Orientador: Marisa Masumi Beppu / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-22T20:50:50Z (GMT). No. of bitstreams: 1 Taketa_ThiagoBezerra_M.pdf: 4178929 bytes, checksum: 10d5bd8df33f074970da2596a3ef43a0 (MD5) Previous issue date: 2013 / Resumo: A busca por materiais que possam constituir superfícies antimicrobianas é relevante uma vez que o contato com micro-organismos patogênicos representa um sério risco à saúde. Além das propriedades naturais biocidas de alguns materiais, a adição de compostos que também atuam como agentes antibióticos como íons metálicos ou peptídeos, podem potencializar essa funcionalidade. Existe também a alternativa de criar-se uma superfície antimicrobiana através da modificação da densidade e da mobilidade de cargas catiônicas dos materiais utilizados, assim como propriedades estruturais dos revestimentos visando dificultar a adesão ou crescimento de micro-organismos. Neste trabalho, os filmes foram construídos pela técnica layer-by-layer, na qual é feita a imersão de um substrato (lâmina de vidro) alternadamente em soluções que contêm cargas positivas ou negativas e, no intervalo entre cada submersão, o filme em formação passa por um processo de lavagem em água deionizada para a retirada do excesso de polieletrólitos. Especificamente, foram utilizados o biopolímero catiônico quitosana (CHI) e os polieletrólitos negativos alginato de sódio (ALG) e ácido hialurônico (HA). Os filmes constituídos de ALG/CHI e HA/CHI foram construídos em diferentes pH e força iônica das soluções polieletrolíticas. Por análises de perfilometria e microscopia de força atômica (AFM) foi possível monitorar mudanças de espessura e rugosidade dos recobrimentos e foi verificado que a presença de sal no meio de deposição faz com que os polímeros apresentem conformações com mais loops e tails e esse arranjo das cadeias em solução é transmitido para os filmes, que se tornam mais rugosos. Além disso, a espessura dos filmes pode ser controlada por meio do ajuste do pH do meio de deposição. A incorporação dos corantes rosa de bengala e azul de alciano, em conjunto com análises de FTIR possibilitou identificar os grupos funcionais responsáveis pela funcionalidade dos recobrimentos formados. Por fim, foram feitos testes dos recobrimentos, com e sem acetato de prata, frente à cepa Candida albicans e foi verificado que filmes contendo Ag+ foram capazes de inibir o crescimento do fungo. O uso sinérgico de polímeros naturais e da técnica LbL viabilizou, de uma maneira simples e versátil, a construção de filmes nanoestruturados com potencial para aplicações antimicóticas / Abstract: The search for materials that can constitute antimicrobial surfaces is relevant since the contact with pathogenic microorganisms is a serious health risk. Besides the natural biocidal properties of some materials, the addition of compounds that also act as antimicrobial agents, such as metal ions or peptides, may enhance this capability. There is also the alternative to create an antimicrobial surface by modifying the density and mobility of cationic charges of the materials used, as well as structural properties of the coatings in order to hinder the adhesion or proliferation of microorganisms. In this work, the nanostructured films were built by the layer-by-layer (LbL) technique, whose interaction among species with opposite electrostatic charges is, in most cases, the primary phenomenon responsible for the formation of multilayers. Specifically, we chose the cationic biopolymer chitosan (CHI) and the negative polyelectrolytes sodium alginate (ALG) and hyaluronic acid (HA). The aim of this study was to evaluate the effect of ionic strength (0 versus 200 mM) and pH (3 versus 5) on ALG/CHI and HA/CHI nanostructured multilayered thin films properties. From profilometry and atomic force microscopy (AFM) analysis, it was possible to monitor changes in thickness and roughness of the coatings and it was found that the presence of salt in polyelectrolyte solutions promoted polymer chains conformations with more loops and tails and this arrangement in solution is transmitted to films, resulting in rougher coatings. Furthermore, the film thickness can be precisely controlled by adjusting the pH of the polyelectrolyte solution. The incorporation of rose bengal and alcian blue dyes in conjunction with FTIR analysis allowed identifying the functional groups responsible for the functionality of the coatings formed. Finally, we evaluated the antifungal activity of the LbL coatings (with and without silver ions) against Candida albicans strain and we observed that films containing Ag+ were able to inhibit the growth of the fungus. The synergistic use of natural polymers and LbL technique made possible, in a simple and versatile way, the construction of nanostructured films with great potential for antifungal surfaces / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Orientador: Rubens Maciel Filho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-19T01:43:50Z (GMT). No. of bitstreams: 1 RuedaMartinez_GuillermoAndres_M.pdf: 4483284 bytes, checksum: 01caeae720e6b42068cb4cc55f6897d9 (MD5) Previous issue date: 2011 / Resumo: O desenvolvimento de materiais para a aplicação em engenharia tecidual vem sendo um dos grandes desafios na pesquisa de biomateriais. Polímeros não tóxicos e biocompatíveis ao corpo humano são estudados para viabilizar sua aplicação em técnicas avançadas de biofabricação, como a prototipagem rápida. Estas técnicas utilizam biomateriais, permitindo manipular e depositar nestes, células vivas em um processo de construção por camadas de matrizes ou -scaffoldsII, possibilitando seu posterior uso como dispositivos médicos. Dentre os biomateriais que podem ser utilizados na prototipagem rápida para uso biomédico, encontra-se o poli (ácido láctico) ou PLA, o qual é sintetizado a partir do ácido láctico que pode ser obtido por fermentação de açúcares extraídos de fontes renováveis, tais como cana-de-açúcar e milho. O PLA é um polímero biocompatível usado em várias aplicações biomédicas, devido à sua degradabilidade em contato com fluidos corpóreos e capacidade de ser absorvido pelo corpo humano. Trata-se de um polímero muito versátil que pode ser produzido com ampla gama de propriedades. Devido a estas características, encontrar os valores ótimos de todas as variáveis para atingir propriedades específicas do produto, torna-se inviável experimentalmente, visto que há elevado custo e grande tempo requerido pelos experimentos. Neste contexto, o objetivo deste trabalho foi desenvolver uma planta de processamento virtual para estudar e simular o processo de síntese do PLA a partir de fontes renováveis usando o simulador comercial ASPEN PLUS®. Através das simulações foram identificadas as relações das propriedades do polímero com as condições operacionais (temperatura, pressão, entre outras) e de projeto (volume reacional), visando obter um produto final com alta massa molar e pureza / Abstract: The development of successful materials for use in tissue engineering has been one of the major challenges in biomaterials research. Biocompatible polymers as well as advanced biomanufacturing techniques, such as rapid prototyping, have been extensively studied. These techniques use biomaterials that allow the manipulation and deposition of living cells in a layer-by-layer building process to create- scaffoldsII for further use as medical devices. Poly (lactic acid) or PLA, which is synthesized from lactic acid obtained by fermentation of sugars derived from renewable sources such as sugar cane and corn, is one of the most common biomaterials employed in rapid prototyping. PLA is a biocompatible polymer used in several biomedical applications due to its high biodegradability in contact with body fluids and its ability to be absorbed by the human body. Furthermore, it is a very versatile polymer that can be produced with a wide range of properties. Therefore, the experimental process to adjust and optimize all the variables in order to achieve specific properties of the product is impractical, not only because of the high economic cost it involves, but also because of the time-consuming nature of the process. In this context, the study and simulation of the synthesis of PLA from renewable sources was proposed using the commercial simulator ASPEN PLUS® in order to identify the relationship between the polymer properties and the operating conditions (temperature, pressure, etc.) as well as the design conditions (reaction volume) so as to achieve a final product with high molecular weight number / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Orientador: Rubens Maciel Filho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-19T01:45:14Z (GMT). No. of bitstreams: 1 RinconLasprilla_AstridJuliana_M.pdf: 3221598 bytes, checksum: 770b6e18d53feb7a64bc70fd5a1e0f6a (MD5) Previous issue date: 2011 / Resumo: Os recentes avanços em biomateriais, como polímeros biodegradáveis e bioreabsorvíveis, juntamente com o desenvolvimento de novas técnicas de biofabricação, estão permitindo criar dispositivos médicos que auxiliam na recuperação de tecidos e/ou órgãos danificados por traumas ou doenças, proporcionando melhor qualidade de vida e saúde pública. O Poli (ácido láctico) (PLA) é, dentre os biomateriais, um dos mais importantes para a produção destes dispositivos, devido às suas propriedades e por ser produzido a partir do ácido láctico, um ácido orgânico de origem biológica, o qual pode ser sintetizado via fermentativa, utilizando açúcares derivados de cana-de-açúcar, no qual o Brasil tem grande destaque mundial. O PLA pode ser obtido por diferentes rotas, mas independente da rota utilizada, requer um rigoroso controle de processo. As condições de operação deste tipo de síntese influenciam amplamente as características finais do produto. Neste contexto, estudar o comportamento do processo de produção de PLA é necessário para desenvolver estratégias de controle que permitam escolher as condições operacionais para obter um produto com as propriedades desejadas. Neste estudo, foi apresentada a síntese e caracterização de PLA por duas rotas convencionais: condensação direta de ácido láctico e síntese por abertura do anel a partir do lactídeo previamente sintetizado a partir de ácido láctico. Também foi realizada a análise das variáveis operacionais (temperatura e tempo de reação), assim como seus efeitos sobre as características do produto, através dos testes de polimerização realizados e da análise das propriedades dos polímeros obtidos. O projeto foi realizado em três partes: síntese do polímero, caracterização deste e comparação dos resultados obtidos pelos dois métodos. As duas rotas de polimerização do ácido láctico resultaram ser adequadas para a obtenção do PLA a partir de ácido láctico nas condições estudadas / Abstract: Recent advances in biomaterials as biodegradable and bioabsorbable polymers, along with the development of new biomanufacturing techniques, are allowing to create medical devices that assist in tissue and/or organs repair damaged by trauma or disease, providing a better quality of life and public health. The Poly (Lactic Acid) (PLA) is, among the biomaterials, one of the most important for the production of these devices due to its properties and because it is produced from lactic acid, an organic acid of biological origin, which can be synthesized through fermentation using sugars derived from sugar cane, in which Brazil has great global leadership. The PLA can be obtained by different routes, but independent from that used, it requires a rigorous process control. The operating conditions of this kind of synthesis largely influence the final characteristics of the product. In this context, studying the behavior of the production process of PLA is required to develop control strategies that allow choosing the operating conditions for a product with the desired properties. In this study is presented the synthesis and characterization of PLA by two conventional routes: direct condensation of lactic acid and ring opening synthesis of lactide previously synthesized from lactic acid. Also carried out analysis of the operating variables (temperature and reaction time), as well as its effects on the characteristics of the product through of the polymerization tests performed and the analysis of the properties of polymers. The project was undertaken in three parts: polymer synthesis, characterization and comparison of the results obtained by two methods. The two routes of lactic acid polymerization were adequate for obtaining the PLA from lactic acid under the conditions studied / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Le milieu marin constitue la plus grande partie de la biosphère et contient les formes les plus anciennes et les plus variées de la vie. Les espèces microbiennes, relativement négligées jusqu’à présent, pourraient bien être le principal gisement de nouvelles molécules des prochaines décennies grâce à leurs adaptations à un environnement marin atypique et/ou à des conditions extrêmes (zones hydrothermales, sédiments des fonds sous-marins, lagunes hyper-salines, continent arctique et antarctique, tapis microbiens…). La Nouvelle-Calédonie est dotée de milieux naturels littoraux, côtiers et marins au sein desquels existent des gradients thermiques, d’hypersalure/dessalure, de chocs UV, de pH, d’évaporation, d’inondation/exondation… qui déterminent des habitats atypiques dans lesquels les micro-organismes doivent développer des stratégies adaptatives et de défense potentiellement uniques. Un travail de bioprospection de ces milieux atypiques a ainsi permis la création d’une souchothèque riche à ce jour de 771 isolats bactériens néo-calédoniens. Sur la base de cette collection, des études ont été engagées pour la recherche et la caractérisation de biopolymères de type exopolysaccharides (EPS) et polyhydroxyalcanoates (PHA). Les EPS sont des complexes osidiques de grande taille dont la composition est variable selon l’organisme producteur. Les PHAs sont des macromolécules formées de liaisons ester présentant de fortes similitudes avec les plastiques issues de la pétrochimie mais sont totalement biodégradables et biocompatibles. Les débouchés pour la valorisation des biopolymères marins sont très variés et touche plusieurs secteurs comme la cosmétique (gélifiant épaississant, antirides, etc.) la santé (immunostimulation, anticoagulant, cicatrisant), l’agroalimentaire, la bioremédiation les emballages, l’enrobage… Les criblages réalisés sur l’ensemble de la collection pour les deux types de polymères ont permis de mettre en évidence qu’une part importante des souches de la collection étaient potentiellement capables de sécréter ces polymères. À l’heure actuelle, 10 types d’EPS et 5 types de PHAs ont été produits et caractérisés afin de cibler des domaines d’applications. L’étude des bactéries marines pour leur faculté à produire des polymères est donc un secteur en pleine expansion et les premiers résultats montrent que ce type de biotechnologies pourrait constituer une perspective de développement intéressante pour la Nouvelle-Calédonie. / Previous works on marine bacteria led to the discovery of molecules of great biotechnological interest. Under unusual physical and chemical conditions some microorganisms have developed various survival strategies including exopolysaccharides (EPS) and Poly-3-hydroxyalkanoates (PHAs) production. Due to their many interesting biological, physical and chemical properties, those polymers have found applications in many industrial sectors. Due to interesting physical and chemical properties, EPS can find applications in many industrial sectors including the food industry, cosmetics, for oil and metal recovery from industrial waste and in the mining industry as well. During the last decades EPS have also been demonstrated as interesting bioactive molecules with many applications for human health. PHAs are biopolyesters accumulated as granules in bacteria in order to endure long starving periods. Those biodegradable biopolymers can be used as an alternative to petroleum derived polymers and can be produced from renewable carbon sources. PHAs exhibit a wide variety of properties and structures depending of the carbon source available and the microorganism used for the production. New Caledonia (NC) is frequently referred as a hotspot biodiversity. During a prospection campaign performed in different marine costal ecosystems of NC, a great number (770) of bacteria were isolated from different locations. Screening showed that 55% of the isolates were able to produce under lab conditions EPS and 53% to produce PHA. Partial chemical characterization was performed on purified samples using colorimetric methods, infrared spectrometry (FTIR), gas chromatography (GC) and nuclear magnetic resonance (NMR). Marine bacteria from New Caledonian ecosystems were shown to produce EPS with unusual chemical composition with potential applications in cosmetics. Preliminary experiments also showed high metal-binding capacity with applications in bioremediation. Different PHAs were also produced using different types of sugars and oil as renewable resources. Blue biotechnologies can have various applications in many industrial sectors (Health, food industry, environment, cosmetics etc…) and there is a great international demand for new molecules issue from marine areas. New Caledonian marine bacteria have proved their capacity for producing innovative biopolymers with a wide range of application that can be valuating in on short time period (environment, cosmetics) or at long time (pharmaceutics, surgeries). These applications are promising in order to develop

This thesis covers the design of an automated multiunit composting system (AMUCS) that was constructed to meet the experimental apparatus requirements of the ASTM D5338 standard. The design of the AMUCS is discussed in full detail and validated with two experiments. The first experiment was used to validate the operation of the AMUCS with a 15 day experiment. During this experiment visual observations were made to visually observe degradation. Thermal properties and stability tests were performed to quantify the effects of degradation on the polymer samples, and the carbon metabolized from the degradation of samples was measured. The second experiment used the AMUCS to determine the effect of synthetic clay nanofiller on the aerobic biodegradability behavior of poly (3-hydroxybutyrate-co-3-hydroxyvalerate).

Filmes à base de biopolímeros podem ser utilizados para produção de embalagens ativas, que além de proteger os alimentos, podem interagir com o produto. No caso de embalagens ativas com atividade antioxidante, tem-se privilegiado o uso de agentes antioxidantes naturais, considerando-se que o uso de antioxidantes sintéticos tem sido questionado, sobretudo em relação à sua inocuidade. Existem muitos extratos de plantas já conhecidos por sua atividade antioxidante, que têm sido utilizados com frequência em estudos de filmes à base de biopolímeros, não somente por serem ricos em polifenóis, mas principalmente por sua boa interação com a matriz polimérica. O extrato de boldo-do-Chile (Peumus boldus) possui atividade antioxidante comprovada, entretanto, não existem relatos sobre sua adição em filmes. Dessa forma, o objetivo geral desta tese foi o desenvolvimento de filmes à base de colágeno ou gelatina adicionados de extrato de boldo-do-Chile, com propriedades físicas e funcionais para seu emprego como embalagens bioativas. Foram realizadas as caracterizações (fenólicos totais, ABTS, DPPH, cor, °Brix e pH) do extrato aquoso de boldo-do-Chile, preparado em quatro diferentes temperaturas. Além disso, foram avaliadas as propriedades reológicas e térmicas da solução de gelatina, e também foram elaborados filmes com as soluções de gelatina e colágeno a partir de soluções filmogênicas com diferentes concentrações de macromoléculas e extrato de boldo. Esses filmes foram caracterizados para conhecimento de suas propriedades mecânicas (tração e perfuração), propriedades óticas (cor e opacidade), espessura, umidade e solubilidade em água. Uma concentração de macromoléculas foi escolhida para a realização de análises complementares, a saber: análises térmicas (DSC), cristalinidade por difração de raio X (DRX), permeabilidade ao vapor de água (PVA), microscopia eletrônica de varredura (MEV), brilho, espectroscopia de infravermelho com transformada de Fourier (FTIR), ângulo de contato, propriedades de barreira UV/Visível e atividade antioxidante. A adição do extrato de boldo-do-Chile nos filmes de gelatina e colágeno produziu filmes com atividade antioxidante, sem prejuízo às demais propriedades estudadas. Observou-se que o extrato aquoso de boldo-do-Chile apresentou propriedades antioxidantes, mas que foram dependentes da temperatura de extração. O extrato de boldo-do-Chile foi capaz de modificar as propriedades térmicas das soluções filmogênicas de gelatina, não sendo observado efeito nas análises reológicas. Por outro lado, o extrato aquoso de boldo-do-Chile não influenciou as propriedades mecânicas, solubilidade, umidade, cristalinidade e a permeabilidade ao vapor de água dos filmes de gelatina ou colágeno. Algumas propriedades térmicas sofreram efeito dos extratos, mas as análises de FTIR não mostraram a formação de novas interações. As propriedades óticas e de barreira UV/Visível foram influenciadas pelo extrato de boldo-do-Chile, sendo que os filmes se apresentaram mais amarelados com o aumento da concentração do extrato de boldo-do-Chile. As micrografias mostraram filmes de gelatina bastante homogêneos e filmes de colágeno com superfícies mais rugosas. Os resultados de brilho e ângulo de contato corroboraram com estas respostas. Em conclusão, os filmes de ambas macromoléculas apresentaram atividade antioxidante, podendo dessa forma, serem considerados como filmes ativos. / Biopolymers based films can be used for the production of active packaging, which in addition to protecting food, can interact with the product. In the case of active packaging with antioxidant activity, natural antioxidants has been privileged, considering the use of synthetic antioxidants has been questioned, especially in relation to their safety. There are many plant extracts known for their antioxidant activity, which have been frequently used in studies of biopolymers based films, not only for being rich in polyphenols, but particularly by their good interaction with the polymer matrix. The boldo extract (Peumus boldus) has antioxidant activity, however, there are no reports on its addition in films. Thus, the objective of this thesis was the development of collagen- or gelatin-based films adding boldo extract, and the analysis of their physical and functional properties for its use as bioactive packaging. The analysis (total phenolics, ABTS, DPPH, color, Brix and pH) of the aqueous extract of boldo were realized under four diverse temperatures. Furthermore, rheological and thermal properties of gelatin solution were evaluated, and in addition, films were prepared with filmogenic solutions of gelatin and collagen in different concentrations of macromolecules and boldo extract. These films were characterized for understanding of their mechanical properties (tensile and puncture tests), optical properties (color and opacity), thickness, moisture and solubility in water. A concentration of macromolecules has been chosen to carry out further analysis, namely: thermal analysis (DSC), crystallinity by X-ray diffraction (XRD), water vapor permeabillity (WVP), scanning electron microscopy (SEM), gloss, Fourier transform infrared spectroscopy (FTIR), contact angle, UV / Visible barrier properties and antioxidant activity. The addition of boldo extract at gelatin and collagen films produced films with antioxidant activity, without prejudice to other properties studied. It was observed that aqueous extract of boldo presented antioxidant properties, but they were dependent on the extraction temperature. Boldo extract was able to modify the thermal properties of filmogenic solutions of gelatin, without effect on rheological analysis. Moreover, the aqueous extract of boldo did not influence the mechanical properties, solubility in water, moisture, crystallinity and water vapor permeability of films of gelatin or collagen. Some thermal properties were affected by extracts, although FTIR analysis did not show formation of new interactions. Optical and UV/Visible barrier properties were infuenced by the addition of boldo extraction, and the films presented had high yellowness with increasing concentration of boldo extract. The micrographs showed gelatin films quite homogenous and collagen films with rough surfaces. Gloss and the contact angle results corroborated these answers. In conclusion, the films of both macromolecules have antioxidant activity and can, thus, be considered as active films.

O processo de extração do óleo de mamona gera, como subproduto, uma torta rica em proteínas, que tem sido utilizada como adubo e contra fitonematóide, devido à sua toxicidade. Entretanto, as proteínas da torta de mamona são ricas em aminoácidos que permitem modificação química com aldeídos bifuncionais, como o glutaraldeído e o glioxal, o que pode ser interessante para a produção de filmes biodegradáveis com propriedades físicas adequadas ao emprego na agricultura. Assim, o objetivo geral deste trabalho foi a produção e caracterização de filmes à base de proteínas extraídas da torta de mamona e reticuladas com glioxal ou glutaraldeído e plastificados com glicerol. Especificamente, estudaram-se o efeito da concentração de proteína e do tipo de reticulante, e o efeito da concentração do reticulante sobre algumas propriedades dos filmes. Os filmes foram produzidos com uma técnica conhecida como tipo \"casting\", que consiste na desidratação de uma solução filmogênica (SF). Os filmes foram submetidos a testes para determinação da umidade, espessura, propriedades mecânicas (testes de tração e perfuração), permeabilidade ao vapor de água, solubilidade em água, cor, opacidade, brilho, além da microestrutura, por microscopia eletrônica de varredura. A concentração da proteína e o tipo de reticulante não influenciaram a umidade, espessura, microestrutura e propriedades óticas. Mas, de maneira geral, os filmes produzidos com o glioxal apresentaram melhores propriedades mecânicas e menor solubilidade em água que aqueles produzidos com glutaraldeído, sendo que a concentração de 6g de proteínas/100g de SF foi a formulação que apresentou os melhores resultados para os testes de tração e de solubilidade em água. Este resultado é muito importante para o emprego dos filmes na agricultura. Por outro lado, a concentração do glioxal não teve efeito sobre a umidade, espessura, propriedades óticas, microestrutura e nem sobre a permeabilidade ao vapor de água, influenciando apenas a solubilidade e as propriedades mecânicas. O teor de glioxal que proporcionou melhores propriedades mecânicas e baixa solubilidade em água foi de 5g/100g de proteínas. Filmes produzidos nessas melhores condições foram submetidos a análises complementares envolvendo testes de hidrofobicidade, propriedades térmicas, espectroscopia de infravermelho com transformada de Fourier, isoterma de sorção e biodegradabilidade. Finalmente, pode-se concluir que as proteínas da torta de mamona são capazes de formar uma matriz bem estruturada e que suas propriedades podem ser melhoradas com a adição de glioxal. / The extraction process of castor oil produces, as a co-product, a cake rich in proteins which has been used as a fertilizer and against plant parasitic nematode, because of its toxicity. However, the proteins of castor bean cake are rich in amino acids which allow chemical modification with bifunctional aldehydes such as glutaraldehyde and glioxal. This may be interesting for the production of biodegradable films with adequate physical properties to the use in agriculture. The objective of this work was the production and characterization of films based on proteins extracted from the castor bean cake and crosslinked with glyoxal or glutaraldehyde and plasticized with glycerol. Specifically, we studied the effect of protein concentration and type of crosslinker and the effect of the crosslinker concentration on some properties of the films. The films were produced with a technique known as \"casting\", which consists of drying a film solution (FS). The films were tested for determination of moisture content, thickness, mechanical properties (tensile and puncture tests), water vapor permeability, water solubility, color, opacity, gloss, and the microstructure by scanning electron microscopy. The protein concentration and type of crosslinking did not affect the moisture content, thickness, microstructure and optical properties. But, in general, films made with glyoxal showed improved mechanical properties and lower water solubility than those produced using glutaraldehyde. And, the concentration of 6g proteins/100 g of FS was the formulation that presented the best results for the tensile tests and water solubility. This result is very important for the use of films in agriculture. Moreover, the concentration of glyoxal had no effect on the moisture content, thickness, optical properties, or on the microstructure and permeability to water vapor, influencing only the solubility and mechanical properties. The concentration of glyoxal that provided the best mechanical properties and low water solubility of proteins was 5g/100g of gelatin. Films produced in the best conditions were subjected to further analyzes involving tests of hydrophobicity, thermal properties, spectroscopy, Fourier transform infrared spectroscopy, water vapor sorption isotherm and biodegradability. Finally, it can be concluded that the protein of castor bean cake are capable of forming a matrix structured and that their properties can be improved with the addition of glyoxal.

Tesis por compendio / [ES] El aprovechamiento de subproductos para producir biocombustibles, energía y compuestos químicos básicos es cada vez más necesario en la situación actual de escasez de petróleo y preocupación por el medioambiente. Muchos compuestos que tradicionalmente han sido producidos a partir del petróleo pueden sintetizarse hoy día de forma biotecnológica empleando recursos renovables. En este contexto, los microorganismos pueden aprovecharse eficazmente como biocatalizadores para llevar a cabo estas transformaciones. Con este tipo de procesos se pueden aprovechar residuos o materias primas renovables para la obtención de productos de interés como bioplásticos de origen microbiano o productos químicos que pueden servir como monómeros para la síntesis de plásticos biodegradables u otro tipo de aplicaciones. La contaminación ambiental causada por los residuos de polímeros sintéticos no biodegradables es un problema en aumento debido a la estabilidad de los compuestos derivados de los combustibles fósiles. En contraste, los bioplásticos pueden obtenerse de fuentes renovables, lo que posibilita el desarrollo de procesos de producción sostenible. En este trabajo de investigación se han estudiado y desarrollado bioprocesos para la producción de polihidroxialkanoatos, 2,3-butanodiol y ácido D-láctico de forma sostenible empleando materias primas renovables como el suero lácteo de quesería, aceite de camelina, glicerina, fracción orgánica de residuos urbanos y residuos de naranja. La caracterización de las materias primas de partida se realizó mediante técnicas de análisis composicional, análisis en HPLC, cromatografía de gases y técnicas espectrofotométricas. Con estos resultados se hizo una selección de cepas bacterianas capaces de sintetizar los productos de interés a partir de los sustratos seleccionados. Una vez seleccionadas las cepas, el trabajo se centró en el desarrollo de los procesos para conseguir buenos rendimientos de fermentación y su escalado. Por lo tanto, este trabajo de investigación aporta conocimientos sobre la identificación y selección de biocatalizadores industriales para el uso de materias primas renovables y residuos industriales para la producción de productos químicos y polímeros de base biológica. Estos estudios allanan el camino para el futuro desarrollo de procesos biotecnológicos sostenibles en el marco de las biorrefinerías y de la bioeconomía circular. / [CA] L'aprofitament de bioproductes per produir biocombustibles, energia i compostos químics bàsics és cada vegada més necessari en la situació actual d'escassetat de petroli i preocupació pel medi ambient. Molts compostos que tradicionalment s'han produït a partir de petroli es poden sintetitzar hui en dia biotecnològicament utilitzant recursos renovables. En aquest context, els microorganismes es poden utilitzar eficaçment com a biocatalitzadors per dur a terme aquestes transformacions. Amb aquest tipus de processos es poden utilitzar residus o matèries primeres renovables per obtenir productes d'interès com bioplàstics d'origen microbià o químics que puguen servir de monòmers per a la síntesi de plàstics biodegradables o altres aplicacions. La contaminació ambiental causada per residus de polímers sintètics no biodegradables és un problema creixent a causa de l'estabilitat dels compostos de combustibles fòssils. Per contra, els bioplàstics es poden obtenir a partir de fonts renovables, permetent el desenvolupament de processos productius sostenibles. En aquest treball de recerca s'han estudiat i desenvolupat bioprocessos per a la producció de polihidroxialcanoats, 2,3-butanodiol i àcid D-làctic de manera sostenible utilitzant matèries primeres renovables com sèrum de llet, oli de camelina, glicerina, fracció orgànica de residus urbans i residus de taronges. La caracterització de matèries primeres inicials es realitza mitjançant tècniques d'anàlisi composicional, anàlisi HPLC, cromatografia de gasos i tècniques espectrofotomètriques. Amb aquests resultats es crea una selecció de soques bacterianes capaç de sintetitzar els productes d'interès dels substrats seleccionats. Una vegada seleccionades les soques, el treball es va centrar en el desenvolupament dels processos per aconseguir uns bons rendiments de fermentació i el seu escalat. Per tant, aquest treball de recerca aporta coneixements sobre la identificació i selecció de biocatalitzadors industrials per a l'ús de matèries primeres renovables i residus industrials per a la producció de productes químics i polímers de base biològica. Aquests estudis amplien el coneixement per al futur desenvolupament de processos biotecnològics sostenibles en el marc de la biorefineria i la bioeconomia circular. / [EN] The use of by-products to produce biofuels, energy and basic chemicals is increasingly necessary in the current situation of oil shortages and environmental concern. Many compounds that have traditionally been produced from oil can now be synthesised in a biotechnological way using renewable resources. In this context, microorganisms can be effectively used as biocatalysts to carry out these transformations. With this type of process, waste streams or renewable raw materials can be used to obtain products of interest such as bioplastics of microbial origin or chemical products that can serve as monomers for the synthesis of biodegradable plastics or other types of applications. Environmental pollution caused by non-biodegradable synthetic polymer waste is a growing problem due to the stability of compounds derived from fossil fuels. In contrast, bioplastics can be obtained from renewable sources, which enables the development of sustainable production processes. In this research work, bioprocesses for the production of polyhydroxyalkanoates, 2,3-butanediol and D-lactic acid using renewable raw materials such as cheese whey, camelina oil, glycerine, organic waste and orange waste were studied and developed. The characterisation of the raw materials was carried out using compositional analysis, HPLC analysis, gas chromatography and spectrophotometric techniques, among others. With these results, a selection of bacterial strains capable of synthesising the products of interest from the selected substrates was made. Once the strains were selected, the work was focused on process development in order to optimize fermentation yields and scale-up. Therefore, this research work provides knowledge on the identification and selection of industrial biocatalysts for the use of renewable feedstocks and industrial wastes for the production of bio-based chemicals and polymers. These studies pave the way for further development of sustainable biotechnological processes in the framework of biorefineries and circular bioeconomy. / Bustamante Jaramillo, DA. (2021). Production of Bio-Based Chemicals and Polymers from Renewable Feedstocks: Bioprocesses Development [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/175819 / TESIS / Compendio

This master thesis deals with the using of microcalorimetry in the study of hydration of biopolymers. Lactose has been selected together with the other biopolymers although it is not among biopolymers but disaccharides. Selected biopolymers are alginate, dextrane, chitosan and hyaluronan of two molecular weights. Lactose has been selected for these purposes mainly because it is a model example to determine whether or not the reaction to moisture between the other samples and the saturated salt solution occurs. The biopolymer hydration study, as opposed to the commonly used perfusion calorimetry method using the possibility of measuring with adjustable moisture has been used an isothermal microcalorimetry method where at two constant temperatures the reaction of the sample to the different moisture released by the saturated salt solution was monitored.

The presented doctoral thesis is focused on preparation of nanoparticles and nanofibers with natural active ingredient and testing their biological effects. Modern types of application forms were prepared from biomaterials based on one or more natural polymers. Chitosan particles were prepared from cross-linked polymer using ultrasonication. A mixture of soy lecithin and cholesterol was used for preparation of liposomes. Poly-3-hydroxybutyrate was used for preparation of combined liposomes, too. All liposome particles were prepared by ultrasonication. Nanofibers were obtained from polyhydroxybutyrate using electrospinning. Mixtures of low-molecular antioxidants obtained by extraction from natural sources were used as active ingredients. Different types of teas, barks, herbs, spices, fruits and vegetables were selected as sources of natural antioxidants. Total phenolic and flavonoid content and total antioxidant activity of extracts were determined using spectrophotometrical methods. Obtained natural extracts were subsequently used for encapsulation. Prepared application forms were characterized in terms of their physicochemical properties. Particle size was monitored by dynamic light scattering. Colloidal stability of particles in suspension was determined using zeta potential. Spectrophotometry was used to evaluate the efficiency of encapsulation of active compounds into particles. The morphology of the new type of combined PHB liposomes was monitored by electron microscopy. Chromatography was used for quantification of individual components of particles. Morphology of nanofibers and incorporation of active agent into their structure were monitored using FTIR-ATR spectroscopy and electron microscopy. Afterwards, antimicrobial, cytotoxic and genotoxic effects of preparations were evaluated. It was found that the most suitable types of extracts for liposome preparation are aqueous and lipid extracts of natural antioxidants. Prepared particles showed excellent stability and good encapsulation efficiency. The study confirmed that incorporation of polydroxybutyrate into liposome structure does not reduce neither the colloidal stability of the particle, nor the efficiency of encapsulation process. Antimicrobial and antimycotic effect of preparations against model microorganisms Micrococcus lutues, Serratia marcescens and Candida glabrata was detected. It was found that process of encapsulation increases the inhibitory effect of natural extracts of antioxidants. The safety of preparations was assessed using two human cell cultures: epidermal keratinocytes and HaCaT cell line. Assays of cell viability and plasma membrane integrity were used to determine cytotoxicity of preparations. Low toxicity of liposome particles was confirmed by a series of cytotoxic tests. Obtained data showed that association of phospholipid with PHB polymer does not cause a significant increase in cytotoxicity in human skin cells. Genotoxicity testing on model procaryotic organism confirmed zero genotoxic potential of preparations. The new type of combined particles and polymeric fibers cant thus be used as a carrier for active ingredients, complex natural extracts, antimicrobial agents and many others.