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The skin is the largest and most easily accessible organ of the human body thus making it the ideal route for systemic drug delivery. The transdermal route of drug delivery offers several advantages compared to the traditional routes including elimination of first pass metabolism and higher patient compliance. However, many drugs are topically and systemically ineffective when applied onto the skin, due to their almost complete failure to penetrate the skin. The main limitation lies in the stratum corneum, the barrier of the skin, which prevent the drug from reaching the deeper skin strata. 5-Fluorouracil is a polar hydrophilic drug and is therefore not a good penetrant through skin. A popular technique to increase transdermal permeation is to use a penetration enhancer, which reversibly reduce the permeability barrier of the stratum corneum. The primary aim of this study was to determine the effect of Brij 97 in the presence and absence of carrageenan on the transdermal delivery of 5-fluorouracil. The formulations were identified by means of confocal laser scanning microscopy and measurement of the particle size. The zeta-potential was measured to determine whether the formulations were stable and the pH was measured to determine if the internal structures of the formulations were affected by the drug. The drug released from the formulations was measured with a VanKel dissolution apparatus. In vitro transdermal diffusion studies were performed using vertical Franz diffusion cells with human epidermal skin. Histopathological studies were carried out on human epidermis skin to determine if the surfactant, Brij 97, had any effect on the skin. Through confocal laser scanning microscopy and particle size measurements, the 4 and 8% Brij 97 formulations without carrageenan could be identified as emulsions while the 15 and 25% Brij 97 formulations without carrageenan could be identified as microemulsions. The 4, 8, 15 and 25% Brij 97 formulations containing carrageenan could be identified as gels. The results obtained from the zeta-potential analysis indicated that the 4 and 8% Brij 97 formulations without carrageenan and 4% Brij 97 formulation with carrageenan are the most electronegative and thus the most stable. The pH measurements confirmed that the internal structure of the formulations was not influenced by the drug. 5-Fluorouracil was released from the formulations. The 4 and 8% Brij 97 formulations without carrageenan had an enhancing effect on the penetration of 5-fluorouracil while the 4, 8, 15 and 25% Brij 97 formulations with carrageenan and the 15 and 25% Brij 97 formulations without carrageenan had an hindering effect on the penetration of 5-fluorouracil. Although carrageenan led to good adhesiveness of the formulation on the skin, it did not lead to the enhancement of the penetration of 5-fluorouracil through the skin. When histopathological studies were carried out on female human abdominal skin, Brij 97, the surfactant, was found to have no damaging effect on the skin structure. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2006.

The skin is the largest and most easily accessible organ of the human body thus making it the ideal route for systemic drug delivery. The transdermal route of drug delivery offers several advantages compared to the traditional routes including elimination of first pass metabolism and higher patient compliance. However, many drugs are topically and systemically ineffective when applied onto the skin, due to their almost complete failure to penetrate the skin. The main limitation lies in the stratum corneum, the barrier of the skin, which prevent the drug from reaching the deeper skin strata. 5-Fluorouracil is a polar hydrophilic drug and is therefore not a good penetrant through skin. A popular technique to increase transdermal permeation is to use a penetration enhancer, which reversibly reduce the permeability barrier of the stratum corneum. The primary aim of this study was to determine the effect of Brij 97 in the presence and absence of carrageenan on the transdermal delivery of 5-fluorouracil. The formulations were identified by means of confocal laser scanning microscopy and measurement of the particle size. The zeta-potential was measured to determine whether the formulations were stable and the pH was measured to determine if the internal structures of the formulations were affected by the drug. The drug released from the formulations was measured with a VanKel dissolution apparatus. In vitro transdermal diffusion studies were performed using vertical Franz diffusion cells with human epidermal skin. Histopathological studies were carried out on human epidermis skin to determine if the surfactant, Brij 97, had any effect on the skin. Through confocal laser scanning microscopy and particle size measurements, the 4 and 8% Brij 97 formulations without carrageenan could be identified as emulsions while the 15 and 25% Brij 97 formulations without carrageenan could be identified as microemulsions. The 4, 8, 15 and 25% Brij 97 formulations containing carrageenan could be identified as gels. The results obtained from the zeta-potential analysis indicated that the 4 and 8% Brij 97 formulations without carrageenan and 4% Brij 97 formulation with carrageenan are the most electronegative and thus the most stable. The pH measurements confirmed that the internal structure of the formulations was not influenced by the drug. 5-Fluorouracil was released from the formulations. The 4 and 8% Brij 97 formulations without carrageenan had an enhancing effect on the penetration of 5-fluorouracil while the 4, 8, 15 and 25% Brij 97 formulations with carrageenan and the 15 and 25% Brij 97 formulations without carrageenan had an hindering effect on the penetration of 5-fluorouracil. Although carrageenan led to good adhesiveness of the formulation on the skin, it did not lead to the enhancement of the penetration of 5-fluorouracil through the skin. When histopathological studies were carried out on female human abdominal skin, Brij 97, the surfactant, was found to have no damaging effect on the skin structure. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2006.

Carrageenans are sulfated polysaccharides found in the cell walls of red algae with 20 – 30 % of the dry weight coming from sulfate esters. The understanding of how heterotrophic bacteria desulfate and depolymerize carrageenan has become a rather arduous endeavor as there are 15 different classes of carrageenan distinguished by the degree of sulfation and the presence or absence of a unique galactose derivative, the 3,6-anhydro-D-galactose. The depolymerization of carrageenan requires the removal of the sulfate substituents, a role fulfilled by sulfatases, which hydrolyze sulfate esters playing a key role in the regulation of sulfation states that determine the function of sulfated biomolecules. Through structural, mechanistic, and sequence-based studies a highly conserved sulfate-binding motif has been identified among sulfatases; however, the molecular determinants for substrate specificity remain largely speculative. Additionally, the largest sulfatase family S1, requires a unique catalytic residue resulting from a post-translationally modified cysteine in order to be functional thus making them difficult to study in vitro. Using a strain of Pseudoalteromonas sp. PS47 isolated in the Boraston Lab I show that the depolymerization of carrageenan is dependent on the degree of sulfation and that recognition of the leaving group is the driving force behind S1 specificity. With little information on the recognition of sulfated biomolecules, the X-ray crystal structures of the three sulfatases from PS47; PsS1_19A, PsS1_19B, and PsS1_NC in complex with their biological substrates provides a deeper understanding of how carbohydrate specific sulfatases recognize their cognate substrate and how this recognition of the leaving group can be extended to other S1 sulfatase families. Furthermore, I show that an exo-acting glycoside hydrolase (PsGH42) requires desulfation of carrageenan oligosaccharides before it can hydrolyze the β-glycosidic linkage, a new specificity of family 42. This research demonstrates how carrageenan depolymerization is entirely dependent on the functionality and specificity of the sulfatases found within the carrageenan utilization locus. / Graduate / 2019-12-07

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / VÃrias estratÃgias tÃm sido utilizadas para que materiais, quando em contato com sangue, possam reduzir a adsorÃÃo de proteÃnas do plasma e, consequentemente, a probabilidade de formaÃÃo de trombos. AlÃm disso, outro problema associado à a calcificaÃÃo, descrita como um processo de formaÃÃo de fosfato de cÃlcio, que à a causa primÃria de falhas em tecidos moles e implantes devido à deposiÃÃo destes sais. A quitosana e a carragenana sÃo dois polÃmeros que apresentam propriedades que os tornam promissores para utilizaÃÃo como biomateriais. A quitosana, em funÃÃo dos grupos amino em sua estrutura, pode promover a adesÃo plaquetÃria, sendo necessÃria uma modificaÃÃo quÃmica, como reaÃÃes de sulfonataÃÃo, que visam diminuir a adsorÃÃo de proteÃnas plasmÃticas. A presenÃa de grupos sulfato na carragenana pode contribuir para a obtenÃÃo de superfÃcies com propriedades antitrombogÃnicas sem a necessidade de modificaÃÃo quÃmica da estrutura. A formaÃÃo de complexos polieletrolÃticos (PECs) alia a biocompatibilidade superior da quitosana com a densidade de carga da carragenana, gerada pela presenÃa dos grupos sulfato. Esse trabalho teve por objetivo estudar os efeitos da calcificaÃÃo e da trombogenicidade de filmes de quitosana e carragenana caracterizando-os atravÃs de tÃcnicas de microscopia e espectroscopia, assim como realizar estudo de revestimento de superfÃcie metÃlica utilizando estes polÃmeros. Observou-se uma diminuiÃÃo nos efeitos de calcificaÃÃo para as blendas de quitosana e carragenana e nos filmes sulfonatados (Ca/P 0,11 ou ausÃncia de fÃsforo), reduzindo a formaÃÃo e deposiÃÃo de sais de cÃlcio quando comparados com a quitosana natural (Ca/P 2,78). Ensaios de adesÃo plaquetÃria mostraram melhoria das superfÃcies de quitosana quando modificadas pela sulfonataÃÃo, ou quando misturadas com carragenana, apresentando adesÃo, em mÃdia, de 1 a 2 plaquetas/0,01 mmÂ, contra a formaÃÃo de trombos em filme de quitosana. No ensaio de revestimento, a modificaÃÃo da superfÃcie metÃlica foi evidenciada pela alteraÃÃo da quantidade percentual de carbono e oxigÃnio na composiÃÃo quÃmica da superfÃcie quando comparado o aÃo eletropolido bruto e apÃs a inserÃÃo da quitosana. As sucessivas mudanÃas sofridas pelo Ãngulo de contato reforÃam o sucesso do grafting dos polÃmeros, atravÃs da formaÃÃo de uma camada hidrofÃlica tanto para quitosana natural quanto para a sulfonatada. Pelos resultados obtidos, pode-se inferir que a quitosana sulfonatada e as blendas de quitosana/carragenana mostram-se promissoras para serem utilizadas como biomateriais em contato com sangue. / Various strategies have been proposed to reduce the plasma proteins adsorption and consequently the probability of thrombus formation on materials when contacted with blood. Furthermore, another problem associated with biomaterials is the calcification process, which is described as calcium phosphate formation, which is the primary cause of failures in soft tissues and implants. Chitosan and carrageenan are two polymers that show properties that make them promising for use as biomaterials. Chitosan, due to amino groups in its structure, may promote platelet adhesion, being necessary to perform a chemical modification on it, such as sulfonation reactions, in order to reduce plasma protein adsorption. The presence of sulfate groups in carrageenan structure may contribute to obtain surfaces with antithrombogenic properties without the need of chemical modification on its structure. The formation of polyelectrolyte complexes (PECs) combines the high biocompatibility of chitosan with the charge density of carrageenan, generated by the presence of sulfate groups. This work aimed to study the effects of calcification and thrombogenicity of chitosan and carrageenan films, characterizing them by microscopy and spectroscopy techniques. We also conducted the study of metal surfaces coating using these polymers. A reduction in the effects of calcification for chitosan and carrageenan blends and for sulfonated chitosan films (Ca/P 0.11 or phosphate absence) was observed, reducing the formation and deposition of calcium salts when compared with pristine chitosan (Ca/P 2.78). Assays of platelet adhesion for chitosan surfaces when modified by sulfonation reaction or when blended with carrageenan, showed adhesion on average of 1 to 2 platelets/0.01mm2 against thrombus formation on chitosan film. For the coating essays, the modification on metal surface was characterized by the changing of carbon and oxygen percentage amount on the chemical composition surface, comparing the raw electropolished steel and grafted chitosan. The successive changes observed in the contact angle reinforce the success of the grafting of polymers, forming a hydrophilic layer both for pristine and sulfonated chitosan. From the results obtained, it can be inferred that the sulfonated chitosan and chitosan/carrageenan blends are promising for use as biomaterials in blood contact.

A estimulação química das fibras aferentes nociceptivas através da injeção de diferentes substâncias álgicas vem sendo estudada em modelos de dor muscular em animais. A carragenina é um dos agentes que produz inflamação aguda e é freqüentemente utilizada em modelos de dor muscular. O nosso objetivo é aprofundar nossa compreensão e explorar em maior detalhe a participação das células gliais (astrócitos e microglia), de citocinas pró-inflamatórias, prostanóides e do óxido nítrico, após a indução de miosite aguda, correlacionando com modelos comportamentais nociceptivos. Para tanto, serão avaliadas as atividades dos mediadores, previamente descritos, na medula espinal dos ratos com e/ ou sem indução de miosite, através do método de Western blotting. Tais investigações poderão vir a ser uma abordagem totalmente inovadora para tentar entender quais são alguns dos mediadores envolvidos neste modelo de dor. Assim, os dados obtidos neste projeto poderão elucidar os mecanismos envolvidos na dor músculo-esquelética, a qual se enquadra nas patologias de difíceis tratamentos e de grande relevância clínica. / Chemical stimulation of nociceptive afferent fibers through the injection of different substances has been studied in different models of muscle pain in animals. Carrageenan is one of the agents that produce inflammation and is often used in models of muscle pain. Our goal is to explore in greater detail the involvement of glial cells (astrocytes and microglia), pro-inflammatory cytokines, prostanoids and nitric oxide after induction of acute myositis and correlate it with nociceptive behavioral models. It will be assessed the activity of these mediators in the spinal cord after induction of myositis in rats, using Western blotting assay. Such investigations may be a totally new approach to try to understand how some mediators are involved in this kind of pain. Thus, the data obtained in this project will elucidate the mechanisms involved in musculoskeletal pain, which are of difficult treatment and of great clinical relevance.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A Angiotensina II (Ang II) exerce suas aÃÃes via receptores AT1 e AT2. Estudos recentes demonstraram que o sistema-renina-angiotensina (SRA) participa da inflamaÃÃo. O objetivo desse estudo foi avaliar o efeito da Ang II em modelos de inflamaÃÃo aguda. Ratos Wistar foram separados nos grupos: salina (Sal), Ang II (1 Âg), losartan (LOS, antagonista de AT1, 62,5 Âg) e CGP42112A (agonista de AT2, 142,5 Âg). O edema de pata foi induzido pela injeÃÃo subplantar (sp) de carragenina (Cg, 100 Âg) ou dextran (DXT, 100 Âg) e foi medido com pletismÃmetro em 0, 1, 2, 3 e 4h. Nos grupos Sal e Ang II, foi colhido tecido da pata para se determinar os nÃveis de mieloperoxidase (MPO), IL-1e TNF-α . Tecidos subcutÃneo e mesentÃrico foram removidos para avaliaÃÃo da degranulaÃÃo de mastÃcitos atravÃs da coloraÃÃo com azul de toluidina. Os grupos Sal e Ang II do edema de pata induzido por DXT foram tratados com mepiramina (MEP, anti-histamÃnico, 10mg/kg) ou metisergida (MET, anti-serotonÃnico, 1,5mg/kg) 1h antes da injeÃÃo de DXT. Ang II (0,5Âg/cavidade, ip) foi injetada 1h antes da injeÃÃo ip de Cg para analisar a migraÃÃo de neutrÃfilos para a cavidade peritoneal. Ang II, LOS e CGP amplificaram o edema de pata induzido por Cg e DXT e essa amplificaÃÃo foi significativa jà na primeira hora. A administraÃÃo de Ang II nÃo alterou a dosagem tecidual de MPO, TNF-α e IL-1 e nÃo induziu ou preveniu a migraÃÃo de neutrÃfilos para a cavidade peritoneal, mas induziu amplificaÃÃo significativa da degranulaÃÃo de mastÃcitos. MEP e MET reduziram a potenciaÃÃo do edema do DXT pela Ang II. Nossos resultados sugerem que a Ang II potenciou a resposta inflamatÃria provavelmente atravÃs de receptores AT2, jà que o antagonista de AT1, o agonista de AT2 e a Ang II amplificaram o edema de pata. Os dados apresentados aqui sugerem que Ang II aumentou a permeabilidade vascular atravÃs da induÃÃo da degranulaÃÃo de mastÃcitos, uma vez que houve amplificaÃÃo precoce do edema de pata da Cg e do edema vascular do DXT, e os antagonistas de serotonina e de histamina inibiram significativamente o aumento do edema de pata. / Angiotensin II (Ang II) exerts its actions via AT1 and AT2 receptors. Recent studies have demonstrated that the renin-angiotensin system (RAS) participates in inflammation. The aim of this study was to evaluate the effect of Ang II on models of acute inflammation. Wistar rats were separated in the groups: saline (Sal), Ang II (1Âg), losartan (LOS, AT1 antagonist, 62.5Âg) and CGP42112A (AT2 agonist, 142.5Âg). Paw edema was induced by subplantar injection of carrageenan (Cg, 100Âg) or dextran (DXT, 100Âg) and was measured with a plethysmometer at 0, 1, 2, 3 and 4h. In the Sal and Ang II groups, paw tissue was taken to determine myeloperoxidase (MPO), IL-1 and TNF-α levels. Subcutaneus and mesenterium tissue were taken to evaluate mast cell degranulation through the toluidine blue staining. Sal and Ang II groups of DXT-induced paw edema were treated i.p. with mepyramine (MEP, anti-histamine, 10mg/kg) or metisergyde (MET, anti-serotonin, 1.5mg/kg) 1h prior to the injection of DXT. Ang II (0.5Âg/cavity, ip) was injected i.p. 1h before the i.p. injection of Cg to analyse the leukocytes migration to the peritoneal cavity. Ang II, LOS and CGP enhanced the Cg and DXT-induced paw edema and this enhancement was already significant at 1h. The administration of Ang II did not change the tissue content of MPO, TNF-α and IL-1 and did not induced or prevented neutrophil migration to peritoneal cavity, but induced significant enhancement of mast cell degranulation. MEP and MET reduced the Ang II-facilitated DXT-induced edema. Our results suggest that Ang II enhances the inflammatory response probably through the AT2 receptors since the AT1 antagonist, AT2 agonist and Ang II potentiated the paw edema. The data presented here also suggest that Ang II increases the vascular permeability through induction of mast cells degranulation, since there was early amplification of Cg paw edema and DXT vascular edema, and antagonists of serotonin and histamine significantly inhibited the increase in paw edema.

Les produits laitiers d’aujourd’hui contiennent souvent des polysaccharides qui permettent de les texturer et de les stabiliser. La compréhension et le contrôle de ces mélanges sont essentiels pour la fabrication et le développement de nouveaux produits. Le carraghénane est un polysaccharide sulfaté provenant des algues. Il existe principalement trois types de carraghénanes : le λ-carraghénane, le κ-carraghénane (KC) et l’ τ-carraghénane (IC). Les deux derniers sont ceux utilisés pour notre étude. Le KC et l’IC présentent une transition pelote-hélice en dessous d’une température critique qui dépend du type et de la concentration de cations. Dans la conformation hélice, les chaînes peuvent s’agréger, puis gélifier. La caséine est la protéine majoritaire du lait. Dans le lait, elle est présente sous forme d’un complexe stabilisé par le phosphate de calcium colloïdal (CCP). Le caséinate de sodium (SC) est obtenu à partir de la caséine native en enlevant le CCP par acidification, puis par addition de soude. Dans l’eau, les particules de SC ont un rayon de 11nm et sont constituées d’environ 15 molécules de caséines. Les mêmes particules peuvent être formées par chélation du CCP par le triphosphate de sodium. Elles sont alors appelées submicelles de caséines. Le projet de cette thèse vise à approfondir les connaissances sur la nature des interactions dans les systèmes mixtes caséinates/carraghénane. Ce mélange est un modèle pour certains produits laitiers. Les principaux résultats de cette étude sont les suivants : Etude des mélanges de SC et de KC sous forme pelote. Nous avons établi un diagramme de phase à l’aide de la microscopie confocale à balayage laser (MCBL), de la spectroscopie UV et de la rhéologie. Deux domaines ont été définis : un domaine biphasique aux fortes concentrations de SC où la séparation de phase est ségrégative et un domaine monophasique aux faibles concentrations des deux composés. Dans les mélanges monophasiques ou biphasiques, nous avons observé des agrégats riches en protéines qui sont irréversibles. Ces agrégats contiennent très peu de carraghénane et ont un impact sur la viscosité du mélange. La teneur en protéine dans ces agrégats augmente linéairement avec l’augmentation de la concentration de KC mais est indépendante de la concentration de SC. Cette fraction est également influencée par le pH et la force ionique. Gélification des mélanges monophasiques de SC et de KC. Les caséines n’influencent pas la température critique de gélification, mais augmentent la température critique de fonte ainsi que le module du gel. Nous avons montré que le système forme un gel mixte. Ce gel mixte contient deux types de liaisons : des liaisons entre SC-KC et des liaisons entre KC-KC purs. La compétition entre ces deux types d’interactions dépend de la force ionique et de la nature du sel. Etude comparative des SC et des submicelles de caséines. On n’observe aucune différence entre les deux systèmes, à part la diminution de la température critique de gélification due au triphosphate de sodium. Etude comparative de KC et d’IC en présence de SC. La séparation de phase ségrégative des mélanges d’IC est déplacée vers les hautes concentrations de SC. Le pourcentage d’agrégats dans le mélange est négligeable. On observe également la présence d’un gel mixte, mais de module plus faible. En conclusion, cette thèse a permis de mieux comprendre le comportement complexe des carraghénanes dans les suspensions de caséines, ce qui devrait permettre le développement plus rationnel de certains produits laitiers. / The carrageenan is a sulphated polysaccharide extracted from red algae. In a acqueous solution carrageenan change its conformation when we cool from a coil to a helix, this coil-helix transition is thermoreversible. In generally, Helical carrageenan aggregates and can form a gel. Rheology shows that carrageenan forms gel during cooling at a critical gelation temperature Tc and that upon heating, the gel melts at a critical melting temperature Th. These critical temperatures depend on the nature and the concentration of kations that are present in the solution, but not on the carrageenan concentration. The shear modulus depends both on nature and concentration of salt and on the carrageenan concentration. Casein is the major milk protein component and consist of 4 kinds of casein molecules: alpha s1, alpha s2, beta and kappa casein. In milk, the caseins form a large complex with a size of about 200nm. This complex is stabilized by colloidal calcium phosphate. SC (sodium caséinate) can be prepare by precipitation of casein micelles at pH 4, washing the precipitate to remove the colloidal calcium phosphate and returning to pH 7 by adding NaOH. The SC is present in water in the form of small particles with a radius of about 11 nm that contain approximately 15 casein molecules. The objective of this work is to study the structure and mechanical properties of SC/carrageenan (kappa carrageenan (KC) and iota carrageenan (IC)) mixtures and to better understand the nature of the interaction between them. mixtures of KC and SC show a segregative phase separation at high concentrations of either. Cluster containing mostly SC and little KC are formed by association between KC and SC. With time, the clusters flocculate and precipitate, but they can be redisperse in solution by heating and shaking. The fraction of protein in the clusters depends on the pH, the ionic strength and the KC concentration, but very little on the protein concentration. During cooling, SC associates with helical KC and forms a mixed network. These mixed gels have two types of crosslinks: links between protein free KC chain sections and links involving of proteins. The break up of these two types of bonds can be seen during the melting process depending on the relative amounts of SC and KC. The gel strength depends on the KC and SC concentration and also the type and the concentration of salt. Mixtures of τ-carrageenan (IC) and sodium caseinate (SC) were investigated and the results are compared with a similar study of mixture of κ-carrageenan (KC) and SC. Segregative phase separation was observed at high biopolymer concentrations and the binodal was determined. At low IC concentrations SC formed aggregates involving a very small amount of IC that were characterized with light scattering. The influence of adding SC on the gelation of IC during cooling and the shear modulus of the gels, was studied in the presence of NaCl or KCl. The main conclusion of this work is that SC binds to both IC and KC, in the coil conformation as well as in the helix conformation, but that its effect on the rheology is much weaker for IC than for KC.

Orientadores: Florencia Cecilia Menegalli, Rosiane Lopes da Cunha / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-14T14:28:38Z (GMT). No. of bitstreams: 1 CiroVelasquez_HectorJose_D.pdf: 3600504 bytes, checksum: efd0571f00b5ea398f5836590f0165bb (MD5) Previous issue date: 2009 / Resumo: Suspensões de gomas xantana e de l-carragena foram secas usando um secador de leito de jorro fluidizado com partículas inertes de vidro e plásticas de ABS (acrylonitrile butadine styrene). O processo de secagem foi avaliado quanto ao desempenho do secador (eficiência de produção de pó e retenção de sólidos), características fluidodinâmicas (velocidades da partícula inerte no jorro e ânulo, queda de pressão no leito, largura da fonte, altura máxima de jorro, distribuição de temperaturas no leito) e qualidade do produto final obtido (propriedades reológicas e teor de umidade). Um planejamento fatorial 23 com 2 pontos centrais e 6 pontos axiais e superfícies de resposta foi usado para determinar o efeito das condições de secagem (temperatura de ar, vazão de suspensão e vazão de ar no jorro e ânulo) sobre o processo e na qualidade do produto final. Os resultados mostraram que foi possível obter produto reconstituído de pó de xantana usando vidro ou ABS como inerte. No entanto, para suspensões de l- carragena não foi possível a secagem com partículas esféricas de vidro devido à alta tensão superficial e baixo ângulo de contato. De acordo com os resultados do planejamento experimental, a eficiência de produção média de pó de goma xantana usando vidro como inerte foi de 28% com uma retenção de sólidos de 65%, enquanto que usando ABS a produção média foi de 45% e a retenção de sólidos de 49%, ou seja, o melhor desempenho do secador ocorreu quando ABS foi empregado como partícula inerte. Para a secagem de suspensões de l-carragena com partículas de ABS a eficiência de produção média de pó foi de 23% e a retenção media foi de 71%. A variável mais relevante na secagem das suspensões de gomas xantana e carragena foi a vazão de suspensão, sendo que um aumento desta variável produziu um baixo rendimento de pó e aumentou a retenção de sólidos dentro do leito. A queda de pressão do leito apresentou uma variação periódica indicando uma instabilidade fluidodinâmica. A distribuição de temperatura no leito mostrou uma operação quase isotérmica e que o processo evaporativo ocorreu principalmente na zona do jorro e base do ânulo. A velocidade da partícula no jorro foi dependente da vazão de ar na região do jorro, enquanto que a velocidade da partícula dentro no ânulo foi função da vazão de suspensão e também da vazão de ar que passava pelo jorro. A xantana obtida pela secagem em jorro fluidizado formou suspensões de natureza altamente pseudoplástica e com propriedades viscoelásticas de gel fraco. A vazão de alimentação da suspensão (=1 g/min) foi um fator importante para a preservação da qualidade reológica. A secagem de suspensões de goma xantana realizada em condições ótimas, tanto em leitos com partículas de ABS quanto de vidro, não mostrou efeito na qualidade reológica do produto. O produto reconstituído de l-carragena obtido nas condições otimizadas de secagem também formou suspensões de natureza altamente pseudoplástica, porém com propriedades viscoelásticas características de suspensões altamente diluídas (G''>G'), mostrando valores de viscosidade, módulos elástico (G') e de perda (G'') menores que o produto comercial e portanto uma perda de qualidade do produto. Nas condições de melhor desempenho do secador, as suspensões de l-carragena foram mais susceptíveis a sofrer mudanças em sua estrutura molecular que a goma xantana / Abstract: Xanthan and l-carrageenan suspensions were dried using a two dimensional spouted fluidized bed dryer with inert particles of glass and ABS (acrylonitrile butadine styrene).The dryer performance (powder production and solid retention), fluid flow characteristics (particle velocity in the spout and annulus, pressure drop, fountain width, maximum spout height, distribution of temperatures inside the bed) and quality properties of final product (rheological properties and moisture content) were evaluated. A complete 23 factorial design with 2 central points and 6 axial points together with response surfaces analysis was used to determine the effect of the drying conditions (drying temperature, suspension mass flow and air flow in the spout and annulus) on the drying process and final product. The results showed that it is possible obtain a reconstituted powder of xanthan gum using glass and ABS as inert particles. However, for suspensions of l- carrageenan was not possible the drying with glass spherical particles due to high superficial tension (low angle of contact). According to results of experimental design the mean powder production of xanthan gum using glass as inert was of 28% with a solid retention of 65%, whereas using ABS the mean powder production was of 45% with a solid retention of 49%, thus the best performance of the drier occurs when the bed with ABS is operated. In addition, the drying of l carrageenan suspensions with ABS particles showed a me n production of 23% with a solids retention of 71%. The most significant variable in the drying of the suspensions of xanthan and l carragena gum was the suspension mass flow rate where an increases produces a diminishing of the powder production increasing the solids retention in the bed. The pressure drop in the bed presented a periodic variation with the processing time indicating a hydrodynamics instability. The temperature distribution in the bed showed that annulus zone operated almost isothermally and that the spout zone and the annulus base are the zones where occurs the evaporative process. The particle velocity in the spout depends upon of the air flow in the spout, whereas the particle velocity in the annulus is function of the aeration and suspension mass flow rate. The reconstituted xanthan powder produced suspensions of highly pseudoplastic nature and with viscoelastic weak gel properties. The suspension mass flow rate (=1 g/min) was a factor important to preserve its rheological quality. To xanthan gum the drying operating conditions evaluated in the optimum point showed that the inert particle (ABS and glass) not influenced on the rheological quality of the reconstituted product. The l-carrageenan suspensions evaluated in the drying optimum conditions formed suspensions of highly pseudoplastic nature with viscoelastic properties of suspensions highly diluted (G''>G'). Also, the rheological and viscoelastic characteristics as viscosity, storage (G') and loss moduli (G'') are lower than commercial gum indicating a severe loss of product quality. In the conditions of better performance of the dryer, the suspensions of l- carrageenan were more sensitive to suffer changes in its molecular structure than the xanthan gum / Doutorado / Doutor em Engenharia de Alimentos

Kappaphycus alvarezii (Doty) Doty ex P. C. Silva é uma alga vermelha comercialmente importante por ser a principal fonte de carragenana kappa, hidrocolóide utilizado como agente espessante e estabilizante em alimentos, fármacos e cosméticos. Devido à sua importância, é fundamental desenvolver bases tecnológicas visando sua maricultura sustentada e a seleção de linhagens mais produtivas com carragenanas de melhor qualidade. Esse trabalho teve como objetivos: 1. desenvolver a cultura de tecidos para a propagação de plantas matrizes, selecionar as melhores linhagens para cultivo in vitro e produzir novas linhagens; 2. testar a espécie como biofiltro em cultivos integrados com peixes e 3. analisar os efeitos de diferentes condições de cultivo no rendimento e na qualidade das carragenanas, segundo parâmetros comerciais. Para o primeiro objetivo, foram testadas cinco linhagens (tetrasporófitos marrom, verde e vermelho, gametófito feminino e linhagem “Edison de Paula”, EP, selecionada a partir da germinação de tetrásporos) para definir o sistema experimental mais adequado para a micropropagação. Explantes da linhagem EP foram tratados com colchicina com a finalidade de induzir linhagens poliplóides. Essa linhagem foi selecionada por apresentar maior tolerância aos procedimentos de esterilização utilizados na cultura de tecidos. Apesar das altas taxas de indução de calos observadas em todas as linhagens, a regeneração de talos a partir dos calos (regeneração indireta) foi difícil. A regeneração de talos a partir dos explantes (regeneração direta) foi estimulada pela utilização de fitorreguladores e da colchicina. A contaminação dos cultivos por uma espécie filamentosa Acrochaetium no talo da linhagem EP foi inibida com a adição de 90 mM de glicerol. A formação de novas linhagens poliplóides através da utilização de colchicina não foi demonstrada. Os resultados indicaram que é possível utilizar a micropropagação através da produção de explantes para manutenção de um estoque de plantas matrizes de diferentes linhagens em laboratório. Para o segundo objetivo, o tetrasporófito marrom da espécie foi cultivado em tanques com água do mar e com efluente da criação de peixes da espécie Trachinotus carolinus (pampos) por 10 dias. As taxas de crescimento das algas cultivadas nos tanques foram mais baixas que às obtidas em cultivo no mar. Os valores máximos da taxa de remoção nos efluentes foram: NO3- = 18,2%; NO2- = 50,8%; NH4+ = 70,5% e PO43- =26,8%, nas condições testadas. Todas as plantas sobreviveram até o final do período experimental, mas apresentaram sinais de "ice-ice", doença associada ao estresse fisiológico. Diferenças entre os rendimentos de carragenana de algas cultivadas em água do mar ou em efluente de criação de peixes não foram significativas. Esses resultados demonstraram que é possível utilizar K. alvarezii como biofiltro de águas eutrofizadas derivadas da criação de peixes embora a espécie seja típica de águas oligotróficas. Para o terceiro objetivo, o gametófito feminino foi cultivado em balsas flutuantes segundo diferentes condições de cultivo (período de cultivo, profundidade e densidade do plantio). As carragenanas das plantas cultivadas nesses tratamentos foram extraídas e algumas propriedades foram determinadas. As taxas de crescimento variaram de 5,2 a 7,2% dia-1, com as maiores taxas obtidas em 28 dias de cultivo, em profundidade de 0 e 0,5 m e densidade do plantio de 12 e 8,4 plantas m-2. As condições de cultivo que forneceram melhor carragenana, segundo padrões comerciais foram: 45 dias de cultivo, na superfície, com densidade de 12 plantas m-2. Considerando que esse cultivo foi realizado na estação menos favorável do ano (inverno) para o crescimento das plantas, esses resultados indicam que o local onde a espécie foi introduzida é adequado para a implementação do cultivo comercial. Através dos resultados obtidos nesse trabalho, desejamos contribuir com a maricultura sustentável de uma espécie promissora no Brasil, com excelente potencial econômico reconhecido mundialmente, além de deixar algumas sugestões e propostas para novos estudos. / Kappaphycus alvarezii (Doty) Doty ex P. C. Silva is a red seaweed commercially important for being the main source of kappa carrageenan, hydrocolloid utilised as thickener and stabiliser in foods, medicaments and cosmetics. Due to its importance it is fundamental to develop technological bases on purpose of its sustainable mariculture and the selection of more productive strains with best qualities carrageenans. The objectives of this work were: 1. to develop the tissue culture for micropropagation of matrix plants, to select the better strains for in vitro culture and to produce new strains; 2. to test the species as biofilter in integrated cultivation with fishes and 3. to analyse the effects of different cultivation conditions in carrageenan yield and quality, according to commercial parameters. For the first objective, five strains (brown, green and red tetrasporophytes, female gametophyte and "Edison de Paula" strain, EP, selected from tetraspores progeny) were tested to define the experimental system suitable for micropropagation. Explants from EP strain were treated with colchicine with the aim of induce polyploid strains. This strain was selected by presenting high tolerance to sterilization procedures used in tissue culture. Despite the high rates of callus induction observed in all strains, thallus regeneration from callus (indirect regeneration) was difficult. Thallus regeneration from explants (direct regeneration) was stimulated by phytorregulators and colchicine. The culture contamination by a filamentous species Acrochaetium in the tallus of EP strain was inhibited with addition of 90 mM glycerol. The formation of polyploid strains by colchicine treatments was not proved. The results indicated that it is possible to use the micropropagation through the production of explants for maintaining matrix plants stocks from different strains in laboratory. For the second objective, the brown tetrasporophyte was cultivated in tanks with seawater and with effluents of the fish Trachinotus carolinus (pampos) rearing for 10 days. Growth rates of seaweeds cultivated in tanks was lower than those cultivated in the sea. The maximum values of removal rates from the effluents were: NO3- = 18.2%; NO2- = 50.8%; NH4+ = 70.5% and PO43- =26.8% in the conditions tested. All plants survived until the end of experimental period, but they presented signals of "ice-ice", disease associated to physiological stress. Differences between the carrageenan yields from plants cultivated in seawater and in effluents of fish rearing were not significant. These results showed that it was possible utilised the seaweed K. alvarezii as biofilter in effluents from fish rearing, although the species is typical of oligotrophic waters. For the third objective, the female gametophyte was cultivated from floating raft according to different cultivation conditions (i.e. cultivation period, depth and planting density). Carrageenan from the plants cultivated under these treatments was extracted and some properties were determined. Growth rates ranged from 5.2 to 7.2% day-1, with the higher rates obtained in 28 day cultivation period, at 0 and 0.5 m of depth and planting density of 12 and 8.4 plants m-2. The cultivation conditions that supplied the best carrageenan, according to commercial patterns were: 45 days of cultivation, in surface, with planting density of 12 plants m-2. Considering that this cultivation was conducted in the unfavourable season of the year (winter) for the growth of K. alvarezii, the results indicated that the site where the species was introduced is adequate to the implementation of commercial cultivation. Through the results obtained in this work, we wish to contribute with sustainable mariculture of a successful species in Brazil, with excellent economic potential recognised in all world, besides leave some suggestions and proposes for new studies.