Orientador: Rubens Maciel Filho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-20T08:38:40Z (GMT). No. of bitstreams: 1 Bonon_AndersonDeJesus_M.pdf: 18231652 bytes, checksum: 5f90aa98f05330f8a92f9b1163036e84 (MD5) Previous issue date: 2012 / Resumo: Uma das olefinas de fontes renováveis de maior importância no Brasil é o Limoneno, terpeno que compõe cerca de 90% do óleo da casca da laranja. O Brasil é o maior produtor mundial de laranja, com uma produção, entre 2010-2011, de cerca de 15,33 milhões de toneladas do fruto, dos quais 89% da produção são destinadas à produção de suco, sendo a casca e o óleo fixo, resíduos do processo. A parte volátil do óleo é constituída majoritariamente de (R)-limoneno (90 %). Terpenos como o limoneno, podem ser submetidos a reações de oxidação catalítica nos quais os epóxidos são os principais produtos, e podem ser utilizados como precursores para uma ampla variedade de produtos como fármacos, fragrâncias e na fabricação de biopolímeros e resinas. Mediante ao exposto, este trabalho tem por objetivo o estudo da epoxidação de limoneno para a obtenção de epóxidos que possam ser utilizados como monômeros para a síntese de biomateriais para a construção de dispositivos médicos, sendo que avaliou-se sistemas epoxidativos contenho metiltrioxorênio, montmorilonita e alumina. O sistema mais promissor, utilizando H2O2 como oxidante, ?-Al2O3 como catalisador em acetato de etila, foi avaliado em condições reacionais brandas, a 80 °C em pressão atmosférica, caracterizando um sistema verde. As variações na concentração inicial de reagentes a fim de entender o sistema foram estudadas, o que direcionou o estudo para sua otimização via planejamento de experimentos, sendo atingida uma conversão de 100 % em 10 h de reação. A obtenção de limoneno por evaporação de passo curto do óleo de laranja também foi estudada e otimizada, chegando-se à pureza de 99,6 %. O ensaio nas condições ótimas de reação com o limoneno obtido do óleo de laranja mostrou-se idêntico ao limoneno comercial. Os resultados obtidos demonstram a eficácia tanto do processo de obtenção do limoneno, como do sistema reacional com uma produção limpa, uma característica imprescindível para biofabricação / Abstract: One of the most important olefins from a renewable source of in Brazil is limonene. The orange peel oil is about 90% limonene. Brazil is the largest producer of orange in the world wild, with a 2010-2011 production about 15.33 million tons of fruit. About 89% of the fruits are intended for the production of juice, which peel and fixed oil are residue from the process. The volatile oil portion is composed predominantly of (R)-limonene. Terpenes such as limonene, may be subjected to catalytic oxidation reactions where the epoxides are the main products, and can be used as precursors for a wide variety of products such as pharmaceuticals, fragrances and the manufacture of biopolymers and resins. By the above, this work is dedicated to study the epoxidation of limonene in order to obtaining epoxides that may be used as monomers for the synthesis of biomaterials with chemical quality to medical devices manufacturing. Thus, some systems like methyltrioxorhenium, montmorillonite and alumina were tested. The most promissory system, using H2O2 as oxidant, ?-Al2O3 as catalyst and ethyl acetate as solvent, was evaluated in mild reaction conditions, at 80 °C at atmospheric pressure, featuring a green system. It was carried out the initial concentration of the substrate, oxidant and catalyst variation studies in order to understand the system, which directed for the optimization by experimental design. It was achieved a 100% of conversion in 10 hours of reaction. It was also studied the limonene purification by short path evaporation of the orange oil. It was achieved a limonene with 99.6 % of purity. The optimum reaction conditions were performed with limonene obtained from orange oil, the comparative result showed and an identical behavior between the commercial and the distillated limonene. These results demonstrate the effectiveness of both the process, the limonene obtainment and the reaction system with a clean and no toxic production, an essential feature for biofabrication / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Nous proposons l’innovation «TR-NEWS retardée» comme une extension des méthodes TR-NEWS,issues de la symbiose du retournement temporel (RT) et des méthodes de spectroscopie d’ondes élastiques non linéaires (NEWS), avec pour principales applications le contrôle non destructif (CND) et l’imagerie ultrasonore médicale. Nous confirmons expérimentalement les bonnes performances des méthodes TR-NEWS pour : (i) des échantillons de composite CFRP aux propriétés dispersives ultrasonores autour de 10 MHz, favorisant ainsi la réverbérabilité de la propagation acoustique; (ii) des mesures de propriétés non classiques de la peau porcine par une instrumentation multi-échelles acousto-mécanique élaborée dans le cadre du projet PLET(Propriétés Locales Visco-Élastiques de la peau par TR-NEWS) financé par la Région Centre Val de Loire. via les simulations numériques 1D pseudo spectrales de propagations acoustiques non linéaires dans les CFRP, nous identifions et localisons les sources locales de défauts et de microendommagements. Elles valident l’identification d’un crack unique proche de la zone de focalisation. La non linéarité supposée de type contact acoustique (CAN),mesurée par «TR-NEWS retardée»et comparée aux techniques classiques d’inversion d’impulsion utilisées en imagerie médicale, permet une identification préservant la représentation temporelle de l’information. Ainsi, ce système d’instrumentation acousto-mécanique envisage la mesure de paramètres multi-échelles de non linéarité des tissus biologiques via les paramètres de Preisach-Mayergoyz (espaces PM) permettant de décrire leur vieillissement. Le chargement basse fréquence uniaxial (0.1-10Hz) synchronisé aux caractérisations ultrasonores haute fréquence (20MHz) via «TR-NEWS retardé» suggère une nouvelle classe de dispositifs dotée d’une perspective de multimodalité dédiée à l’imagerie ultrasonore non invasive des propriétés biomécaniques des organismes vivants. / In this thesis the possibility of nonlinear ultrasonic NDT is investigated for complex materials and biological tissues. The delayed TR-NEWS signal processing methodis developed, which is based on the TR-NEWS method. TR-NEWS is a method well-suited for materials with complex structure: it allows spatio-temporal focusing of a long ultrasonic chirp signal to the region near the receiving transducer, forming an impulse pulse. The received signal power and SNR are increased as a result.Delayed TR-NEWS allows the use of this focused wave pulse as a new basis for either the signal optimisation or, alternatively, for the detection of nonlinearity by the breakdown of linear superposition. This method is used in physical experiments and simulations. The physical experiments are made on an undamaged CFRP block and a porcine skin sample. The skin is tested in a synchronised acoustomechanical setup specially designed in the course of this thesis. In 1D pseudospectral simulations for CFRP, it is determined that while classical nonlinearity cannot probably be detected in ultrasonic NDT, it could be possible to detect nonclassical nonlinear effects such as those from cracks and microdamage.Physical experiments and 2D FEM simulations of linear, undamaged CFRP are compared for studying the delayed TR-NEWS method, its applicability in optimising the focused wave, and also for creating an interaction of waves at the focusing region with a linear superposition prediction. This suggests the possibility of detecting nonlinearities by comparing the actual signal from interaction to the linear prediction.Finally, more 2D simulations are conducted for CFRP with a single contact gap nonlinearity near the focusing region. The nonlinearity is measured by PI and delayed TR-NEWS. It is determined that delayed TR-NEWS is able to detect the defect at least as well as the PI method. It is ascertained that the PM hysteresis model could describe the nonclassical nonlinearity of damaged materials and biological tissues. Asynchronised acoustomechanical test setup is created to test such multiscale nonlinearity. The simultaneous mechanical load test and ultrasonic delayed TR-NEWS test can be used to measure the mechanical properties of skin

Tissue engineering is an interdisciplinary field which aims to create substitutes of damaged tissues by combining cells with biomaterials. Cells are extremely sensitive to their microenvironment and so the cell response to biomaterials can be regulated by different extrinsic stimuli and alterations of biomaterial properties. Successful implant integration into the tissue can therefore be promoted by appropriate surface roughness, chemical composition, adhesion ligand density, as well as the availability of growth factors. This thesis mainly focuses on the development of orthopedic replacements and the improvement of the currently used blood vessel prostheses. Through the study of cell-biomaterial interactions, it was demonstrated that superimposed topography with features ranging from the nano to micro scale promotes cell spreading, proliferation, and the metabolic activity of osteoblast-like cells. Moreover, when comparing the chemical composition of biomaterials for orthopedic implants, higher osteoblast densities were observed on composites with 5-15 vol. % of calcium phosphate nanoparticles, while concentrations of 25 vol. % did not support cell proliferation. Cell viability, however, was not affected. In vivo, a more intensive formation of new bone tissue, was found on samples containing...

In this study the properties of composites made of wood flour and thermoplastics have been investigated. In order to improve the interfacial adhesion between hydrophobic and nonpolar thermoplastics and hydrophilic and polar wood flour different additives have been used as compatibilizers in composites systems. The interaction between a wood filler and thermoplastic matrix, with and without compatibilizers, has been studied using conventional mechanical testing, impact testing, dynamic mechanical thermal analysis (DMTA), electron microscopes and infrared spectroscopy. Tests of mechanical properties, such as maximum tensile strength, tensile modulus and impact strength have shown that maleic anhydride grafted styrene-ethylene/butylene-styrene triblock copolymer (SEBS-MA) acts as a compatibilizer in the composite system. The SEBS-MA improves the stress transfer from the matrix to the wood particles and forming an flexible interphase around the wood particle and therefore improves the impact properties. The DMTA measurements indicated that there is an interaction between the wood surfaces and the maleic anhydride part of the SEBS-MA copolymer, and also between PS and wood. Morphological studies with SEM and TEM showed that the addition of SEBS-MA improved the adhesion between the wood particles and polymer matrix and that the compatibilizer is located at the interphase region between them. An infrared spectroscopy study indicated that the MA in the SEBS may react with the wood by forming hydrogen- and esterbonds and also possibly interaction between PS and wood. / Godkänd; 1997; 20061128 (haneit)

It is projected that by 2020, there will be 138 million Americans over 45, the age at which the increased incidence of heart diseases is documented. Many will require stents. This multi-billion dollar industry, with over 2 million patients worldwide, 15% of whom use Nitinol stents have experienced a decline in sales recently, due in part to thrombosis. It is a sudden blood clot that forms inside stents. As a result, the Food and Drug Administration and American Heart Association are calling for a new generation of stents, new designs and different alloys that are more adaptable to the arteries. The future of Nitinol therefore depends on a better understanding of the mechanisms by which Nitinol surfaces can be rendered stable and inert. In this investigation, binary and ternary Nitinol alloys were prepared and subjected to various surface treatments such as electropolishing (EP), magnetoelectropolishing (MEP) and water boiling & passivation (W&P). In vitro corrosion tests were conducted on Nitinol alloys in accordance with ASTM F 2129-08. The metal ions released into the electrolyte during corrosion tests were measured by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). Biocompatibility was assessed by observing the growth of human umbilical vein endothelial cells (HUVEC) on the surface of Nitinol alloys. Static and dynamic immersion tests were performed by immersing the Nitinol alloys in cell culture media and measuring the amount of metal ions released in solution. Sulforhodamine B (SRB) assays were performed to elucidate the effect of metal ions on the growth of HUVEC cells. The surfaces of the alloys were studied using Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS) respectively. Finally, wettability and surface energy were measured by Contact Angle Meter, whereas surface roughness was measured by Atomic Force Microscopy (AFM). All the surface treated alloys exhibited high resistance to corrosion when compared with untreated alloys. SRB assays revealed that Ni and Cu ions exhibited greater toxicity than Cr, Ta and Ti ions on HUVEC cells. EP and MEP alloys possessed relatively smooth surfaces and some were composed of nickel oxides instead of elemental nickel as determined by XPS. MEP exhibited lowest surface energy and lowest surface roughness.

Hyaluronic acid (HA) is an essential molecule in the development of many tissues in the organism, as well as in their regeneration. Although, its physicochemical properties greatly limit its use as a cell support material in clinical applications unless its chemical structure is modified or is accompanied by other molecules. In this thesis a tridimensional scaffold has been made consisting of hyaluronic acid and a second material, an acrylic polymer (poly[ethyl acrylate] or PEA) able to be polymerized by free-radical polymerization inside HA after lyophilisation. The resultant interpenetrating polymer network (IPN) has been analyzed in order to measure its properties and compare them to similar scaffolds made from the two separate polymers, with the aim to compare the effects produced by the synthesis technique in the physical and chemical properties of HA. The viability of these materials in cell applications has been tested through in vitro assays using L929 fibroblasts. Additionally, several modifications have been made to the initial synthesis technique in order to obtain different proportions from the two components - HA and PEA - in the materials. The properties of these IPNs have been measured to reveal the effects produced by every step along their synthesis. The biomaterials produced though the techniques described here may offer interesting systems for cell culture and/or cell transplants in future clinical applications that wish to incorporate hyaluronic acid in the shape of a stable tridimensional scaffold. / El ácido hialurónico (HA) es una molécula imprescindible en la formación de muchos tejidos del organismo, así como en la regeneración de los mismos. No obstante, sus propiedades físico-químicas limitan enormemente su uso como material para el soporte de células en aplicaciones clínicas si no se modifica su estructura química o se acompaña de otras moléculas. En esta tesis se ha sintetizado un constructo tridimensional de ácido hialurónico acompañado por un segundo material, un polímero acrílico (el poliacrilato de etilo, o PEA) capaz de polimerizar por vía radical en el interior del HA tras liofilizarlo. La red interpenetrada polimérica (IPN) resultante ha sido analizada para medir sus propiedades y compararlas con constructos semejantes realizados a partir de ambos polímeros por separado, con el objetivo de comprobar los efectos de la técnica de síntesis en las propiedades físico-químicas del HA. La viabilidad de estos materiales en aplicaciones con células ha sido comprobada mediante la realización de ensayos in vitro con fibroblastos L929. De forma adicional, se han llevado a cabo varias modificaciones de la técnica inicial de síntesis para obtener distintas proporciones de ambos componentes - HA y PEA - en los materiales. Las propiedades de esta serie de IPNs han sido medidas y comparadas con su método de síntesis y composición final con tal de dilucidar el efecto que produce cada paso de la síntesis en las mismas. Los biomateriales producidos mediante las técnicas aquí descritas pueden ofrecer sistemas interesantes para el cultivo y/o trasplante de células en futuras aplicaciones clínicas que deseen incorporar el ácido hialurónico en forma de constructo tridimensional estable. / L'àcid hialurònic (HA) és una molècula imprescindible en la formació de molts teixits de l'organisme, així com en la regeneració dels mateixos. D'altra banda, les seves propietats físico-químiques limiten enormement el seu ús com a material per al suport de cèl¿lules en aplicacions clíniques si no se'n modifica l'estructura química o se l'acompanya d'altres molècules. En aquesta tesi s'ha sintetitzat un constructe tridimensional d'àcid hialurònic acompanyat d'un segon material, un polímer acrílic (el poliacrilat d'etil, o PEA) capaç de polimeritzar per via radical a l'interior del HA després de liofilitzar-lo. La xarxa interpenetrada polimèrica (IPN) resultant ha sigut analitzada per mesurar les seves propietats i comparar-les amb constructes semblants realitzats a partir d'ambdós polímers per separat, amb l'objectiu de comprovar els efectes de la tècnica de síntesi en les propietats físiques y químiques del HA. La viabilitat d'aquests materials en aplicacions amb cèl¿lules ha sigut comprovada mitjançant la realització d'assajos in vitro amb fibroblasts L929. Addicionalment, s'han dut a terme vàries modificacions en la tècnica inicial de síntesi per tal d'obtenir diferents proporcions d'ambdós components - HA i PEA - als materials. Les propietats d'aquesta sèrie de IPNs han sigut mesurades per tal de revelar l'efecte que produeix cada pas de la síntesi sobre les mateixes. Els biomaterials produïts mitjançant les tècniques aquí exposades poden oferir sistemes interessants pel cultiu y/o trasplantament de cèl¿lules en futures aplicacions clíniques que desitgin incorporar l'àcid hialurònic en forma de constructe tridimensional estable. / Rodríguez Pérez, E. (2017). Diseño de nuevos biomateriales basados en redes poliméricas interpenetradas de ácido hialurónico y polímeros acrílicos [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/90632 / TESIS

付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラム / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22469号 / 工博第4730号 / 新制||工||1739(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 秋吉 一成, 教授 近藤 輝幸, 教授 梅田 眞郷 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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The aim of the proposed diploma thesis is to optimize the procedure of collagen isolation from animal tissues and methods for molecular characterization of isolates. In experimental part, isolations of collagens from animal tissues (chicken, hen, carp, and pork skin) were performed. Total protein concentration was determined by Biuret method and by TNBSA method. Both methods were used also in order to study physiological and thermal stability of the isolates under model conditions. Isolated collagens were characterized at molecular level using PAGE–SDS and microfluidic electrophoresis. Further, amino acids composition and microelement content were analyzed. Finally, the stability of isolated collagens in several types of simulated physiological and pathological conditions was tested too. During isolation relatively sufficient collagen yields were obtained (about 15 % of purified collagen per original mass of biological material). In all analyzed tissues Type I collagen was found. Thermal stability of individual samples differed according to biological source type and tissue age. Viscosimetry measurements confirmed higher stability in collagen samples of older animals. Collagenase exhibited the lowest degradation effect to bovine collagen, while selected mixed microbial hydrolases differed according to enzyme preparative type. Incubation of collagen isolates with selected human pathogens confirmed higher resistance of bovine collagen to biofilm formation when compared with the chicken one.

The aim of this thesis was the preparation of a biomaterial ink for the fabrication of chemically crosslinked hydrogel scaffolds with low micron sized features using melt electrowriting (MEW). By developing a functional polymeric material based on 2-alkyl-2-oxazine (Ozi) and 2-alkyl-2-oxazoline (Ox) homo- and copolymers in combination with Diels-Alder (DA)-based dynamic covalent chemistry, it was possible to achieve this goal. This marks an important step for the additive manufacturing technique melt electrowriting (MEW), as soft and hydrophilic structures become available for the first time. The use of dynamic covalent chemistry is a very elegant and efficient method for consolidating covalent crosslinking with melt processing. It was shown that the high chemical versatility of the Ox and Ozi chemistry offers great potential to control the processing parameters. The established platform offers straight forward potential for modification with biological cues and fluorescent markers. This is essential for advanced biological applications. The physical properties of the material are readily controlled and the potential for 4D-printing was highlighted as well. The developed hydrogel architectures are excellent candidates for 3D cell culture applications. In particular, the low internal strength of some of the scaffolds in combination with the tendency of such constructs to collapse into thin strings could be interesting for the cultivation of muscle or nerve cells. In this context it was also possible to show that MEW printed hydrogel scaffolds can withstand the aspiration and ejection through a cannula. This allows the application as scaffolds for the minimally invasive delivery of implants or functional tissue equivalent structures to various locations in the human body. / Das Ziel dieses Projekts war die Herstellung einer Biomaterialtinte, welche die Herstellung chemisch vernetzter, mikrostrukturierter Hydrogelgerüste mittels Melt Electrowriting (MEW) ermöglicht. Die Verwendung von speziell auf den schmelzbasierten 3D Druck angepassten polyoxazinbasierten Polymeren und die Anwendung von dynamisch kovalenter Chemie ermöglichte es, dieses Ziel zu erreichen. Dies ist ein wichtiger Schritt für die aufstrebende, additive Fertigungstechnologie MEW, da nun erstmals weiche und hydrophile Strukturen erzeugt werden können. Speziell die Verwendung der dynamischen Diels-Alder (DA) Chemie ist ein effizienter Weg, die Fertigung von kovalent vernetzten Strukturen mit der Schmelzprozessierung zu vereinen. Es wurde weiterhin gezeigt, dass die hier etablierte Materialplattform die Möglichkeit zur Modifikation mit biologischen und chemischen Signalen bietet. Dies ist besonders für biologische Anwendungen unerlässlich. Die physikalisch-chemischen Eigenschaften des Materials lassen sich leicht auf potentielle Anwendungen anpassen und das Potential für den 4D Druck wurde ebenfalls hervorgehoben. Alles in Allem legt diese Arbeit den Grundstein für eine Vielzahl von verschiedenen Anwendungen sowohl in der Biomedizin als auch in anderen Bereichen.