Orientadores: Rubens Caram Junior, Conrado Ramos Moreira Afonso / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-06T17:14:04Z (GMT). No. of bitstreams: 1 Aleixo_GiorgiaTaiacol_M.pdf: 13698827 bytes, checksum: 10117398b384c5a1eda6c62fbfc74507 (MD5) Previous issue date: 2006 / Resumo: Ligas de titânio formam a classe mais versátil de materiais metálicos utilizados para aplicações biomédicas. As ligas de Ti tipo ß usadas em dispositivos ortopédicos envolve, além de excelentes propriedades como baixa densidade, elevada resistência mecânica e excepcional resistência à corrosão, a biocompatibilidade com elementos de liga, tais como Nb, Ta, Zr e Mo. O objetivo deste trabalho foi analisar a estabilidade e metaestabilidade de fases em ligas tipo ß no sistema Ti-Nb através da verificação da influência do teor de nióbio sob diversas condições de tratamento térmico. Para tanto variou-se a adição de Nb de 5% a 30% em peso na liga, obtendo amostras que foram submetidas a condições distintas de resfriamento a partir do campo ß. Amostras obtidas foram caracterizadas no tocante à microestrutura via microscopia ótica, eletrônica de varredura e de transmissão, difração de raios-X, enquanto o comportamento mecânico foi preliminarmente avaliado através de ensaios de dureza Vickers e de medidas de módulo de elasticidade através de técnicas acústicas. Os resultados obtidos indicam que baixas taxas de resfriamento conduzem à microestrutura de equilíbrio (a+ß) enquanto que altas taxas de resfriamento levaram à formação de estruturas metaestáveis. À medida que o teor de Nb foi incrementado e sob altas taxas de resfriamento, obteve-se, respectivamente, martensita a¿ (hexagonal compacta), martensita a¿ (ortorrômbica), fase ? (trigonal) e finalmente, fase ß metaestável. Em relação ao módulo de elasticidade, observou-se que esse parâmetro decresce entre 0 e 15% de Nb e após este último valor, tal constante elástica se eleva como resultado da precipitação de fase ? bem como da possível alteração de dimensões da estrutura cristalina. As ligas Ti-Nb apresentaram uma variabilidade de microestruturas e propriedades que dependem fortemente da composição e condição de resfriamento / Abstract: Titanium alloys form one of the most versatile classes of metallic materials used for biomedical applications. ß Ti alloys for orthopaedic devices involves, besides excellent properties like low density, high mechanical strength and good corrosion resistance, great biocompatibility with alloying elements, such as Nb, Ta, Zr and Mo. The objective of this work was to analyze the stability and metastability of phases in ß Ti-Nb alloys through the evaluation of the influence of percentage of Nb obtained in different heat treatment conditions. In this way, Nb addition was varied from 5 to 30wt% in Ti-Nb system. Samples were obtained and microstructural characterization was made through optical microscopy, scanning and transmission electron microscopy and X-ray diffraction, while mechanical behavior was primarily evaluated by Vickers hardness and elasticity modulus through acoustic techniques. The results obtained indicate that lower cooling rates resulted in the equilibrium microstructures (a+ß), otherwise higher cooling rates led to formation of metastable structures. As the Nb content was increased and under greater cooling rates, it was obtained, respectively, martensite a¿ (hexagonal closed packed), martensite a¿ (orthorhombic), ? phase (trigonal) and finally, metastable ß phase. Regarding modulus of elasticity it was observed that it decreases as the %Nb increases up to 15% and beyond this percentage the modulus increases due the precipitation of ? phase as well as possible variation of crystalline structure dimensions. Ti-Nb alloys presented a great variety of combinations between microstructures and properties that strongly depends on composition and cooling conditions / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Orientadores: Rubens Caram Junior, Conrado Ramos Moreira Afonso / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-15T14:37:29Z (GMT). No. of bitstreams: 1 Aleixo_GiorgiaTaiacol_D.pdf: 25669452 bytes, checksum: 43f10d141f1b3e5a6d696930ee2f86ec (MD5) Previous issue date: 2009 / Resumo: Este trabalho trata da preparação, processamento e caracterização microestrutral e mecânica de ligas Ti-Nb-Sn tipo ß visando a fabricação de dispositivos ortopédicos para implante. Amostras contendo Ti com teores de 25, 30 e 35% em peso de Nb e 2, 4 e 8% em peso de Sn foram preparadas por fusão a arco, homogeneizadas a 1000ºC/8 h e deformadas plasticamente por forjamento rotativo. Tais amostras foram submetidas a ensaios de resfriamento contínuo objetivando avaliar condições de obtenção de fases metaestáveis. Em seguida, amostras aquecidas a 1000ºC foram resfriadas rapidamente e submetidas a ensaios de calorimetria diferencial de varredura e de raios-X com aquecimento até médias temperaturas, o que permitiu avaliar a decomposição martensítica. Em seguida, amostras aquecidas no campo ß foram resfriadas ao ar, o que resultou em microestruturas com a fase a precipitada na matriz ß. Tais amostras foram caracterizadas no tocante à microestrutura via microscopia ótica, eletrônica de varredura e de transmissão e difração de raios X, enquanto que o comportamento mecânico foi avaliado por meio de testes de dureza Vickers, de medidas de módulo de elasticidade usando técnicas acústicas, ensaios de tração e ensaios de fadiga. Os resultados obtidos indicam que a decomposição da martensita resulta nas fases ß, ? e finalmente, a e também, que a fase ? atua como substrato na nucleação da fase a. O comportamento mecânico das amostras depende diretamente das fases presentes na microestrutura, bem como de suas frações volumétricas. Constatou-se também que o módulo de elasticidade, a dureza e o limite de resistência à tração de amostras resfriadas ao ar exibem valores superiores aos valores obtidos com as amostras resfriadas rapidamente, enquanto que a ductilidade se reduz. Finalmente, observou-se que o limite de fadiga de amostras resfriadas ao ar é máximo para baixos teores de Nb e se reduz com a adição de Sn / Abstract: This work deals with preparation, processing and microstructural and mechanical characterization of ß type Ti-Nb-Sn alloys aiming the manufacturing of orthopedic devices for implants. Ti samples containing Nb at levels of 25, 30 and 35 wt % and Sn at levels of 2, 4 and 8 wt % were prepared by arc melting, homogenized at 1000ºC/8 h and plastically deformed by swaging. These samples were submitted to continuous cooling experiments to evaluate conditions for obtaining metastable phase. Then, samples heated to 1000ºC were rapidly cooled and analyzed by using differential scanning calorimetry and X-ray diffraction at medium temperatures, which allowed the evaluation of martensite decomposition. Next, samples in the ß field were air-cooled, which resulted in microstructures with a phase precipitated into ß matrix. These samples were characterized concerning the microstructure by applying optical, scanning electron and transmission electron microscopies and X-ray diffraction, while the mechanical behavior was evaluated by Vickers hardness test, elastic modulus measurement using acoustic techniques, tensile and fatigue tests. The results obtained indicate that martensite decomposition results in ß, ? and finally a phases. It was also found that ? phase acts as substrate for a phase nucleation. The sample mechanical behavior directly depends on the phases present in the microstructure, as well as their volumetric fraction. It was also observed that elastic modulus, hardness and tensile strength of air cooled samples show higher values than those of rapidly quenched samples, while ductility decreases. Finally, it was observed that fatigue resistance of air cooled samples is higher for low Nb content alloys, however, it decreases with Sn addition / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Este trabalho tem por objetivo a caracterização comparativa do comportamento de degradação e/ou decomposição térmica da esponja sintética dupla face, base poliuretana (parte amarela e parte verde), e da palha de aço, a partir das técnicas termoanalíticas. As esponjas sintéticas para limpeza doméstica, em substituição à palha de aço, apesar da vantagem econômica, podem apresentar restrições de descartes para o meio ambiente ou expor o usuário a riscos de contaminação. Amostras de esponja sintética dupla face (verde e amarela) e de palha de aço foram caracterizadas por análise térmica (TG/DTG, DTA e DSC) empregando atmosfera dinâmica de ar e de N2. Essas amostras foram estudadas por métodos cinéticos por termogravimetria isotérmica e não isotérmica. Os parâmetros cinéticos obtidos permitiram estimar os tempos necessários para a decomposição de ambas as partes da amostra da esponja sintética e também da palha de aço sob atmosfera de ar. Os resultados evidenciaram claramente que a matriz polimétrica da esponja sintética para ser degradada completamente exige um tempo muito longo, acima de 20.000 anos. Por outro lado, os resultados indicaram comportamento similar entre as amostras de esponja sintética e de palha de aço considerando apenas o efeito temperatura e tipo de atmosfera. Contudo, no cotidiano sabe-se que a palha de aço se oxida muito facilmente sob atmosfera de ar na presença de umidade. / This work aims at a comparative characterization of degradation behavior and/or thermal decomposition of synthetic double-face sponge, polyurethane base (yellow part and green part), and steel wool, from thermoanalytical techniques. Synthetic sponges for household cleaning, replacing steel wool, despite the economic advantage, may have restrictions on discharges to the environment or expose the user to risks of contamination. Samples dual synthetic sponge face (green and yellow) and steel wool were characterized by thermal analysis (TG/DTG and DTA DSC) employing an atmosphere of air and N2. These samples were studied by kinetic methods isothermal and non-isothermal thermogravimetric analysis. The kinetic parameters obtained allowed the estimation necessary for decomposition of the sample both sides of the synthetic spomge and also of steel straw times under air atmosphere. The results clearly showed that polymetric matrix of synthetic sponge to be degraded completely requires a very long time, over 20,000 years. Moreover, the results showed similar behavior among synthetic sponge and steel wool sample considering only the effect of temperature and type of atmosphere. However, in daily life it is known that the steel wool oxidizes very easily under air atmosphere in the presence of moisture.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-04-26T16:59:53Z No. of bitstreams: 1 Dissert-LeonardoFrazão.pdf: 2516279 bytes, checksum: 48923c148348e036ced167489ad1b5d2 (MD5) / Made available in DSpace on 2017-04-26T16:59:53Z (GMT). No. of bitstreams: 1 Dissert-LeonardoFrazão.pdf: 2516279 bytes, checksum: 48923c148348e036ced167489ad1b5d2 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica Ambiental. Niterói, RJ / O potencial de bioacumulação de metais; capacidade de expressar biomarcadores moleculares (como a indução de proteínas semelhantes a metalotioneínas, MTLPs); e biomarcadores histológicos (quantidade de canais aquíferos, câmaras coanocitárias e fibras de colágeno) foram estudados na esponja Hymeniacidon heliophila. Em aquário, foi realizada exposição da esponja a diferentes concentrações de cádmio (controle; 0,05; 0,4 e 4 mg L-1 de Cd) ao longo de determinados períodos de tempo (tempo zero, 24 horas, 7 dias e 14 dias). Também foi avaliada a ocorrência de MTLPs e as concentrações de metais potencialmente indutores da síntese dessas proteínas (Cd, Ni, Cu e Zn) em H. heliophila proveniente diretamente da praia da Boa Viagem, situada na Baía de Guanabara (RJ). No experimento em aquário, a esponja acumulou uma concentração máxima de 114 mg Cd Kg-1, após 14 dias de exposição a 4 mg L-1 deste metal. Este valor corresponde a 14 vezes o encontrado em esponjas do aquário controle. Por meio da técnica de eletroforese (SDS-Page) aliada a derivatização com monobromobimano, foi possível observar forte indução de MTLPs apenas nas amostras expostas a 0,4 mg L-1 de Cd nos períodos de 24 horas e 7 dias. As técnicas de histologia utilizadas para evidenciar os efeitos morfológicos causados pela exposição ao Cd revelaram que em 24 horas houve diminuição na quantidade das estruturas analisadas. A partir desse período, nas esponjas submetidas a 4 mg L-1 de Cd, houve tendência de diminuição (exceto para fibras colágenas) das estruturas, enquanto em 0,4 mg L-1 de Cd houve tendência de estabilização e, em 0,05 mg L-1 de Cd, recuperação. No estudo na praia da Boa Viagem, em nenhuma das cinco coletas realizadas, foi constatada indução de MTLPs. As médias das concentrações de metais encontradas no tecido das esponjas foram: 0,28 mg Cd kg-1, 46,3 mg Cu kg-1, 2 mg Ni kg-1 e 965 mg Zn kg-1. Estes valores são elevados quando comparados às concentrações reportadas para outros organismos da Baía de Guanabara. Assim, a alta eficiência em acumular metais (observada na praia da Boa Viagem) e a capacidade de induzir MTLPs e respostas histológicas (frente à exposição ao Cd), indicam possibilidades para utilização de H. heliophila em futuros programas de biomonitoramento. / The metal bioaccumulation potential, the expression of molecular biomarkers (induction of metallothionein-like proteins, MTLPs) and histological biomarkers (number of channels, choanocyte chambers and collagen fibers) were studied in the sponge Hymeniacidon heliophila. Exposure experiments to different concentrations of cadmium (<0.01, 0,05, 0,4 and 4 mg L-1 Cd) along different time intervals (t = 24 hours, 7 days and 14 days) were performed under controlled (aquarium) conditions. The occurrence of MTLPs and metal concentrations potentially involved in inducing the synthesis of these proteins (Cd, Ni, Cu and Zn) were also investigated in H. heliophila directly sampled from the Boa Viagem beach, located in Guanabara Bay (RJ). In the aquarium experiment, the sponge accumulated a maximum concentration of 114 mg Cd kg-1 after 14 days of exposure to 4 mg L-1 of this metal. This corresponds to 14 times the concentration found in sponges found in a control aquarium. Electrophoresis (SDS-PAGE) combined with monobromobimano derivatization indicated a strong induction MTLPs only in samples exposed to 0,4 mg L-1 Cd in periods of 24 hours and 7 days. The histological techniques used to reveal the morphological effects caused by exposure to Cd revealed that within 24 hours there was a decrease in the quantity of the analyzed structures. In the study carried out in Boa Viagem beach, there was absence of MTLPs induction along the five sampling periods evaluated. The mean concentrations of metals found in the tissue of the sampled sponges were: 0,28 mg kg-1 Cd, 46,3 mg kg-1 Cu, Ni 2 mg kg-1 and 965 mg kg-1 Zn. These values are higher than concentrations reported for other organisms from Guanabara Bay. Thus, the high efficiency in accumulating metals (found in the Boa Viagem beach) and the ability to induce MTLPs and histological responses (under high Cd exposure) indicate possible uses of H. heliophila in future biomonitoring programs

Face aux problèmes de résistance aux médicaments actuels sur le marché, issus pour la grande part du milieu terrestre, les molécules isolées du milieu marin ont suscité un grand intérêt ces dernières années. Pour notre part, nous nous sommes intéressés au R1864-03, un macrocycle a 16 chaînons qui a été extrait d¿une éponge marine présente en Nouvelle Calédonie et qui possède des propriétés anticancéreuses. La synthèse de ce produit naturel a été envisagée à partir de deux fragments principaux, qui ont été rassemblés grâce à un couplage chimiosélectif de Suzuki. Dans un premier temps, une réaction intramoléculaire de Diels-Alder a été envisagée pour construire le motif cis- décaline du R1864-03 avant de réaliser le couplage des deux fragments. Suite à la mauvaise stéréosélectivité inverse observée pour la réaction de Diels-Alder intramoléculaire, une réaction de Diels-Alder transannulaire sur le macrocycle à 24 chaînons du R1864-03 a été envisagée. Nous avons pu accéder au précurseur de macrocyclisation, ayant le squelette carboné complet du R1864-03, en 16 étapes avec un rendement global de 4.2%. La macrocyclisation sur ce dernier, suivie de la Diels-Alder transannulaire semble avoir conduit au R1864-03 protégé ou à un diastéréoisomère. Ces étapes restent à optimiser et a réaliser sur plus grosse échelle pour pourvoir réaliser la détermination structurale complète du produit de Diels-Alder transannulaire et de compléter la synthèse totale du R1864-03. / Due to resistance problems faced by existent drugs on the market, originated most from terrestrial sources, a great attention has recently been devoted to marine natural products. In this context, we have been interested in the total synthesis of R1864-03, a new 16-membered macrolide isolated from a Caledonian marine sponge and with important anticancer properties. The synthesis of this natural product was designed around the chimiosélective Suzuki-Miyaura coupling of two main fragments. A key intramolecular Diels-Alder reaction was first planed to install the cis-decalin motif of R1864-03 to generate one of these fragments. Due to an inverse stereoselectivity of the intramolecular Diels-Alder reaction, a transannular Diels-Alder reaction on the 24-membered macrocycle of R1864-03 was considered. We have been able to obtain the macrocyclisation precursor with the complete carbon skeleton of R1864-03 in place in 16 steps (4.2% overall). Macrocyclisation of the latter, followed by the transannular Diels-Alder reaction, seems to have provided the protected R1864-03 or a diastereoisomer. These last steps have to be optimized and carried out on larger scale in order to achieve complete structural determination of the transannular Diels-Alder product and to complete the total synthesis of R1864-03.

This project focuses on the use of sponge genetic transcripts in the form of expressed sequence tags (ESTs) readily available in Genbank to search for novel genes using bioinformatics analysis tools. Marine sponge species are known to house a diversity of marine microbes and are known as the ‘living fossils’ of the animal kingdom because of the large number of ancient genes they house. Genomic mining can be a useful tool in discovering these orthologous genes. This study utilized the techniques of genomic mining of 11 previously described sponge species transcripts. The results of this study provide a better understanding of the genomic structure of the organisms studied by creating a more detailed genetic map and examining a specific environmental snapshot of the genes in each sponge. Novel methods for dissecting beneficial information from large scale data sets available in genomic libraries utilizing bioinformatics search tool MGRAST were examined. The results of this study indicate that sponges house numerous genes that are likely to be evolutionary predecessors of genes in higher eukaryotes. Support was also given to the notion that microbial communities play a role in metabolic pathways of sponges.

Les membranes biologiques, qui compartimentent les différents éléments du vivant, jouent un rôle essentiel dans les processus biologiques comme la signalisation, le transport, la transmission du message nerveux, etc. Envisagées comme des fluides à deux dimensions, l’étude de leurs propriétés physiques peut nous aider à comprendre certains mécanismes biologiques. Ce travail de thèse s’est intéressé à la mobilité des molécules au sein des membranes, et notamment à deux paramètres essentiels, la viscosité membranaire, et la diffusion latérale. Après avoir optimisé la technique de recouvrement de fluorescence après photoblanchiment (FRAP) au microscope confocal, nous avons étudié la mobilité des molécules au sein de deux types de membranes modèles in vitro : la phase éponge d’un surfactant non-ionique (C12E5) et les vésicules géantes unilamellaires (GUVs) lipidiques. 1) La phase éponge (ou L3) : après avoir déterminé son diagramme de phase et montré que les protéines membranaires restent actives dans cette phase, nous avons mesuré la mobilité de protéines par recouvrement de fluorescence après photoblanchiment sur un motif à franges (FRAPP). Cela nous a permis d’obtenir les constantes d’association de protéines de la pompe d’efflux OprM-MexAB, impliquée dans la résistance aux antibiotiques de la bactérie Pseudomonas aeruginosa. Ces interactions dépendent très fortement du degré de confinement de chacune des protéines. 2) Les GUVs : après avoir développé une méthode simple de formation des GUVs, au sein desquelles les protéines membranaires restent actives, nous avons mesuré la diffusion des lipides par FRAP, et montré que dans certaines conditions, ils se déplacent en groupe, ce qui permet d’expliquer la diversité des résultats de la littérature. En mesurant la viscosité membranaire par imagerie microscopique du temps de vie de fluorescence (FLIM), nous avons également montré qu’elle ne se déduit pas nécessairement des modèles hydrodynamiques de diffusion. / Biological membranes, which divide the elements of life, are a key factor in biological processes such as signaling, transport, transmission of an nerve impulse, etc. Seen as two-dimensional fluids, the study of their physical properties could help us understand some unsolved biological mechanisms. This work focused on molecule mobility within membranes, and specifically on two essential parameters: membrane viscosity and lateral diffusion. After optimizing the Fluorescence Recovery After Photobleaching (FRAP) technique on confocal microscopes, we studied the mobility of molecules within two types of in vitro model membranes: the sponge phase made of a non-ionic surfactant (C12E5) and the giant unilamellar lipidic vesicles (GUVs). 1) Sponge phase (or L3) : after having established its phase diagram and shown that membrane proteins stay active in this phase, we measured protein mobility by Fluorescence Recovery After fringe Pattern Photobleaching (FRAPP). This allowed us to obtain the association constants of the proteins of the efflux pump OprM-MexAB involved in the resistance to antibiotics of the bacteria Pseudomonas aeruginosa. These interactions heavily depend on the degree of confinement of each protein. 2) GUVs : after having developed a simple method for the formation of GUVs, in which membrane proteins stay active, we measured the lipid diffusion by FRAP. We showed that, under certain conditions, they can move together, which explains the diversity of results in the literature. By measuring membrane viscosity by Fluorescence Lifetime Imaging Microscopy (FLIM), we also showed that viscosity should not be necessarily deduced from hydrodynamic diffusion models.

Postoperative Wundheilungsstörungen nach herzchirurgischen Eingriffen sind seltene, jedoch gefürchtete und ernstzunehmende Komplikationen, die zu schwerwiegenden Konsequenzen bis hinzu einer Poststernotomie-Mediastinitis mit möglicherweise letalen Ausgang führen können. In einer prospektiven, monozentrisch angelegten Studie wird angestrebt, ein infektionspräventives Behandlungskonzept herauszuarbeiten, mit dem das Risiko für thorakale Wundinfektionen verringert werden kann. Ob mit der Anwendung eines vor operativen Thoraxverschlusses retrosternal eingelegten Gentamicin-Kollagenschwammes eine Reduktion der Inzidenz von Wundheilungsstörungen nach medianer Sternotomie erreicht werden kann, wird in der vorliegenden Studie geprüft. Dazu kommt eine Kombination aus dem Desinfektionsmittel ChloraPrep® und dem Resorbaschwamm Genta-Coll resorb® zum Einsatz.

En industrie alimentaire et notamment dans le domaine des produits céréaliers, les ingrédients utilisés et les procédés associés ont des impacts sur les réactions chimiques des constituants ainsi que sur la structure des produits fabriqués. Les réactions peuvent avoir des impacts positifs (arômes, couleur) ou négatifs (développement de composés néoformés potentiellement toxiques). Bien que très étudiées dans des systèmes simplifiés, une meilleure connaissance et maitrise des réactions dans des conditions plus réalistes permettrait de mieux piloter la qualité des produits et de favoriser la balance bénéfices/risques. L’objectif de ce travail était de rendre possible l'étude des réactions dans un milieu solide, certes, simplifié, mais maîtrisé en composition et structure, et fidèle aux procédés de fabrication et à la structure à des produits réels. La génoise a été choisie comme produit de référence.La première étape a consisté à développer un produit modèle constituant une base d’étude de la réactivité. Pour cela, une étude des fonctionnalités apportées par chaque ingrédient à chaque étape du procédé de fabrication a permis d’identifier les dérivés de cellulose comme candidats intéressants pour remplacer les ingrédients réactifs (oeuf, sucre et protéines de la farine). Une étude multiéchelles a permis de mieux comprendre l’impact des principales propriétés apportées par les dérivés de cellulose (viscosité à froid, stabilisation des interfaces, gélification à chaud) sur la structuration du produit. Enfin, le produit modèle a été validé comme étant non-réactif vis-à-vis de la réaction de Maillard et de caramélisation.Dans une seconde étape, des composés réactifs (glucose, leucine) ont été réintroduits dans le produit modèle et un suivi cinétique de marqueurs de la réactivité dans les vapeurs et dans le produit a été réalisé au cours de la cuisson. Ainsi, l’enrichissement du modèle en glucose + leucine a permis de suivre le développement de composés typiques de la réaction de Maillard (aldéhydes de Strecker et pyrazines), qui n’apparaissent pas dans le cas où le produit n’est enrichi qu’en glucose, où seuls les composés issus de la caramélisation ont été identifiés. De plus, la modification des conditions de cuisson (température, convection) a permis de mettre en évidence l’impact des transferts thermiques et du séchage sur les voies réactionnelles. Ces résultats ouvrent ainsi la voie à de futures études cinétiques, couplant expérimentation systématique et modélisation. / In the food industry and notably in the field of cereal products, the type of ingredients used and their associated processes have several effects on the structure of the products and on the chemical reactions occurring during the manufacturing process. These reactions could have positive impacts (aroma, color) as well as negative outcomes (formation of potentially toxic compounds). Although being thoroughly studied in model systems, a better understanding of reactions in more realistic conditions would allow to improve the quality of the products. The aim of this work was to enable the study of chemical reactions occurring in a simplified solid system where the composition and structure were controlled while remaining representative regarding the conditions of the processes and the structure of the real product. Sponge cake was chosen as the product of reference.The first step consisted in developing a model product constituting a basis for studying the reactivity. In this regard, a study on new functionalities brought by each ingredient during each step of the manufacture process allowed to identify the cellulose derivatives as candidates to replace the reactive ingredients (eggs, sugar and wheat flour proteins). A multi-scale study allowed to better understand the impact of the main properties brought by the cellulose derivatives (viscosity at cold temperature, interface stabilization, gelation at high temperature) on the structure of the product. Finally, the model product was validated as a non-reactive media regarding the Maillard reaction and the caramelization.In a second step, reactive compounds (glucose and leucine) were placed in the model product and a kinetic monitoring on reaction markers was set up in the vapors and in the matrix during the baking. Thus, the addition of glucose and leucine in the model allowed to follow the formation of typical compounds coming from the Maillard reaction (Strecker’s aldehyde and pyrazines). These compounds did not developed when the model product was only enriched in glucose, whereas compounds generated by the caramelization reaction were identified. Moreover, changes in baking conditions (temperature, convection) allowed to emphasize the impact of heat transfer and drying on reaction pathways. These results pave the way of future kinetic studies, coupling systemic experiment and reaction modelling.

Xestospongia muta, the giant barrel sponge, is a key component of coral reef benthic communities in Southeast Florida and the Caribbean. Xestospongia muta increases habitat complexity and stability, and filters large volumes of water, enhancing water quality and facilitating nutrient cycling. Therefore, it is important to investigate trends in the X. muta population on Southeast Florida reefs in response to anthropogenic stressors, changing environmental conditions and acute disturbances and how these events affect its ecological role in the benthic community. This study identified trends in X. muta population density, volume, and size class distribution over time and across reef habitats on the Southeast Florida Reef Tract (SEFRT). Density and volume changes were also investigated following acute physical disturbance caused by Hurricane Irma in September of 2017. Images and demographic data collected at 41 permanent sites from two long-term monitoring projects, The Southeast Florida Coral Reef Evaluation and Monitoring Project (SECREMP) and the Broward County Biological Monitoring Project (BC BIO), were used to evaluate the X. muta population trends. My analysis of the data from 2003 to 2018 shows that Xestospongia muta densities and volume increased over time regionally on the SEFRT and increased on the nearshore, middle, and outer reefs of the SEFRT. Xestospongia muta was found to be more abundant on the SEFRT compared to other locations including the Bahamas, the Florida Keys, Colombia, Belize and Saba. Highest mean density on the SEFRT was 0.35 individuals m-2 ±0.04 SEM, which was higher than the mean densities between 0.21 and 0.29 individuals m-2 at the Caribbean sites previously mentioned. Xestospongia muta individuals were categorized into size classes by volume to investigate density distribution of size classes on the SEFRT. Greater abundances in the smallest of five size classes (≤143.13 cm3) drove the increasing density trends. Despite the increasing trends from 2003 to 2017 with a peak in density and volume in 2017, Hurricane Irma caused a region-wide decline in population density and volume as well as a loss of individuals within the largest size class by volume (>17383.97 cm3). These results indicate that the X. muta population is exhibiting increasing long-term trends on the SEFRT, but also demonstrate that acute physical disturbances have a significant impact on the demographics of the population. Because of this sponge’s multiple roles in the reef communities, these trends have implications for structural complexity, nutrient cycling, water filtration, as well as carbon sequestration on the SEFRT.