A indústria alimentícia tem oferecido ao consumidor muitas opções para aquisição de pães, dentre essas estão os pães enriquecidos e os integrais. A linhaça é um alimento com alegação funcional que vem se destacando pela presença do Omega-3, fibra solúvel e proteína, porém seu consumo é baixo devido à falta de hábito e também por escassez de informação dos consumidores. O objetivo do estudo foi formular pães com adição de grãos de linhaça nas concentrações de 3%, 6% e 9% e compará-los ao controle, sem adição de linhaça. Foram realizadas análises de determinação do perfil de ácidos graxos, composição centesimal, quantificação do teor de minerais, determinação de antinutricionais (ácido fítico, taninos, compostos fenólicos totais), digestibilidade de proteína in vitro, análise da qualidade dos pães através do peso da massa crua, peso da massa assada, perdas durante a cocção e índice de conversão. As propriedades físicas dos pães também foram avaliadas através da textura, volume e cor. As características sensoriais foram analisadas através de teste de aceitabilidade realizado em padaria com 116 provadores e também pela Análise Descritiva Quantitativa (ADQ) com 13 provadores treinados. Com os dados obtidos das análises químicas, elaborou-se um rótulo nutricional para cada formulação. Dentre os ácidos graxos quantificados, o palmítico, o oléico e o linoléico foram os maiores representantes nas 4 amostras de pães o que contribuiu para a frágil estabilidade dos produtos e para a formação de compostos indesejáveis, porém a presença de antioxidantes naturais nas sementes de linhaça controlou a oxidação lípidica. Nenhuma das amostras pode ser considerada fonte de fibra alimentar pelo fato de não conter 3g/100g de alimento pronto para consumo. O teor de fitatos presente nas amostras aumentou de acordo com a adição de sementes de linhaça. Nas 4 formulações de pães o teor de fitato diminuiu significativamente quando comparado ao da semente de linhaça. As amostras controle e com 6% de linhaça foram classificadas como volume específico Muito bom e as amostras com 3% e 9% de linhaça foram classificadas como volume específico Bom. Entre as amostras que receberam adição de linhaça, a amostra com 9% foi a melhor aceita pelos provadores e na ADQ, essa amostra apresentou médias superiores às demais em relação a maioria dos atributos levantados pelo provadores. Não foram identificados atributos indesejáveis para nenhuma das amostras através da ADQ. / Food industries offer to consumer several types of breads options which vary from whole wheat to enrich with multigrain such with flax seed. Flax seed is considered a functional food that has important content of omega 3 fat acids, soluble fiber and protein, however it intakes is very low in our diet. The aim of the research was to prepare a wheat bread enrich with flax seed at 3% or 6% or 9% concentration and to compare with a wheat bread control with no flax seed added. Analysis of fat acids composition, mineral composition, antinutritionals content (phytic acid, tannin, total phenolic compounds) and in vitro protein digestibility were carried out in the bread samples. Bread quality was evaluated analyzing the weight of the raw dough, the baked bread, and the lost during baking process and its conversion index. Physical properties of breads were evaluated for texture, volume and color. The sensory characteristics were evaluated using acceptability test with 116 panelists and by quantitative descriptive analysis (QDA) with 13 trained panelists. A nutritional label was formulated to each one of the bread preparations. The quantified fat acids profile showed that palmitic, oleic and linolenic acids were the most representative fat acids in the 4 bread sample analyzed. The presence of those fat acids possibly contributes to poor stability of product and for the development of undesirable compound. However, the presence of natural antioxidants in flax seed may help to control fat acid oxidation. None of the samples were considered source of dietary fiber because they have less then 3g/100 g of bread. The phytate content present in the samples increased according to the increase of flax seed concentration in the bread. Compared to raw flax seed, the phytate content in the bread samples were lower. The control and the sample with 6% of flax seed had the ranking for specific volume described as Very good and the samples with 3% and 9% of flax seed as Good. Between the bread samples, the best score in the acceptability test was obtained in the sample with 9% of flax seed. The same was observed for QDA which showed that the panel had high attributes for this sample compared to other ones. No undesirable attributes were identified in any other sample analyzed in QDA.

No description available.

A combinação de agentes quimiopreventivos com diferentes mecanismos de ação tem sido considerada uma estratégia promissora para a prevenção do câncer. Dentre os diversos compostos bioativos em alimentos, destacam-se a tributirina, um pró-fármaco do ácido butírico presente em laticínios e produzido pela fermentação de fibras dietéticas, e o óleo de linhaça, fonte de ácido alfa linolênico. Nesse contexto, foi avaliada a atividade quimiopreventiva de lipídios estruturados obtidos a partir da interesterificação enzimática de tributirina e óleo de linhaça durante a fase de promoção inicial da hepatocarcinogênese experimental. Ratos Wistar machos submetidos ao modelo do hepatócito resistente receberam diariamente, por via intragástrica (i.g), maltodextrina, óleo de linhaça, tributirina, a mistura não esterificada ou lipídios estruturados durante a fase de promoção inicial. O tratamento com lipídios estruturados demonstrou atividade quimiopreventiva comparável à da tributirina, mesmo resultando em menor concentração hepática de ácido butírico. Tanto a tributirina quanto os lipídios estruturados não inibiram a proliferação celular em lesões preneoplásicas, mas induziram a apoptose naquelas em remodelação. Os efeitos inibitórios da tributirina em fases iniciais da hepatocarcinogênese experimental estão relacionados ao aumento da acetilação de histonas e à modulação de processos de translocação nuclear da p53. No presente estudo, foi observado aumento substancial da razão nuclear/citoplasmática de p53 e importina-alfa em fígados de animais submetidos ao modelo e tratados com tributirina, mas não nos tratados com lipídios estruturados. Por outro lado, o tratamento com lipídios estruturados reduziu a expressão dos oncogenes Bcl2, Ccnd2, Pdgfa, Vegfa e aumentou a expressão dos genes supressores de tumor Cdh13, Fhit e Socs3. Assim, embora o potencial quimiopreventivo dos lipídios estruturados seja comparável ao da tributirina, os resultados sugerem que o novo composto não exibe atividade de HDACi, e que seus efeitos inibitórios na hepatocarcinogênese possam ser atribuídos à modulação da expressão de oncogenes e genes supressores de tumor. / Combination of chemopreventive agents with different mechanisms of action has been considered a promising strategy to cancer prevention. Among several bioactive food compounds, tributyrin, a butyric acid prodrug obtained from dairy products and dietetic fiber fermentation, and flax seed oil, a rich source of alpha linolenic acid have shown chemopreventive potential. Here, we evaluated the chemopreventive activity of structured lipids obtained by enzymatic interesterification of tributyrin and flax seed oil during the early promotion phase of experimental hepatocarcinogenesis. Male Wistar rats subjected to the resistant hepatocyte model were treated daily, i.g, with maltodextrin, flax seed oil, tributyrin, non-sterified blend, or structured lipids. Treatment structured lipids showed similar chemopreventive activity compared to tributyrin, even when structured lipids yielded lower concentrations of butyric in the liver. Tributyrin and structured lipids did not inhibit cell proliferation in preneoplastic lesions, but both of them induced apoptosis in remodeling preneoplastic lesions. In addition, histone acetylation and p21 restored expression tributyrin molecular mechanisms were related to modulation of p53 nuclear shuttling mechanisms. In the present study, it was observed a substantial increase in p53 nuclear/cytoplasmic ratio and importin-alpha in preneoplastic livers of tributyrin treated rats, but not in those treated with structured lipids. In contrast, treatment structured lipids downregulated expression of major oncogenes Bcl2, Ccnd2, Pdgfa, and Vegfa; and upregulated expression of critical tumor suppressor genes, Cdh13, Socs3 and Fhit. Hence, although structured lipids and tributyrin show similar chemopreventive potential, the results suggest that the new compound does not exhibit HDACi activity, and that its inhibitory effects may be attributed to the modulation of oncogenes and tumor suppressor genes expression.

Durant les dernières décennies, les composites polymères renforcés par des fibres végétales ont reçu une attention importante de la part des scientifiques. L’utilisation de fibres végétales permet en effet d’améliorer les performances environnementales de ces matériaux tout en atteignant des propriétés spécifiques plus élevées. Néanmoins, un verrou majeur freine encore le développement de ces matériaux. En effet, leur sensibilité au vieillissement hydrique, due à leur caractère hydrophile, restreint leur utilisation. Dans ce contexte, nous proposons, dans le cadre de cette thèse, d’analyser l’effet du vieillissement hydrique sur le comportement statique et dynamique, d’identifier et suivre les mécanismes d’endommagement d’une structure sandwiche biosourcée et ses constituants. Les composites utilisés sont constitués d'une résine greenpoxy associée à des fibres de lin et à une âme en liège pour les sandwichs. Dans la première partie, nous avons étudié le comportement en statique et en dynamique de la résine, du composite, des âmes et des sandwichs. Cette étude a conduit d’une part à la détermination des caractéristiques mécaniques et à l’identification et le suivi des mécanismes d’endommagement par émission acoustique et observations microscopiques et d’autre part à la détermination des caractéristiques dynamiques. Dans la deuxième partie, nous avons analysé la cinétique de diffusion d'eau dans la résine, les peaux, les âmes et les sandwichs par identification de leurs paramètres de diffusion par le modèle de Fick. En suite, nous sommes intéressés à l’impact du vieillissement hydrique sur le comportement et les propriétés mécaniques des sandwichs et ses constituants. / In recent decades, polymer composites reinforced with plant fibers have received significant attention from scientists. The use of reinforcing vegetable fibers makes it possible to improve the environmental performance of these materials reaching higher specific properties. Nevertheless, a major lock still hinders the development of these materials. Indeed, their sensitivity to water ageing, due to their hydrophilic nature, restricts their use. In this context, we propose, as part of this thesis, to analyze the effect of water ageing on static and dynamic behavior, to identify and monitoring the damage mechanisms of a sandwich structure biobased and its constituents. The composites used consist of a greenpoxy resin associated with flax fibers and a cork core for sandwich materials. In the first part of this work, we studied the static an dynamic behavior of the resin, the composites, cores and sandwich structures. This study led on the one hand to the determination of the mechanical characteristics and to the identification and the follow-up of the mechanisms of damage by acoustic emission and microscopic observations and on the other hand to the determination of the dynamic characteristics. In the second part, we first analyzed the kinetics of water diffusion in resin, skins, cores and sandwichs by identification of their diffusion parameters by the Fick model approach. Then, we are interested in the impact of water ageing on the behavior and mechanical properties iof sandwichs and its constituents.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

It has been observed that in certain cases the exposure of dyed fibres to aging techniques results in the strengthening of fibres. This thesis explores the hypothesis that the strengthening is due to radical cross-coupling reactions that could be initiated through metal ion mediated photodecarboxylation. The approaches taken in this research include kinetic experiments (using flash photolysis), examination of possible cross-coupling experiments (using species of opposite charge), and the design and examination of small molecule model systems. A flash photolysis system was developed and used in attempts to determine the rates of photochemical product formation for cobalt(III) amino acid complexes. Lower limits have been established for the rate of product formation in these systems. The lower limits are: 2 x 10⁷ s⁻¹ for [Co(bpy)2(gly)]²⁺; 2 x 10⁷ s⁻¹ for [Co(tpa)(gly)]²⁺; and 5 x 10⁶ s⁻¹ for [Co(tpa)(aib)]²⁺, where bpy is 2,2'-bipyridine; gly is glycinate; tpa is tris(2-pyridylmethyl)amine; and aib is aminoisobutyrate. In past studies, the rates of a series of cobalt(III) amino acid complexes were reported as being the same, and much slower. It is thought that in these cases it may not be the rate of the formation of product that was being measured, but rather the response time of the electronics that was being observed. In this thesis the results obtained for the rate for the aib complex were somewhat lower than those of the gly complexes. This may imply, for the aib complex at least, the rate of the formation of the metallocycle is being observed (and not the response times of the electronics or other limitations of the instrumentation), but the data is poor and there is considerable doubt about this. The steady state photolysis of opposite charged species [Co(bpy)2(gly)]²⁺ and [Co(EDTA)]⁻ is reported. The reactions were carried out on a small scale in deuterated solvent for NMR spectrometry analysis and also on a large scale for the possible isolation and characterisation of the products. Evidence was found for a different reaction occurring when both complexes were present. The exact nature of the product remains elusive. A model system was designed in which a dinuclear ligand would bind to two metal centres and a fibre mimic would be later added. Eight ligands are discussed that could potentially bind two octahedral metal centres. They all had a xylene spacing group linking the two polydentate sites together. Five of the ligands have two bidentate binding sites. The other three had two tridentate sites. The binding sites in three of the bis(bidentate) ligands were based on ethane-1,2- diamine (en). Two of these ligands produced hypodentate monocobalt and sundentate dicobalt complexes. The other two bidentate ligands were based on 2- aminomethylpyridine (ampy). Both of these ligands degraded in the complexation reaction conditions. The binding sites in the tridentate ligands were all based on tacn. Once again, the principal products isolated were hypodentate systems in which only one metal ion was coordinated by the ligands. There is a distinct pattern observed in the xylene spaced ligands to form hypodentate complexes with cobalt(III) metal centred complexes. There is evidence of the di-nuclear species from a reaction with a charcoal catalyst in the bis(bidentate) system. ¹H NMR spectrometry, ¹³C NMR spectrometry, elemental analysis, X-ray crystallography and UV-vis spectroscopy were used to study and characterise the complexes and ligands that were prepared in this project.

Dans cette étude doctorale, nous proposons d’étudier la durabilité de deux matériaux composites à matrices thermodurcissable et thermoplastique renforcées par des tissus sergé de lin. Nous analysons d’abord la cinétique de diffusion d'eau dans les deux composites par identification de leurs paramètres de diffusion 3D, via une approche d’optimisation basée sur les modèles de Fick et de Langmuir 3D. Nous étudions ensuite l’effet de plusieurs paramètres géométriques et l’orientation des fibres sur la cinétique de diffusion d’eau au sein des deux composites. Nous analysons par la suite l'effet du vieillissement hydrique sur leurs propriétés élastiques et à la rupture. Enfin, nous proposons une analyse numérique par éléments finis de la diffusion d’eau au sein des deux composites et de leur comportement hydro-élastique. Nous estimons ainsi les paramètres de diffusion de la fibre de lin et des matrices à travers une approche numérique inverse, en décrivant la section et l’ondulation des mèches de lin au sein des deux matériaux. Nous montrons en particulier que les composites non vieillis présentent un comportement mécanique proche de l'effet Kaiser. Cependant, les composites vieillis présentent clairement un effet Felicity, ce qui indique la présence significative d’endommagements induits par l’absorption d'eau. Nous affirmons enfin que l’analyse numérique permet d’identifier d’importantes concentrations de contraintes pouvant induire des endommagements microstructuraux au sein des composites étudiés. / In this thesis work, we study the durability of two twill flax fabrics reinforced thermosetting and thermoplastic composites. Firstly, the diffusion behaviour of these composites is investigated by identifying their 3D Fick’s and Langmuir’s diffusion parameters using an optimization algorithm. The influence of several geometric parameters and fibre orientation on their 3D moisture diffusion is also studied. Then, we analyse the effect of water ageing on their elastic and failure properties. Finally, a numerical finite element analysis is performed in order to study their diffusive and hydro-mechanical behaviour. The water diffusion parameters of the flax fibre and the used resins are estimated by a numerical inverse analysis exploiting experimental water uptake data. The heterogeneity of the studied composites is considered by modelling the twill weave fabrics undulation of their unit-cell. In particular, the mechanical behaviour of the unaged composites is found to exhibit a Kaiser effect contrary to the aged materials which exhibit a significant Felicity effect synonymous of substantial damage induced by water ageing. Besides, it is found that high mechanical stress concentrations are developed at the fibre-matrix interface, which could cause damage initiation and lead to the final composite failure.

L’objectif de ce travail est d’étudier l’effet de différents types de vieillissement sur le comportement mécanique en traction de matériaux composites à fibres de lin et de verre et hybrides lin-verre. L’effet de plusieurs types de vieillissement a été d’abord analysé dans le cas de matériaux composites stratifiés à fibres de lin. Cette étude a permis de suivre l’absorption d’eau dans ces matériaux, et de déterminer leurs paramètres de diffusion en utilisant les modèles de Fick 1D et 3D. Ces paramètres ont été estimés en utilisant une procédure itérative développée à l’aide du logiciel Matlab. Ensuite, une caractérisation des propriétés élastiques et ultimes, à partir des essais de traction des matériaux composites non vieillis et vieillis a été réalisée. Dans le but de réduire l’absorption d’eau et d’améliorer les propriétés mécaniques des composites à fibres de lin, l'hybridation des renforts sergé lin-verre a été choisie. Après l’analyse du comportement mécanique des différents matériaux, l’identification des mécanismes d’endommagement est ensuite menée en utilisant une méthodologie associant la technique d’émission acoustique (EA) et des observations microscopiques. Les signaux d’EA ont été analysés, en considérant une analyse multivariable avec le Logiciel Noesis. La dernière partie aborde une 1ère étape de la modélisation des propriétés élastiques des composites hybrides lin-verre. A partir d’une décomposition de la cellule de base, l’application de la théorie des stratifiés a permis de déterminer les propriétés élastiques du composite en fonction de ses constituants (fibres et matrice) en tenant compte de la géométrie de l’armure. / The main objective of this work is to study the effect of several ageing processes on the tensile mechanical behaviour of flax-glass fibres non-hybrid and hybrid composite materials. First, the effect of several types of ageing was analysed in the case of flax fibre reinforced composites. This study enabled to determine the diffusion parameters of these materials by using 1D and 3D Fick’s model. For this purpose, an analytical modelling was applied, using optimisation toolbox of Matlab. The second part aims at analysing the tensile mechanical properties of the unaged and aged composite materials. With the aim to improve the mechanical properties as well as the moisture resistance behaviour of flax fibre reinforced composites, hybridation of twill flax-glass fibres was proposed. Next, the Acoustic Emission (AE) technique combined with scanning electron microscopy observations was used to identify the damage events leading to overall failure of the studied composites. The AE signals obtained during mechanical tensile tests were analysed and classified using a non-supervised method with Noesis Software. The last part is devoted to the first step in determining the elastic behaviour of flax-glass hybrid composites. By discretizing the unit-cell of the composite, the use of the classical thin laminate theory made it possible to determine the elastic properties of the composite, considering constituents (resin and fibres) and microstructure geometry.

La présente étude traite de l’éco-conception d’une pièce structurale, de type poutre tubulaire, en stratifié bio-composite à base de fibres de lin. A cette pièce à concevoir est associé un cas de charge mécanique combinant flexion et torsion et une tenue face aux produits détergents-décontaminant utilisés en environnement médical. Cette étude a pour objectif de montrer la faisabilité d’employer comme architecture de renfort, une mèche de lin pour la réalisation de la pièce. Ce renfort a la particularité d’être constitué de fibres alignées dont la cohésion est assurée par la présence d’un liant par opposition aux fils constituées de fibres retordues. Tout d’abord, pour établir un cahier des charges de fabrication à partir de ceux déjà en vigueur, le comportement mécanique du bio-composite à l’échelle du pli, puis à celui du stratifié et enfin à l’échelle de la poutre stratifié a été modélisé et des critères de conception et de dimensionnement portant sur la rigidité en flexion et en torsion ont été développés de façon analytique. Associée à cette approche et au choix du renfort, le procédé d’enroulement filamentaire a été retenu pour la mise en oeuvre de la pièce. Afin de montrer la compatibilité de la mèche en entrée et le procédé sélectionné, une étude du comportement en traction de la mèche visant à étudier l’effet des paramètres du procédé sur les propriétés mécaniques de la mèche a été réalisée. Cette deuxième phase a été poursuivie par la réalisation de prototypes, suivant le cahier des charges de fabrication établit, qui ont ensuite été analysés en termes de qualité et de performances mécaniques. La corrélation entre ces résultats et ceux obtenus par l’étape de dimensionnement a permis de valider l’approche. Enfin, dans le but d’intégrer l’interaction avec l’environnement opératoire dans le dimensionnement de la pièce, une étude de la durabilité a été réalisée. Celle-ci permet d’établir des stratégies de dimensionnement pour répondre à l’application. / This study aims at eco-designing a structural part, of a hollow beam type, using a laminated flax fibre based bio-composite. The part needs to satisfy a given bending and torsion load case and show compatibility with the cleaning products used in the medical environment. The objective of the study is to investigate the potential of using a flax tow as the reinforcement input for the manufacturing of the beam. The particularity of the reinforcement is that it consists of an assembly of aligned flax fibres held together by a binder as opposed to spun yarns. First, in order to establish the required manufacturing specifications, the mechanical behaviour of the bio-composite at the ply scale, at the laminated and finally at the laminated beam scale was modelled. From this modelling, design and dimensioning criteria based on bending and torsional stiffness were developed analytically. Combining this approach with the choice of the reinforcement, the wet-filament winding process was chosen to manufacture the part. Thus, the tensile behaviour of the flax tow was studied in relation to the process parameters to demonstrate their compatibility. This second phase was followed by the manufacturing of prototypes according the established specifications which were then analysed in terms of quality and mechanical performance. The correlation between experimental results and the model predictions was used to validate the dimensioning approach. Finally and in order to incorporate the interaction of the part with the environment, a durability study was conducted. The latter allows to put forward different dimensioning strategies to meet the required specification.

Cette thèse s’inscrit à mi-chemin entre l’étude de la déformabilité des structures tissées et la valorisation de la fibre de lin pour des applications dans le renforcement des matériaux composites. Le premier objectif de l’étude est de caractériser expérimentalement le comportement en flexion des mèches de différentes structures constituées de fibres de lin ainsi que des tissus de différentes armures. Les travaux ont abordé aussi des paramètres tels que l’humidité relative et la composition (des mèches comélées ou en lin pure). Le deuxième objectif des travaux est d’étudier le comportement en flexion des tissus en fonction du comportement en flexion des mèches. Cette partie a commencé par la modélisation géométrique des renforts tissés dans le but de suivre l’évolution de la section du tissu qui varie dans la direction de la flexion. La modélisation mésoscopique a permis de calculer analytiquement les propriétés géométriques du tissu en particulier son moment quadratique. Les résultats obtenus ont été utilisés dans la simulation de la flexion du tissu. L’étude a permis de voir jusqu’à quel point le comportement de la mèche et le moment quadratique du tissu pilotent le comportement en flexion du tissu. D’après ces travaux, le comportement en flexion du tissu semble être approché de façon satisfaisante sur toute la gamme de longueurs envisagées à partir de ces deux grandeurs sauf pour les forts taux d’humidité où d’autres phénomènes doivent être considérés. L’étude a souligné que la différence entre deux renforts testés expérimentalement peut être anticipée numériquement. Ainsi, le concepteur de tissus sera capable d’anticiper la rigidité expérimentale du tissu pour faire des tissages adaptés à la mise en forme du renfort. Une étude paramétrique de la flexion a été également réalisée dans le but de déduire les paramètres les plus influents sur lesquels il peut jouer. / This thesis is halfway between the study of the deformability of woven structures and the use of flax fibre as reinforcement of composite materials. The first aim of the study is the experimental characterization of the bending behaviour of tows with different structures made of flax fibres and fabrics with different weaves. Parameters such as relative humidity and the composition (100% flax and commingled tows) were also considered. The second aim of the study is to link the bending behaviour of the fabric to the bending behaviour of its constituent tows. This part starts with the geometric modelling of woven fabrics in order to follow the variation of its section in the bending direction. Mesoscopic modelling allows the analytical calculation of the geometric properties of the fabric in particular its moment of inertia. The results obtained were used in the simulation of the fabrics bending to see how far the behaviour depends on the tows bending behaviour and the moment of inertia. The bending behaviour of the fabric seems to be approached satisfactorily from these two factors. This is verified within the range of lengths considered except for high humidity (in this case, other phenomena must be considered). The study pointed out that the difference between two reinforcements tested experimentally can be predicted numerically. Thus, the fabrics designer will be able to anticipate the experimental bending stiffness of the fabric in order to adapt the weaving to the shape forming. A parametric study of the bending was also achieved in order to deduce the most influential parameters of the fabric for an appropriate weaving.