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Novel biomaterials provide a spectrum of possibilities. They can be engineered in different forms to understand how they would perform as different bioprosthetic conduits. Bacterial cellulose membranes may be suitable candidates as prosthetic valve leaflets in valve replacement surgeries due to their functional properties (hemodynamics, resistant to thrombosis). Biomaterials used for most bioprosthetic heart valves are cut, trimmed and sutured. A major challenge for the bi-leaflet configuration is that the cutting and suturing of biopolymers fabricated as sheets into a cylindrical form increases failure risk due to greater number of suture points and irregular coaptation. The objective was to culture the bacterial cellulose membrane as a continuous cylindrical construct and evaluate its mechanical properties. Various design features of the fabrication process such as culturing media and the hollow carrier-mandrel characteristics were evaluated. A comparative study of how bacterial cellulose grows on different hollow carrier membranes was conducted and thin smooth surface silicone tubes fabricated in the lab were found to be most suitable. A bioreactor for culturing cylindrical bacterial cellulose tubes on the outer surface of the hollow carrier was designed and fabricated. The mechanical properties of the fabricated tubes, specifically, their tensile strength, flexure, suture retention and tear resistance were characterized. Mechanical characterization studies showed the cylindrical bacterial cellulose tubes to be anisotropic, with preferential properties in the longitudinal (axial) direction of the tube. Preliminary results show that cylindrical bacterial cellulose tubes can be a promising candidate for use in prosthetic valve conduits.

Submitted by Luciana Sebin (lusebin@ufscar.br) on 2016-09-21T13:17:25Z No. of bitstreams: 1 TesePBef.pdf: 3148046 bytes, checksum: 168b293a813985fc61f9e1a34e6572fa (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-23T18:22:09Z (GMT) No. of bitstreams: 1 TesePBef.pdf: 3148046 bytes, checksum: 168b293a813985fc61f9e1a34e6572fa (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-23T18:22:17Z (GMT) No. of bitstreams: 1 TesePBef.pdf: 3148046 bytes, checksum: 168b293a813985fc61f9e1a34e6572fa (MD5) / Made available in DSpace on 2016-09-23T18:22:23Z (GMT). No. of bitstreams: 1 TesePBef.pdf: 3148046 bytes, checksum: 168b293a813985fc61f9e1a34e6572fa (MD5) Previous issue date: 2015-10-29 / Não recebi financiamento / Burn injuries represent a high risk of morbidity and mortality worldwide. In severe and deep injuries, the wound healing process is complex and requires the participation of different types of cells. Among the existing treatments, biomaterials and LLLT are highlighted for having properties that favor and stimulate the healing process. Thus, three studies were conducted to evaluate the effects of bacterial cellulose membranes in its pure state or enriched with lidocaine and LLLT (660 nm) in two different fluences (12.5J/cm2 and 25J/cm2) used independently or associated, on third-degree burns in rats. The burn was induced with an aluminum plate at 150°C, pressed onto the animal's back for 10 seconds. In the first study the action of bacterial cellulose membrane in its pure state and enriched with lidocaine, as biological dressings was evaluated. Therefore, the rats were divided in three experimental groups, CG (control group), MG (group treated with the pure bacterial cellulose membrane), and MLG (group treated with the bacterial cellulose membrane with lidocaine). The treated groups showed an advanced wound healing when compared to the control group. In the immunohystochemical analysis of COX-2, the treated groups showed a light immunoexpression, with the characteristics of repaired tissue. Thus, bacterial cellulose-based biological dressings were effective and provided a favorable environment for the development of the healing process. In the second study, the effects of LLLT with two different fluences (12.5J/cm2 and 25J/cm2) in three experimental groups, divided into CG (control group), LG12.5 (burning treated group 12.5 J/cm2) and LG25 (burn group treated with 25 J/cm2) were evaluated. The animals received laser application immediately after the induction of the lesion and the subsequent doses 2, 4, 6 and 8 days after the induction, at five different points, four on the edges of the wound and one in the central region. The LG25 had better results, with higher number of blood vessels, increased immunoexpression of VEGF (Vascular Endothelial Growth Factor) and decreased immunoexpression of COX-2 (Cyclooxygenase-2) when compared to CG and GL12.5 groups. The LG12.5 showed the longest delay in the progression of the healing process, due to its intense inflammation and tissue fibrosis when compared to CG and LG25. In the third study the association of pure bacterial cellulose membrane and LLLT (660 nm, 25 J/cm2) was investigated. Four groups were evaluated, CG (control group), MG (burn group treated with pure bacterial cellulose membrane), LG (burn group treated with laser 25 J/cm2) and MG + L (burn group treated with bacterial cellulose membrane + LLLT). Histological findings demonstrated that the treated group showed better results in the healing process. The (GM + L) showed results similar to those found in the GL, evidencing the stimulatory effects of angiogenesis provided by the laser light. GM showed improvement in the healing process, indicating the proliferative phase. However, although LLLT presented the expected proinflam matory effects, which modulate the inflammatory phase and favor tissue regeneration, the isolated action of the bacterial cellulose membrane proved to be advantageous by presenting tissue characteristics, which are compatible with a more advanced phase of the healing process. / Queimaduras representam mundialmente alto risco de morbidade e mortalidade. Nas consideradas severas ou profundas, o processo de cicatrização é complexo e necessita da participação de diversas linhagens celulares. Dentre os tratamentos existentes, os biomateriais e a Terapia laser de baixa intensidade (LLLT) vêm se destacando por apresentar propriedades que favorecem e estimulam o processo de cicatrização. Assim, foram realizados três estudos com o objetivo de avaliar os efeitos das membranas de celulose bacteriana pura e com lidocaína e da LLLT (660 nm) em duas fluências diferentes (12,5J/cm2 e 25J/cm2), utilizados independentemente ou associados, em queimaduras de terceiro grau em ratos. A queimadura foi realizada através de uma placa de alumínio acoplada a um ferro de solda aquecido a 150°C, pressionado no dorso do animal por 10 segundos. No primeiro estudo a ação das membranas de celulose bacteriana pura e acrescida de lidocaína foram avaliados. Para isso, foram estabelecidos três grupos experimentais divididos em GC (grupo controle), GM (grupo queimadura tratado com a membrana de celulose bacteriana pura) e GML (grupo queimadura tratado com a membrana de celulose acrescida de lidocaína). Os grupos tratados com as membranas demonstraram um processo de cicatrização avançado quando comparado ao grupo controle. Na análise da imunoexpressão da COX-2, os grupos tratados apresentaram a imunoexpressão de forma leve, o que evidencia características de tecido reparado. Assim, concluímos que os curativos biológicos a base de celulose bacteriana, foram efetivos, proporcionando um ambiente favorável para a evolução do processo de cicatrização. No segundo estudo, foram avaliados os efeitos da LLLT com duas diferentes fluências (12,5J/cm2 e 25J/cm2) em três grupos experimentais, divididos em GC (grupo controle), GL12,5 (grupo queimadura tratado com 12,5J/cm2) e GL25 (grupo queimadura tratado com 25J/cm2). Os animais receberam a aplicação da LLLT imediatamente após a indução da lesão e nos dias 2, 4, 6 e 8 subsequentes, em cinco pontos distintos, sendo quatro localizados nas bordas da ferida e um na região central. O GL25 demonstrou os melhores resultados, com maior imunoexpressão do VEGF (Fator de crescimento endotelial vascular), maior quantidade de vasos sanguíneos e menor imunoexpressão da COX-2 Ciclooxigenase-2) quando comparado aos grupos GC e GL12,5. Com isso, foi possível concluir que a maior fluência, bem como a maior energia depositada no tecido foi mais eficaz em estimular o processo de cicatrização em queimaduras de terceiro grau em ratos. No terceiro estudo foi abordada a associação da membrana de celulose bacteriana pura com a LLLT (660 nm, 25J/cm2). Quatro grupos foram avaliados, GC (grupo controle), GM (grupo queimadura tratado com membrana de celulose bacteriana pura), GL (grupo queimadura tratado com laser 25J/cm2) e GM+L (grupo queimadura tratado com membrana de celulose bacteriana + LLLT). Os achados histológicos demonstraram que os grupos que receberam os tratamentos apresentaram melhores resultados no processo de cicatrização quando comparados ao grupo controle. O (GM+L) apresentou resultados similares aos achados no GL, evidenciando os efeitos estimuladores da angiogênese fornecidos pela luz laser. O GM apresentou avanço no processo de cicatrização, evidenciando a fase proliferativa. Assim, apesar da LLLT apresentar os efeitos pró-inflamatórios esperados, que modulam a fase inflamatória e favorecem a regeneração tecidual, a ação isolada da membrana de celulose bacteriana demonstrou vantagens no tratamento por apresentar características morfológicas teciduais compatíveis a um processo de cicatrização mais avançado.

Desde o início da espécie humana, houve quem procurasse auxiliar o corpo na tentativa natural de restaurar suas partes injuriadas. Um dos grandes desafios atuais é a substituição de tecidos do organismo, inclusive em áreas de lesão cutânea. Um biomaterial pode ser utilizado para melhorar, aumentar ou substituir, parcial ou inteiramente tecidos ou órgãos. A membrana de celulose bacteriana (CB) possui moldabilidade, boas propriedades mecânicas, permeabilidade seletiva, permitindo a passagem de vapor d\'água, mas impedindo a passagem de microrganismos. O colágeno (COL) vem sendo amplamente usado como material na fabricação de biomateriais. Neste trabalho obteve-se membrana e hidrogel de CB-COL, caracterizados de diferentes maneiras. Foram realizados, estudos in vivo, análises macroscópica e histológica de coberturas de CB-COL, comparando com os controles (coágulo e a pomada de colagenase), após a aplicação sobre as feridas confeccionadas no dorso de ratos. Os animais foram sacrificados depois de 3, 7, 15 e 30 dias, e os dorsos processados segundo rotina histológica para coloração em HE. As caracterizações realizadas neste trabalho (microscopia eletrônica de varredura (MEV), análise termogravimétrica (TG), espectroscopia no infravermelho com transformada de Fourier (FT-IR) e difratometria de raios-X (DRX)) confirmaram a incorporação do COL às matrizes de CB. A avaliação macroscópica somente demonstrou diferença estatisticamente significante da reparação tecidual entre os tratamentos aos sete dias de pós-operatório, sendo que o hidrogel apresentou uma tendência para uma reparação mais rápida. Os resultados da avaliação histológica demonstraram diferença estatisticamente significante para reação inflamatória tecidual entre os tratamentos em todos os períodos estudados. Na avaliação da qualidade, quantidade e orientação das fibras colágenas, somente o período de três dias que não apresentou diferença estatisticamente significante entre os tratamentos. Conclui-se com esses resultados que as duas coberturas são biocompatíveis. / Since the beginning of the human race, there was those who sought to assist the body in a natural attempt to restore yours injured parts. One of the main current challenges is the replacement of body tissues, including areas of skin lesion. A biomaterial can be used to improve, enhance or replace, partially or fully tissues or organs. The membrane of bacterial cellulose (BC) has moldability, good mechanical properties, selective permeability, allowing the passage of water vapor but preventing the passage of microorganisms. The collagen (COL) has been widely used as material in the manufacture of biomaterials. In this study was obtained hydrogel and membrane BC-COL, characterized in different ways. Were realized in vivo studies, macroscopic and histological analyzes from dressings of BC-COL, comparing with controls (clot and collagenase ointment), after applying in wounds on the backs of rats. The animals were sacrificed after 3, 7, 15 and 30 days, and the scars were processed according to histological routine to HE staining. The characterizations performed in this study (scanning electron microscopy (SEM), thermogravimetric analysis (TGA), infrared spectroscopy with Fourier transform (FT-IR) and X-ray diffraction (XRD)) confirmed the incorporation of the COL to matrices BC. The macroscopic evaluation only demonstrated statistically significant difference of tissue repair between treatments at seven days postoperative, and the hydrogel showed a trend for a faster repair. The results of the histological evaluation showed statistically significant difference in inflammatory tissue reaction between treatments in all periods studied. In quality evaluation, quantity and orientation of collagen fibers, only three days period didnt show statistically significant difference between treatments. We conclude from these results that the two dressings are biocompatible.

Different factors such as growing environmental awareness due to the increasing negative impact of persistent plastic wastes, the uncontrollable price variations of the raw material and the rapid depletion of  reserves have increased the interest in research regarding polymers derived from renewable sources to replace petroleum-based materials. One of the earth’s most abundant macromolecules is cellulose. The production of cellulose from another resource replaces and reduces the demand from plants, the other resource being cellulose from a bacterial system. Bcaterial cellulose film were produced by fermenting apple waste (apple pomace) from cider production donated by Herrljunga Cider in Herrljunga, Sweden and expired fruit juice, produced by LoveJuice Indonesia, containing a mixture of fruits, mainly apple. As inoculum for the fermentations two different Kombucha cultures were used. To optimize the fermentation conditions, factors such as nitrogen source, sugar content, temperature, pH, surface area, sterilization of the substrate, culture condition and fermentation time was varied to obtain the desired result. The bacterial cellulose films were dried at 50-70 °C in an oven, air-dried or freeze-dried to evaluate the impact of drying technique on the final material. The behavior of the microorganism during fermentation was monitored by sampling and observation. The consumption rate of carbohydrates was analyzed using high performance liquid chromatography (HPLC). The properties of the obtained biofilms were analyzed using thermogravimetric analysis (TGA), tensile testing and determination of cellulose content in the obtained biofilms. Two different sugar concentrations (35 g/l and 70 g/l) and three different caffeine concentrations (0 g/l, 150 g/l and 225 g/l) as nitrogen source were investigated to determine the best condition. A control batch of conventional (black tea and 70 g/l table sugar) Kombucha was used as reference. The highest tensile strength (50 MPa) and thermal stability was observed in the biofilms with the highest yield that had been dried in oven. The biofilms obtained by fermenting apple pomace from the cider industry showed the highest tensile strength and highest thermal stability in comparison to fermenting expired fruit juice. The biofilm obtained by fermenting apple waste(sugar concentration 70 g/l) in combination with sterilizing the substrate without adding any nitrogen source, dried in an oven and purified using 0,1 M NaOH resulted in the highest tensile strength, highest thermal stability and the purest biofilm from a visual aspect. The highest yield was observed in the fermentation of apple pomace (sugar concentration 70 g/l) from the cider industry without sterilization of the initial media with an addition of nitrogen of approximately 450 mg/l). The optimal fermentation period was observed to be 14-15 days, at 25-28 °C under static conditions using a glass vessel with a diameter of 20 cm and an initial pH of 5,5.

La cellulose bactérienne (CB) est bien connue pour sa biocompatibilité, moulabilité, pureté et cristallinité ainsi que pour sa structure fibrilleuse nanométrique. Cependant, la production des matériaux par des microorganismes est innovante. La présente thèse initialise ce type de bioproduction dans nos laboratoires. Les bactéries productives de cellulose sont isolées à partir d'un vinaigre Libanais. Plusieurs études cinétiques sont établies. Les isolats sont étudiés dans différents milieux de cultures en variant la source de carbone et la température d'incubation, pour déterminer les conditions optimales recommandées pour la production de meilleurs rendements de CB. La bactérie productive de CB a été étudiée en détails au niveau de son cycle de vie et phases de croissance. La physiologie des cellules a été clarifiée et les mécanismes qui précédent et qui accompagnent la synthèse de CB ont été expliqués. Un modèle mathématique se basant sur l'équation logistique est employé pour standardiser les paramètres étudiés. Le rendement de CB a été accru en appliquant différents chocs aux cellules. Le choc thermique appliqué pendant les étapes précoces d'incubation ainsi que le choc acide ont montré des résultats innovants et accéléré le métabolisme de synthèse de CB. L'aspect environnemental du travail a été valorisé en préparant un milieu de culture extraits des fruits et légumes endommagés. En termes d'application, la CB a été utilisée pour produire des papiers et des papiers résistants à l'eau et comme additive dans un prototype d'industrie de papier. Ainsi des composites de cellulose/Liquides ioniques ont été produits afin de performer des matériaux à haute constante diélectriques / Bacterial cellulose (BC) is a wellknown polymer of this family. Its main attractive properties are the biocompatibility, moldability, purity, crystallinity and fibrillar structure at the nanoscaled level. The production of such materials by microorganisms is an innovative procedure. In order to trigger this production procedure in our laboratories, the present thesis was the preliminary step to go through this huge micro-world. In the first step, we isolated cellulose producers from Lebanese vinegar. Kinetic studies were established to clarify the profile of the producer and to optimize cellulose production. The isolates were studied under different incubation temperatures in different microbiological media and at different carbon sources levels to determine optimal conditions for BC production. In the second step, cellulose producer was studied concerning bacterial phases and life cycles. Cells physiologies were clarified and mechanisms that accompany cellulose formation on the top of cultures were discussed. A mathematical model was set basing on Logistic equation to standardize the parameters. Then, cellulose yield was enhanced by different cells choc methods. Thermal choc was applied on cultures during earlier stages of incubation. Moreover, acids were used as doping agents to the culture media. In parallel, to satisfy the eco-friendly aspect of the work, bacterial cellulose production was optimized using fruits and vegetables wastes juice. Papers and waterproof papers were produced using BC. BC was also used as an additive in industrial paper making and was found to enhance mechanical resistance of the papers. In addition, a high-K material was performed using bacterial cellulose and ionic liquids

O lactato é um metabólito chave formado pelo metabolismo anaeróbico da glicose nos músculos, e tem se tornado um biomarcador importante no âmbito clínico e esportivo. Atualmente, existem biossensores eletroquímicos portáteis que são capazes de determinar os níveis de lactato no organismo em tempo real. No entanto, tal método é invasivo uma vez que requer amostras de sangue. O presente projeto tem como objetivo desenvolver um biossensor eletroquímico descartável para detecção de lactato no suor. Para isto a configuração do dispositivo foi feita utilizando a celulose bacteriana como substrato para obtenção de um dispositivo que seja resistente à deformação mecânica, especialmente quando molhado e, também, permeável ao suor. A impressão dos eletrodos de carbono neste substrato foi efetuada utilizando o processo de serigrafia. Com os dispositivos produzidos foram realizados experimentos de voltametria cíclica e espectroscopia de impedância eletroquímica, a fim de caracterizar o sensor desenvolvido e investigar a influência do pré-tratamento eletroquímico na sua performance analítica. A partir da modificação da superfície eletródica com nanocubos de Azul da Prússia foi possível desenvolver um sensor eletroquímico para detecção de peróxido de hidrogênio. A cronoamperometria foi utilizada para a determinação da curva analítica para o peróxido de hidrogênio. Com todos os parâmetros da cronoamperometria otimizados, uma dependência linear da corrente catódica com a concentração de peróxido de hidrogênio foi obtida, com a equação: Ip = 0,1 + 4,30 [H2O2], com r2 = 0,999 (n = 3). Esta curva analítica mostrou que a metodologia apresenta um Limite de Detecção e de Quantificação de mol L-1 e mol L-1, respectivamente. Para a configuração do biossensor eletroquímico a enzima lactato oxidase foi incorporada à superfície do papel pelo método de ligação covalente. Adotando esta metodologia foi verificado um aumento da área eletroativa que possibilitou uma melhora significativa no desempenho do sensor desenvolvido. No qual se obteve uma região linear de 1-24,0 mmol L-1 em suor sintético, obtendo-se Limites de detecção e Quantificação de e mol L-1. Tais parâmetros se mostraram adequados já que o suor pode apresentar níveis de aproximadamente 25 mmol L-1 de lactato. De modo geral, foi possível desenvolver uma plataforma eletroquímica no substrato de celulose bacteriana para a detecção de lactato em amostras de suor sintético. O dispositivo desenvolvido apresentou uma boa durabilidade e resistência ao se executarem sucessivas medidas corroborando a viabilidade deste substrato na projeção de sensores vestíveis para a aplicação direta na pele e monitoramento dos níveis de lactato em tempo real. / Lactate is a key metabolite formed in the anaerobic metabolism of glucose in the muscles. It has become an important biomarker in the clinical and sport scopes. Currently, there are portable biosensors that are able to determine lactate levels in real time. However, these methods are invasive since they require blood samples. Herein, we aim to develop a disposable wearable electrochemical biosensor for detection of lactate in sweat. For this purpose the configuration of the device was made with bacterial cellulose substrate in order to be permeable to sweat and resistant to mechanical deformation, especially when wet. The fabrication of the electrodes was made through screen printing technique. Electrochemical impedance spectroscopy and cyclic voltammetry were used to characterize the sensor developed in order to investigate the influence of the electrochemical pre-treatment in the analytical performance of the electrodes. To develop an electrochemical sensor for the detection of hydrogen peroxide the screen printed electrode was modified with Prussian blue nanocubes. Chronoamperometry experiments were used to detect of hydrogen peroxide. From optimized chronoamperometry parameters, a linear dependence of the cathodic current with the hydrogen peroxide concentration was obtained with the equation: Ip = 0.1 + 4.30 [H2O2], with r2 = 0.999 (n = 3). The limit of detection (LOD) and the limit of quantification (LOQ) were mol L-1 e mol L-1, respectively. For the configuration of the electrochemical biosensor the lactate oxidase enzyme was immobilized on the paper surface by the covalent bonding method. Adopting this methodology was verified an increase of the electroactive area that allowed a significant improvement in the performance of the developed sensor. In which a linear concentration range of 1-24.0 mmol L-1 was obtained in the synthetic sweat, obtaining LOD and LOQ of mol L-1 e mol L-1, respectively. Such parameters were adequate since sweat may have lactate levels of approximately 25 mmol L-1. Finally, it was possible to develop an electrochemical platform using the bacterial cellulose substrate for the detection of lactate in samples of synthetic sweat. The developed device presented a good durability and resistance when performing electrochemical measurements assuring the feasibility of this substrate in the projection of wearable sensors for the direct application to skin and monitoring of lactate levels in real time.

Denna kandidatuppsats undersöker framtagningen av ett bakteriellt cellulosamaterial (BC-material), samt undersöker om materialets vattenavvisande egenskaper kan förbättras för att kunna möjliggöra användning som textilt material. Arbetet grundar sig i det faktum att BC- materialet är av en hydrofil karaktär, något som den brittiska designern Suzanne Lee utryckt vara ett problem för dess användningsmöjligheter. Arbetet behandlar en litteraturstudie av BC, vilken ligger till grund för en experimentel del där odling, vattenavvisande beredningar och vattenavvisande tester utförts. Gällande BC-produktion och materialframtagning har faktorer som pH-värde, temperaturförhållanden, och recept visat sig påverka cellulosaproduktionen. Ett varmare temperaturförhållande på 30°C jämfört med rumstemperatur (20- 22°C) har uppvisat bättre cellulosatillväxt. Detsamma gäller även för användandet av äppelcidervinäger i odlingmediumet, vilket uppvisat positiva resultat. Testerna av det framtagna BC-membranet har för det första kunnat bekräfta dess påstådda hydrofilitet. Vidare har även de vattenavvisande behandlingarna visat positiva resultat, även om användarmöjligheterna för materialet fortfarande anses vara begränsade inom det textila området. En ökning av kontaktvinkeln från 40,76° till 96,98° uppvisades efter att en behandling med en syntetisk vaxpolymer applicerats. Denna ökning på drygt 100 % skapade en kontaktvinkel över 90°, vilket teoretiskt betyder att materialets karaktär gått från hydrofilt till hydrofobt. Ett likvärdigt resultat uppvisades även efter en behandling med en vaxdendrimer. Materialet uppvisade dock tydliga resultat på att absorbera vatten vid längre tid av blötläggning, oavsett om det behandlats eller ej. / This bachelor thesis is investigating the development of a material based on bacterial cellulose (BC), as well as examine and test the material's hydrophobic properties. This is made in order to improve its user possibilities as a textile material. The motive is based on the fact that BC- materials have a hydrophilic nature, something that the British designer Suzanne Lee expressed as a problem for its user possibilities. The thesis process a literature study of BC, which is used for an experimental study where cultivation, water repellent treatments and water repellent tests are performed. Regarding BC-production and material creation, factors as pH-levels, temperature conditions and the recipes has shown to affect the cellulose production. The cellulose levels occurred to increase during a warmer condition at 30 °C compared to room temperature (20-22°C), both conditions where used for the cultivation. The same positive results also occurred when apple cider vinegar was used in the cultivation bath. The tests on the developed BC-membrane, initially confirmed its alleged hydrophilic nature. Furthermore, positive results occurred for the water repellant-treated materials, even if the user possibilities still is considered to be limited in the textile field. The contact angle increased from 40.76 ° to 96.98 ° on the material treated with a synthetic wax polymer, which results in a 100% increase. The angle of 90°, theoretically means that the character of the material changed from hydrophilic to hydrophobic. Similar results also occurred after treatment with a wax dendrimer. The material, however, showed significant results in absorbing water when subjected for a longer time of soaking, whether it was treated or not.

Cellulose nanofibrils (CNFs) are nanoscale fibers of high aspect ratio that can be isolated from a wide variety of cellulosic sources, including wood and bacterial cellulose. With high strength despite of their low density, CNFs are a promising renewable building block for the preparation of nanostructured materials and composites. To fabricate CNF-based materials with improved inherent rheological and mechanical properties and additional new functionalities, it is essential to tailor the surface properties of individual CNFs. The surface structures control the interactions between CNFs and ultimately dictate the structure and macroscale properties of the bulk material. In this thesis we have demonstrated different approaches, ranging from non-covalent adsorption and covalent chemical modification to modification of cellulose biosynthesis, to tailor the structure and surface functionalities of CNFs for the fabrication of advanced materials. These materials possess enhanced properties such as water-redispersibility, water absorbency, dye adsorption capacity, antibacterial activity, and mechanical properties. In Paper I, CNFs were modified via the irreversible adsorption of carboxymethyl cellulose (CMC). The adsorption of small amounts of CMC onto the surface of CNFs prevented agglomeration and co-crystallization of the nanofibrils upon drying, and allowed the recovery of rheological and mechanical properties after redispersion of dried CNF samples. In Paper II, CNFs bearing permanent cationic charges were prepared through quaternization of wood pulp fibers followed by mechanical disintegration. The activation of the hydroxyl groups on pulp fibers by alkaline treatment was optimized prior to quaternization. This optimization resulted in individual CNFs with uniform width and tunable cationic charge densities. These cationic CNFs demonstrated ultrahigh water absorbency and high adsorption capacity for anionic dyes. In Paper III, via a similar approach as in Paper II, CNFs bearing polyethylene glycol (PEG) were prepared by covalently grafting PEG to carboxylated pulp fibers prior to mechanical disintegration. CNFs with a high surface chain density of PEG and a uniform width were oriented to produce macroscopic ribbons simply by mechanical stretching of the CNF hydrogel network before drying. The uniform grafted thin monolayer of PEG on the surface of individual CNFs prevented the agglomeration of CNFs and facilitated their alignment upon mechanical stretching, thus resulted in ribbons with ultrahigh tensile strength and modulus. These optically transparent ribbons also demonstrated interesting biaxial light scattering behavior. In Paper IV, bacterial cellulose (BC) was modified by the addition of chitin nanocrystals (ChNCs) into the growing culture medium of the bacteria Acetobacter aceti which secretes cellulose in the form of entangled nanofibers. This led to the in situ incorporation of ChNCs into the BC nanofibers network and resulted in BC/ChNC nanocomposites exhibiting bactericidal activity. Further, blending of BC nanofibers with ChNCs produced nanocomposite films with relatively lower tensile strength and modulus compared to the in situ cultivated ones. The bactericidal activity increased significantly with increasing amount of ChNCs for nanocomposites prepared by direct mixing of BC nanofibers and ChNCs. In Paper V, CNFs were isolated from suspension-cultured wild-type (WT) and cellulose-binding module (CBM) transformed tobacco BY-2 (Nicotiana tabacum L. cv bright yellow) cells. Results from strong sulfuric acid hydrolysis indicated that CNFs from transgenic cells overexpressing CBM consisted of longer cellulose nanocrystals compared to CNFs from WT cells. Nanopapers prepared from CNFs of transgenic cells demonstrated significantly enhanced toughness compared to CNFs of WT cells. / <p>QC 20141103</p> / CARBOMAT

Submitted by Thais Silva do Amaral null (thais_rpss@yahoo.com) on 2016-06-03T19:14:32Z No. of bitstreams: 1 Thais Silva do Amaral-Dissertação.pdf: 3804617 bytes, checksum: 8083e47078da73695bac6f8aa62e3778 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-06-08T13:24:26Z (GMT) No. of bitstreams: 1 amaral_ts_me_araiq_par.pdf: 1221750 bytes, checksum: e72ea0e2cee4ebb7654b4a0d18d9289f (MD5) / Made available in DSpace on 2016-06-08T13:24:26Z (GMT). No. of bitstreams: 1 amaral_ts_me_araiq_par.pdf: 1221750 bytes, checksum: e72ea0e2cee4ebb7654b4a0d18d9289f (MD5) Previous issue date: 2015-05-12 / Polímeros derivados do petróleo como polietileno tereftalato (PET) e polietileno naftalato (PEN), são utilizados em larga escala como substratos em diversos dispositivos eletrônicos. A crescente preocupação com o meio ambiente nos leva a buscar alternativas sustentáveis na utilização de materiais para fabricação de novas tecnologias. Neste trabalho, com o intuito de avaliar a viabilidade da substituição destes substratos por polímeros naturais, foi explorada uma biocelulose, a celulose bacteriana (CB), secretada por bactérias Acetobacter xylinum, que é um polímero de obtenção ―verde‖, não gerando resíduos ou altos impactos ambientais para ser produzida, além de possuir características desejáveis para ser utilizado como substrato em novos materiais, como resistência mecânica com módulo de Young de 134 GPa, tamanho nanométrico das fibras e transparência. Membranas funcionais foram obtidas pelo crescimento de nanofios de óxido de zinco na sua superfície. Os nanofios de ZnO foram obtidos com comprimento médio de 1,69 ± 0,08 μm e diâmetro de 37,2 ± 4,2 nm. Os materiais foram avaliados estruturalmente pela Difratometria de Raios-x (DRX) e Microscopia Eletrônica de Transmissão de Alta Resolução (HRTEM), e quimicamente utilizando Espectroscopia de Espalhamento Raman e Espectroscopia Vibracional na Região do Infravermelho (FT-IR). Também foram realizadas de medidas de Impedância Elétrica e Análise termogravimétrica (TG/DTG). Por fim os materiais foram testados em três diferentes aplicações: como membrana para fotodegradação de corantes, sensor piezoelétrico e substrato removível para obtenção de fios de ZnO não suportados que se mostraram aplicações viáveis para o material. / Petroleum-derived polymers such as Polyethylene Terephthalate (PET) and Polyethylene Naphthalate (PEN), are largely used as substrates in various electronic devices. The growing concern with the environment leads us to seek sustainable alternatives in the use of materials for the manufacture of new technologies. In this work, in order to assess the feasibility of replacing these substrates by natural polymers, bacterial cellulose (BC) was explored, secreted by bacteria Acetobacter xylinum is a ―green‖ polymer that don’t generate waste or high environmental impacts to be produced, and has desirable characteristics for use as new substrate materials, such as mechanical strength with Young's modulus of 134 Gpa, nano-sized fibers and transparency. Functional membranes were prepared by growing ZnO nanowires on the BC dried membranes surface. The obtained ZnO nanowires presented an average length of 1.69 ± 0.08 m and diameter of 37.2 ± 4.2 nm. Materials were evaluated structurally by X-ray Diffraction (XRD) and High-resolution Transmission Electron Microscopy (HRTEM), chemically using Raman Scattering spectroscopy and Vibrational Spectroscopy in the Infrared Region (FT-IR). Electrical Impedance measurements and thermal gravimetric analysis (TG / DTG) were performed as well. Finally the materials were tested in three different applications: as a membrane for dyes photodegradation, piezoelectric sensor and removable substrate for obtaining unsupported ZnO nanowires that are viable applications for the material.