durch kovalente und nichtkovalente Mechanismen, wie beispielsweise Mizell- Wechselwirkungen, physikalische Interaktionen von Gelatinketten und physikalische Interaktionen von Gelatinketten und Mizellen, realisiert werden. Das Pfropfen von PEPE führte zu zusätzlichen Netzpunkten, die die mechanischen Eigenschaften der thermosensitiven architekturisierten, porösen Hydrogele beeinflussten. Insgesamt ermöglichten die physikalischen und chemischen Bindungen und die reversiblen physikalischen Wechselwirkungen in den strukturierten, porösen Hydrogelen eine Kontrolle der mechanischen Eigenschaften in diesem sehr komplexen System. Die Hydrogele, die eine Veränderung ihrer mechanischen Eigenschaften ohne Volumenänderung oder Sol-Gel-Übergang zeigen sind besonders interessant für Untersuchungen bezüglich Zellproliferation und –differenzierung.

Membrane filtration is growing in popularity as a viable technology for drinking water treatment to meet high demand and regulatory requirements. While many improvements have been made to the technology in the past decade, fouling continues to be one of the major operational challenges associated with membranes as it increases operating costs and reduces membrane life. Fouling control typically requires some form of pre-treatment. Biofiltration is a ???green??? technique that can minimize chemical usage and waste during water treatment and is a relatively new application as a pre-treatment for membranes. Proteins and polysaccharides (biopolymers) have been found to contribute most to fouling of low pressure polymeric membranes. Biofiltration has recently been demonstrated as an effective pre-treatment method for reducing biopolymer-associated fouling of this type of membrane (Hall?? et al., 2009). Given that the concentration and composition of organic matter in water is variable, there is an opportunity to explore the applicability of this robust technology for different water types. The primary goals of this research were to assess the effectiveness of direct biofiltration in minimizing ultrafiltration polymeric (PVDF) membrane fouling and at the same time evaluate the biofilter development, biofilter performance based on organics removal potential, and the effect of phosphorus addition (as a nutrient) to the biofilter influent. A pilot-scale treatment train was constructed at the Technology Demonstration Facility at the Walkerton Clean Water Centre. It included two parallel dual media (sand/anthracite) biological filters (preceded by roughing filters), followed by an ultrafiltration membrane unit. Experiments were conducted using water from the Saugeen River (Ontario, Canada) whose primary form of carbon is humic material. The biofilters were allowed to acclimate and biofilter performance and organics removal were tested over a fourteen month period, the last four months of which were dedicated to phosphorus enhancement experiments. The membrane fouling experiments started seven months following the start-up of the biofilters, after confirmation of steady-state operation. Biofilter water samples were analyzed for natural organic matter constituents along with other water quality parameters, and biomass quantity and activity in the media were measured. Biomass activity in the biofilter media and biopolymer removal through the biofilter indicated a rapid acclimation period, and also demonstrated similar performance of the parallel biofilters during start-up and steady-state operation. The biofilters achieved 21% removal of the biopolymers on average following acclimation, while reduction of the humic fractions was not observed. A linear relationship between biopolymer removal and its concentration in the river water was observed (first-order process). Membrane fouling experiments were conducted using both untreated and biofiltered river water. The fouling rates were computed by monitoring changes in transmembrane pressure over time. Analysis of the samples with liquid chromatography-organic carbon detection confirmed the significant contribution of biopolymers to irreversible and reversible membrane fouling rates even when only present at low concentrations. During the phosphorus enhancement phase, two different phosphorus doses were fed into the influent of one of the parallel biofilters in order to achieve a target C:N:P ratio of roughly 100:10:1. Although initially (first month of the dosing period) an increase in the removal of dissolved organic carbon and ultraviolet-absorbance was observed in the phosphorus-enhanced biofilter, this was not sustained. Phosphorus addition did not affect biopolymer removal or biomass quantity and activity in the biofilter, and the membrane fouling experiments during this period did not show any significant effect of phosphorus addition.

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

Thesis (PH. D.)--Michigan State University. Chemical Engineering, 2008. / Title from PDF t.p. (viewed on Sept. 6, 2009) Includes bibliographical references (p. 116-119). Also issued in print.

Thesis (M.SC.) - Carleton University, 2007. / Includes bibliographical references. Also available in electronic format on the Internet.

Thesis (Ph.D.)--Texas Christian University, 2008. / Title from dissertation title page (viewed Mar. 10, 2009). Includes abstract. Includes bibliographical references.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-07-09T17:24:53Z No. of bitstreams: 1 AKIDAUANA DANDARA BRITO DE OLIVEIRA - DISSERTAÇÃO (PPGCEMat) 2015.pdf: 4346677 bytes, checksum: 2518460fd25d05c04a1b089149325a5d (MD5) / Made available in DSpace on 2018-07-09T17:24:53Z (GMT). No. of bitstreams: 1 AKIDAUANA DANDARA BRITO DE OLIVEIRA - DISSERTAÇÃO (PPGCEMat) 2015.pdf: 4346677 bytes, checksum: 2518460fd25d05c04a1b089149325a5d (MD5) Previous issue date: 2015-02-26 / CNPq / Os biopolímeros são polímeros ou copolímeros produzidos a partir de matériasprimas de fontes renováveis, como: milho, cana-de-açúcar, celulose, quitina, e outras. Já os biopolímeros verdes também são sintetizados a partir de matériaprima de fontes renováveis, porém, não são biodegradáveis e mantêm as mesmas características dos polímeros obtidos de fontes fósseis. Um exemplo de polímero verde é o polietileno verde (PE verde). Este trabalho teve como objetivo principal desenvolver blendas poliméricas a partir de dois biopolietilenos verdes (BioPEAD/BioPELBD) e avaliar o efeito da composição nas diversas propriedades e morfologia. As blendas foram preparadas em extrusora dupla rosca corrotacional, seguida da moldagem por injeção e caracterizadas a partir de medidas reológicas sob taxa de cisalhamento em regime permanente e oscilatório , análise das propriedades mecânicas, Difração de raios X (DRX), Microscopia Eletrônica de Varredura (MEV), análise térmica por calorimetria exploratória diferencial (DSC) e termogravimétrica (TG). Dos resultados obtidos quanto ao comportamento reológico, verificou-se que a viscosidade aparente obedeceu à regra da aditividade e, a viscosidade e o grau de pseudoplasticidade, variaram proporcionalmente com a concentração. O resultado do comportamento reológico em regime viscoelástico linear mostrou que as blendas apresentaram um aumento no valor da viscosidade complexa a baixas freqüências (região de platô) e com valores intermediários para as blendas, quando comparados ao BioPEAD e BioPELBD. The comportamento semelhante ao obtido em regime permanente, sugerindo a Regra de Cox-Merz. Os ensaios reológicos também sugeriram que o BioPEAD e BioPELBD foram parcialmente miscíveis no estado fundido. Os resultados das propriedades mecânicas mostraram que aumento do teor de BioPELBD diminuiu a resistência à tração e o módulo de elasticidade. Por outro lado, o alongamento até a ruptura, e, por conseguinte a tenacidade, e a resistência ao impacto aumentaram substancialmente. Os resultados obtidos por DRX mostraram que a cristalinida do BioPEAD diminuiu com o aumento do teor de BioPELBD nas blendas BioPEAD/BIOPELBD. A partir das fotomicrografias obtidas por MEV, observou-se que o aumento do teor de BioPELBD nas blendas, reduz significativamente a quantidade de partículas da fase dispersa sendo até imperceptível visualizá-las quando a concentração de 50% em peso de BioPELBD foi alcançada, sugerindo co-continuidade de fases. Os resultados de DSC mostraram uma redução no valor do pico da temperatura de fusão à medida que se aumentou o teor de BioPELBD, indicando uma diminuição do tamanho dos cristalitos e, por conseguinte, uma redução na cristalinidade das blendas. A partir dos resultados de TG, observouse que as blendas exibiram estabilidade térmica mais elevadas do que para o BioPEAD e BioPELBD. / Biopolymers are polymers or copolymers made from raw materials of renewable sources, such as corn, sugarcane, sugar, cellulose, chitin and others. Green biopolymers are also synthesized from renewable raw materials, however, are not biodegradable and maintain the same characteristics of the polymers obtained from fossil sources. An example of green polymer is biopolyethylene (BioPE). The aim of this work is to develop polymer blends from two types of biopolyethylene (Bio High Density Polyethylene - BioPEAD / Bio Linear Low Density Polyethylene - BioPELBD) and to evaluate the effect of the composition on various properties and morphology. The BioPEAD/BioPELBD blends were prepared by extrusion, in a co-rotational twin-screw extruder, followed by injection molding and characterized by rheological measurements under steady and oscillatory shear flows, mechanical properties, X-Ray diffraction (XRD), Scanning Electron Microscopy (SEM), Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC). From the rheological measurements under steady shear flow, it was found that the apparent viscosity followed the rule of additivity, and the viscosity and degree of pseudoplasticity varied proportionally with concentration. Rheological measurements under oscillatory shear flow showed that the complex viscosity values of the blends increased at low frequencies (plateau region) and intermediate values were obtained for the blends, when compared to neat BioPEAD and BioPELBD. The values of the viscosity obtained in the oscillatory shear flow were similar to those obtained under steady shear flow, suggesting that the Cox-Merz rule was obeyed. The rheological measurements also suggested that BioPEAD and BioPELBD were partially miscible. The mechanical properties results showed that the increase in BioPELBD content decreased the tensile strength and elastic modulus. On the other hand, the elongation to break, and thus the toughness, and the impact strength have substantially increased. The XRD results showed that the crystallinity of BioPEAD decreased with the increase in the PELBD content in the BIOPEAD/BioPELBD blends. From SEM micrographs, it was observed that with the increase in the BioPELBD content the amount of dispersed phase particles was substantially decreased, being imperceptible when the concentration of 50% of BioPELBD was reached, suggesting phase cocontinuity. DSC results showed a reduction of the melting temperature peak value as BioPELBD content was increased, indicating a decrease in the crystallite size and therefore a reduction in the crystallinity of the blends. From the TG results, it was observed that the blends exhibited higher thermal stability than that of both BioPEAD and BioPELBD.

Polímeros oriundos de fontes não renováveis são amplamente utilizados na produção de embalagens e para uso na agricultura, em confecção de estufas, sacos para produção de mudas e filmes para cobertura de solo. Estes plásticos são resistentes à degradação e após utilização passam a ser um problema ambiental, portanto, o desenvolvimento de materiais biodegradáveis é uma necessidade, visto que são produzidos de fontes renováveis e decompõem-se rapidamente, diminuindo o impacto sobre o meio ambiente. O reaproveitamento total ou parcial de resíduos perigosos, como os de couro curtido ao cromo III, também tem sido alvo de pesquisas por gerar um ganho ambiental se comparado a disposição em aterros indunstriais para resíduos perigosos. Dentro deste contexto, no presente trabalho foram produzidos filmes de gelatina comercial e filmes de gelatina extraída de resíduo de couro curtido ao cromo III, em associação a plastificante e enzima transglutaminase (TGase) como agente reticulante. A enzima TGase foi estatisticamente significativa nas propriedades de solubilidade, ângulo de contato e elongação dos filmes produzidos com gelatina comercial. Para os filmes produzidos com gelatina extraída de resíduo de couro curtido ao cromo III, a enzima TGase atuou de forma estatisticamente significativa nas propriedades de solubilidade, umidade, ângulo de contato, permeabilidade ao vapor d água e tensão de ruptura dos filmes. As análises térmicas mostraram que a reticulação enzimática aumentou a estabilidade térmica dos filmes. A análise de infravermelho evidenciou a reticluação da enzima transglutaminase nos filmes pelo deslocamento das bandas. No teste de biodegradabilidade em solo simulado, os filmes degradaram-se em 24 horas, comprovando que o polímero é biodegradável. Este estudo demonstrou a viabilidade da utilização de gelatina recuperada de um resíduo para produzir filmes biodegradáveis com melhorias na suas propriedades com adição de um agente reticulante. / Submitted by Ana Guimarães Pereira (agpereir@ucs.br) on 2017-08-07T14:13:35Z No. of bitstreams: 1 Dissertacao Elizete Baggio Brandalise.pdf: 2076499 bytes, checksum: 5907508a0674b933cdbb4d6b11eb4ecc (MD5) / Made available in DSpace on 2017-08-07T14:13:36Z (GMT). No. of bitstreams: 1 Dissertacao Elizete Baggio Brandalise.pdf: 2076499 bytes, checksum: 5907508a0674b933cdbb4d6b11eb4ecc (MD5) Previous issue date: 2017-08-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, CAPES. / Polymers from non-renewable sources are widely used in the production of packaging and for use in agriculture, in the manufacture of greenhouses, bags for the production of seedlings and films for soil cover. These plastics are resistant to degradation and after use become an environmental problem, therefore, the development of biodegradable materials is a necessity, since they are produced from renewable sources and decompose rapidly, reducing the impact on the environment. The total or partial reuse of hazardous wastes, such as chrome-tanned leather III, has also been the subject of research for generating an environmental gain compared to disposal in industrial landfills for hazardous waste. In this context, commercial gelatin films and gelatin films extracted from leather residue to chromium III, in combination with plasticizer and enzyme transglutaminase (TGase) as crosslinking agent were produced in the present work. The enzyme TGase was statistically significant in the properties of solubility, contact angle and elongation of the films produced with commercial gelatin. For the films produced with gelatine extracted from chromium III tanned leather residue, the enzyme TGase was statistically significant in the properties of solubility, humidity, contact angle, water vapor permeability and rupture stress of the films. Thermal analysis showed that enzymatic crosslinking increased the thermal stability of films. Infrared analysis evidenced the reticulation of the transglutaminase enzyme in the films by the bands displacement. In the biodegradability test in simulated soil, the films degraded in 24 hours, proving that the polymer is biodegradable. This study demonstrated the feasibility of using gelatine recovered from a residue to produce biodegradable films with improvements in its properties with the addition of a crosslinking agent.