Tannins represent a heterogeneous group of high-molecular-weight polyphenols that are ubiquitous among plant families, especially in cereals, as well as in many fruits and vegetables. Hydrolysable and condensed tannins, in addition to phlorotannins from marine algae, are the main classes of these bioactive compounds. Despite their low bioavailability, tannins have many beneficial pharmacological effects, such as anti-inflammatory, antioxidant, antidiabetic, anticancer, and cardioprotective effects. Microbiota-mediated hydrolysis of tannins produces highly bioaccessible metabolites, which have been extensively studied and account for most of the health effects attributed to tannins. This review article summarises the effect of the human microbiota on the metabolism of different tannin groups and the expected health benefits that may be induced by such mutual interactions. Microbial metabolism of tannins yields highly bioaccessible microbial metabolites that account for most of the systemic effects of tannins. This article also uses explainable artificial intelligence to define the molecular signatures of gut-biotransformed tannin metabolites that are correlated with chemical and biological activity. An understanding of microbiota–tannin interactions, tannin metabolism-related phenotypes (metabotypes) and chemical tannin-metabolites motifs is of great importance for harnessing the biological effects of tannins for drug discovery and other health benefits.

A two-year study was conducted to assess the effects of cofermentation on red wine varietals. During the winemaking process, wines can be made from two or more varieties by picking, crushing and fermenting them together, a practice known as cofermentation. They can also be blended either after the completion of alcoholic fermentation or after malolactic fermentation. In the first year of the study, two grape varieties, Merlot (Mer), and Malbec (Mal) were cofermented. On the second year, a third varietal, Petite Sirah (PS) was also studied. Cofermented wines containing every possible binomial combination of the varietals was made and one trinomial on 2019. The cofermented wines were compared to monovarietal wines and also to wines that were produced by blending either after alcoholic fermentation or after malolactic fermentation. The phenolic profile of the wines was followed from the onset of fermentation up to 36 months of bottle aging for the 2018 vintage and in the case of the 2019 vintage, up until 250 days after crushing. In 2018, cofermented wines and wines that were blended after malolactic fermentation had an anthocyanin profile that was more similar to Malbec than to Merlot, while the tannin profile was more resemblant of Merlot. In 2019 cofermentation improved the anthocyanin content when compared to post alcoholic and post malolactic blend only when the three varietals were cofermented. A sensory analysis with 10 trained individuals was conducted on the 2018 vintage. It was demonstrated that Malbec wines had a higher amount of red fruit aromas while Merlot wines were perceived as being more astringent. Cofermented and post malolactic fermentation blended wines were indistinguishable to panelists and blending after alcoholic fermentation produced wines that highlighted the individual varietal character.

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Animal welfare is a major concern among livestock producers in the U.S. Heat stress, particularly, compromises animal welfare and productivity, causing >$2B annual economic loss to producers. The presence of toxic alkaloids within tall fescue (Schedonorus phoenix syn Lolium arundinaceum, syn Festuca arundinacea) plants induces a complex of disorders collectively known as fescue toxicosis. Summer slump, a reduction in animal performance due to heat stress, is common and evident of the symptoms. Various techniques for assessing animal physiological and behavioral responses to heat stress were explored in this dissertation, with particular emphasis on fescue toxicosis and its mitigation strategies. In the first study, the physiological and behavioral responses of heifers was evaluated when grazing either toxic tall fescue with wildtype endophyte (WE) or tall fescue with a novel endophyte (NE). Heifers (n = 24) were assigned to either WE or NE pastures for a 56-d grazing study during the summers of 2020 and 2021. Heifer average daily gain (ADG), intravaginal temperature, and degree of hair shedding were recorded during the grazing period. Blood samples were collected through coccygeal venipuncture and hair was collected from the left rump for cortisol analysis. Ear, tail, and hoof temperatures were collected for each heifer using an infrared thermal imaging camera. In 2020, heifers that grazed NE tall fescue had greater (P = 0.0160) ADG over the season (0.22 vs. 0.12 kg day-1). Hair retention score was greater (P = 0.0029) for heifers that grazed WE tall fescue compared to heifers that grazed NE tall fescue across both years. Heifers that grazed WE tall fescue had decreased ear skin temperature (P = 0.0001), tail skin temperature (P = 0.0058), and hoof surface temperature (P = 0.0075) compared to heifers that grazed NE. Heifers that grazed WE had 0.3-0.9 ºC hotter intravaginal temperatures than heifers that grazed NE, especially during daytime. Hair cortisol levels of heifers that grazed WE tall fescue were greater (P < 0.0001) compared to hair cortisol levels of heifers that grazed NE tall fescue. From 1200h-1700h each day, heifers that grazed WE tall fescue spent 1.5 more (P = 0.0003) hours standing and 0.9 fewer (P = 0.0402) hours lying down compared to heifers that grazed NE tall fescue. These results suggest that heat stress and other physiological changes in heifers grazing WE tall fescue could be mitigated by renovating pastures with NE tall fescue that does not impose any negative effects on grazing animals. The second study explored the potential benefits of consuming condensed tannins as a means of negating the effects of toxic alkaloids in tall fescue. Twelve fall-born steers were assigned to one of the two diet supplement treatments - sericea lespedeza pellets (LES) or sericea lespedeza pellets mixed with polyethylene glycol (LES+PEG) for 12 weeks during the summers of 2020 and 2021. The LES+PEG treatment served as a positive control since polyethylene glycol binds tannins, rendering them inactive in the gastrointestinal system. Animal body weight (BW), hair retention score (HRS), rectal temperature, and thermographic images were collected every 4 weeks. Hair and blood samples were also collected for cortisol analysis. Fecal and urine samples were collected and analyzed for total ergot alkaloid (TEA) concentration. Steers on LES had greater (P = 0.0033) ADG compared to steers on LES+PEG in 2021, but not in 2020 (P = 0.8707). In 2021, HRS was greater (P < 0.05) for steers fed LES+PEG compared to steers fed LES. In 2020, ear skin temperature (P < 0.0001) and hoof surface temperature (P = 0.0382) was greater in steers on LES compared to steers on LES+PEG. Rectal temperatures were lower (P = 0.02905) for steers fed LES compared to steers fed LES+PEG in 2021. Plasma cortisol levels did not differ (P ≥ 0.1566) between LES and LES+PEG treatments for both years. In 2020, hair cortisol levels did not differ (P = 0.8295) between treatments while in 2021, the hair cortisol level of steers on LES+PEG was greater (P = 0.0221) compared to hair cortisol levels of steers on LES. This study indicated some changes in animal physiology in response to dietary supplements containing condensed tannins, but results were inconsistent and further studies are needed to better understand the potential benefits of tannins in reducing the effects of toxic alkaloids consumption. In the third study, behavioral and physiological responses of ewes that grazed either mid-stage hardwood silvopastures or open pasture (OP) were compared. The study site consists of 0.27-ha of black walnut (Juglans nigra; BSP) and honeylocust (Gleditsia triacanthos; HSP) silvopastures and open pasture treatments, each replicated three times. During the summers of 2020 and 2021, thirty-six Katahdin ewes were assigned to one of the treatments for a 6-week summer grazing trial. Ewe weights were recorded for two consecutive days at the beginning and end of the study and intravaginal temperatures were recorded for two consecutive days at every 3-week intervals. Trail cameras captured animal behavior. Blood was collected via jugular venipuncture. Hair grown during the trial was collected from the loin region. Blood and hair cortisol concentrations were determined by ELISA. Ewe ADG was greater in HSP compared to OP (P = 0.0456) but did not differ with BSP (P = 0.4686) across both years. Ewes on OP had hotter (P ≤ 0.0343) intravaginal temperatures than ewes on both silvopasture treatments between 1100h-1700h. Plasma cortisol level was lower in ewes on BSP compared to ewes on OP (P = 0.0400) but did not differ with ewes on HSP (P = 0.6954) across both years. Ewes that grazed OP had greater hair cortisol levels compared to ewes on silvopasture treatments both in 2020 and 2021 (P < 0.0001). In 2020, ewes on BSP spent about 20% more time grazing than ewes on OP (P = 0.0054) while in 2021 ewes on BSP spent about 36% more time grazing than ewes on HSP (P = 0.0014). Ewes on OP spent 400% more time standing than ewes on BSP (P < 0.0001) and 750% more time standing than ewes on HSP (P < 0.0001). Ewe on OP spent 20% less time lying down compared to ewes on BSP (P < 0.0001) and 33% less time lying down compared to ewes on HSP (P < 0.0001). Hair cortisol measures and intravaginal temperature sensors can be utilized as reliable and relatively non-invasive techniques for measuring heat stress response in livestock managed in extensive grazing systems. / Doctor of Philosophy / Heat stress compromises animal welfare and productivity, causing > $2B annual economic loss to producers in the U.S. In the southeastern U.S, heat stress in livestock is largely due both to an environmental condition and to the effect of fescue toxicosis caused by toxic alkaloids. Various management strategies to mitigate the effect of heat stress in livestock due to environmental conditions or due to the effect of tall fescue toxicosis are explored in this dissertation. In the first study, behavioral and physiological responses of heifers that grazed either toxic (WE) or novel (NE) endophyte-infected tall fescue was compared. Heifers that grazed WE tall fescue had lower gains, rough hair coat, higher hair cortisol level (stress measure), cooler extremity temperature, and hotter intravaginal temperature compared to heifers that grazed NE tall fescue. These results suggest that heat stress and other physiological changes in heifers grazing WE tall fescue could be mitigated by renovating pastures with NE tall fescue, a forage cultivar that does not impose any negative physiological effects on grazing animals. In the second study, we tested the effect of condensed tannins in reducing the severity of fescue toxicosis in steers. We fed sericea lespedeza pellets to steers in a study to test this effect. All steers were fed sericea pellets, but pellets for half (6) of the steers were treated with polyethylene glycol, which inactivates the condensed tannins in the sericea lespedeza. In our study, we found that the steers fed the sericea lespedeza had higher temperatures at their extremities (ears and tail), but lower rectal temperatures than the control steers. Interestingly, the steers fed the sericea lespedeza pellets also had slicker hair coats and lower levels of hair cortisol (indicating reduced stress) in the second year compared to the control steers. This study showed some potential of condensed tannins in reducing the effects of fescue toxicosis, but needs further study to better understand the potential benefits of tannins in reducing the post-ingestive effects of fescue toxicosis. In the third study, we compared behavioral and physiological (temperature, hair, and blood cortisol) responses of ewes that grazed either mid-stage hardwood silvopastures or open pastures (OP). Ewes on OP showed signs of heat stress with higher hair cortisol levels and hotter intravaginal temperatures during the daytime compared to ewes on silvopasture treatments. Ewes on OP spent 400% more time standing compared to ewes on BSP and 750% more time standing than ewes on HSP. Ewe on OP spent 20% less time lying down compared to ewes on BSP and 33% less time lying down compared to ewes on HSP. Ewes on silvopasture treatments spent 70% less time drinking water compared to ewes on OP. Trees within the silvopasture systems can alter the micro climatic condition thus creating a suitable environment for livestock. This can ultimately reduce stress and improve overall behavioral and physiological responses of livestock in silvopastures compared to open pastures.

<u>Endothia parasitica</u> (Murr.) P. J. & H. E. Anderson (syn: <u>Cryphonectria parasitica</u>(Murr.) Barr), the causal agent of chestnut blight, was able to grow in total aqueous and tannin extracts from blight-susceptible American chestnut as well as in blight-resistant Chinese chestnut bark extracts, from winter and summer bark. Differences in the amount of conidial germination and growth in extracts of the two species were small. The, <u>E. parasitica</u> tannase was more abundant intracellularly than extracellularly. Total tannase activities from cultures in American chestnut aqueous and tannin extracts were greater than in the Chinese chestnut extracts, for both winter and summer bark. The tannase was isolated from the mycelium of E. parasitica and purified 142-fold with a 10% yield by anion exchange chromatography and gel filtration. The estimated molecular weight was 240 kD and the molecule may be a tetramer composed of four subunits with a molecular weight of 58 kD. The pH optimum of the purified tannase was 5.5 and the temperature optimum for activity was 30 C. The enzyme was separated into six bands in the pH range of 4.6 to 5.1 which may represent isoenzymes or post-translational modifications. / Ph. D.

La vigne Vitis vinifera, appelée aussi «vigne européenne», est l’espèce la plus cultivée mondialement pour la production de vin. Dans les régions froides comme le Québec, les vins sont majoritairement produits à partir de cépages hybrides interspécifiques (CHI) qui offrent une plus grande tolérance au froid et aux maladies. Les vins rouges issus des CHI sont généralement décrits comme étant moins astringents et plus colorés que les vins rouges européens issus de V. vinifera, ce qui ne répond pas toujours aux goûts des consommateurs. Ces caractéristiques sont attribuables à des différences de composition entre les baies de CHI et de V. vinifera. Une meilleure compréhension des molécules affectant la rétention et la composition en tanins des vins de CHI rouges et des procédés de vinification affectant leurs profils pourrait permettre de modifier leur astringence et contribuer à augmenter la compétitivité des vins rouges issus de CHI sur le marché.Trois études ont été conduites sur ce thème dans le cadre de cette thèse. La première étude avait pour but d’étudier l’impact de l’utilisation de marc de raisin blanc (MRB) en co-fermentation avec du marc de raisin rouge (MRR) sur la teneur en tanins des vins, en utilisant les CHI Frontenac et Vidal. Les résultats ont montré que les vins produits avec du MRB présentaient plus de flavan-3-ols monomériques et oligomériques et davantagede terpènes. La manipulation du ratio MRR/MRB a permis de modifier le profil en anthocyanes des vins finis, résultant dans certains cas en des vins plus clairs. L’utilisation d’un ratio MRR/MRB approprié (30% MRR/6% MRB) a permis une meilleure stabilisation de la couleur des vins sans affecter significativement la couleur. L’utilisation de MRB en co-fermentation avec du MRR s’est avérée un outil intéressant pour moduler la couleur des vins ainsi que leur composition phénolique et volatile. La seconde étude avait pour objectif d’étudier l’impact de différents traitements seuls ou en combinaison (traitements pré-fermentaire du moût, fermentation en présence et absence de marc, addition de tanins œnologiques) sur la teneur en tanins, en protéines et en pigments des vins de Frontenac. L’élimination des protéines par chauffage du moût ou ajout de bentonite n’a pas permis une meilleure rétention des tanins dans le vin. Néanmoins, fermenter le moût sans marc de raisin a amélioré significativement leur rétention dans le vin, notamment celle des flavan-3-ols polymériques (jusqu’à 27,8%). L’addition de 3 g/L de tanins œnologiques dans les vins, fermentés en présence et absence de marc, s’est montrée nécessaire pour augmenter significativement la concentration en tanins des vins de Frontenac. La troisième étude consistait en une étude exploratoire et comparative de la teneur et de la nature des polysaccharides des vins de CHI Frontenac et Frontenac blanc avec celles du V.vinifera Cabernet Sauvignon. Les vins de Frontenac ont montré une concentration plus élevée en polysaccharides totaux et des polysaccharides plus ramifiés que les vins de Cabernet Sauvignon. Ces différences pourraient contribuer à la faible astringence des vins rouges issus de CHI par rapport à celle des vins rouges de variété V. vinifera. Ce projet a permis d’apporter de nouvelles connaissances sur le profil d’extraction et la rétention des tanins dans les vins de CHI cultivés au Québec. Une meilleure compréhension des facteurs impliqués dans la rétention des tanins dans ces vins a permis de fournir des pistes à envisager pour élaborer des procédés de vinification adaptés à la composition physico-chimique atypique des CHI rouges afin de produire des vins plus riches en tanins, ayant un potentiel accru de répondre aux goûts des consommateurs. / Vitis vinifera is the most cultivated grapevine species for wine production, worldwide. But in cold areas such as Quebec, Canada, most wine is produced from interspecific hybrid grape varieties (CHI) that better respond to harsh growing conditions such as cold temperature and high disease pressure. Red CHI wines are generally described as less astringent and more colourful than European V. viniferared wines, but those characteristics do not fully align with consumers taste and preferences. The low astringency of red CHI wine is largely attributable to differences between the respective chemical composition of CHI and V. vinifera berries. A better understanding of the molecules affecting tannin retention and composition of red CHI wines, and of the winemaking processes that affect their tannin profiles could provide solutions to impact their astringency and improve their competitiveness on the market. Three studies conducted on this topic as part of this thesis are presentedin this manuscript.The first study aimed at investigating the impact of the co-fermentation of white (WP) and red (RP) grape pomace on the tannin content of red wine, using the CHI varieties Frontenac and Vidal. The results showed that wines produced with WPcontained higher levels of monomeric and oligomeric flavan-3-ols and terpenes than wines issued from the RP treatment. Modifying the ratio of RP to WP during alcoholic fermentation modified the anthocyanin profile of the wines, sometimes resulting in lighter coloured wines. A ratio of 30% RP to 6% WP improved colour stabilisation without significantly affecting wine colour. The use of WP in co-fermentation with RP proved to be an interesting tool to modulate wine colour as well as its phenolic and volatile composition.The second study aimed at exploring the impact of different wine making treatments (pre-fermentative treatment of the must, fermentation with andwithout pomace, additionof enological tannins), alone or in combination, on the tannin, protein and pigment content of Frontenac wines. Wine protein removal by heat or bentonite addition did not improve tannin retention in wine. In contrast, fermenting the must without pomace significantly improved tannin retention, especially for polymeric flavan-3-ols (up to 27.8%). With or without pomace, the addition of enological tannins at a minimal rate of 3 g/L, was necessary to increase tannin concentration in Frontenac wine significantly.The third study explored the content and, to some extent, the molecular weight and structure of the polysaccharides from the CHI Frontenac and Frontenac Blanc, in comparison with wines from theV. vinifera variety Cabernet Sauvignon. Frontenac wines showed a higher concentration of total polysaccharides with more branched polysaccharides than wines from Cabernet Sauvignon. Results showed that significant differences exist between the polysaccharides content and structure of the studied CHI varieties and Cabernet Sauvignon variety. Those differences could contribute to the low astringency of CHI wines when compared with red wines from V. vinifera varieties. This project has brought new knowledge on the tannin, protein and polysaccharide content of red CHI varieties grown in Quebec and how they impact tannin retention in CHI wines. Understanding the chemistry of phenolic compounds and macromolecules in CHI wines made possible the development of new wine making processes adapted to the atypical biochemical composition of red CHI wine. As such, results from this study provide new venues to vary and improve the style and the quality of CHI wines and better meet consumers taste and preferences.

La qualité nutritive et allélochimique de la plante hôte joue un rôle déterminant dans la dynamique des populations des défoliateurs forestiers. La tordeuse des bourgeons de l’épinette (Choristoneura fumiferana (Clem.)) (Lepidoptera : Tortricidae) (TBE) est un lépidoptère considéré comme le plus important ravageur des forêts d’Amérique du Nord et attaque principalement le sapin baumier (Abies balsamea (L.)) et l’épinette blanche (Picea glauca (Moench) Voss). Le feuillage de ces essences hôtes contient des composés polyphénoliques (les tannins) lesquels sont souvent rapportés dans la littérature comme composés chimiques utilisés par les plantes pour limiter les impacts des espèces herbivores. Certains traitements sylvicoles comme les éclaircies sont parmi un ensemble de facteurs aptes à influencer la composition polyphénolique des essences ligneuses. Ainsi, l’éclaircie dans de jeunes peuplements de sapins baumiers a déjà été reliée à des baisses en contenu de tannins et des hausses en azote foliaire un an après le traitement. De plus, lors d’une étude sur le terrain, les effets à court terme de l’éclaircie sur ces composés chimiques ont été corrélés à des augmentations de survie larvaire et de vitesse de développement chez la tordeuse des bourgeons de l’épinette. Toutefois, la relation de cause à effet entre les effets de l’éclaircie sur la chimie de l’essence hôte et les performances de l’insecte reste à être établie. Dans la présente étude, l’impact des variations en tannins et azote foliaire induites par l’éclaircie sur la survie, le développement, la croissance et l’utilisation de la nourriture par les larves de TBE a été étudié à l’aide d’extraits polyphénoliques purifiés et de diverses sources d’azote incorporés à diverses concentrations dans une nourriture artificielle. Les résultats de cette étude supportent l’hypothèse que les variations polyphénoliques et azotées foliaires, induites par l’éclaircie des jeunes peuplements de sapin baumier, sont responsables des effets positifs à court terme de ce traitement sur la survie et le développement de l’insecte de même que sur les augmentations de défoliation observées suite au traitement. Des expériences sur l’utilisation de la nourriture par la TBE en fonction des contenus en tannins de sa nourriture ont aussi été menées à l’aide de tannins extraits et purifiés de feuillage de sapin baumier et incorporés à diverses concentrations dans une nourriture artificielle. Ces travaux visaient à documenter le degré de plasticité de l’insecte en terme de processus d’utilisation de nourriture face aux variations en contenus polyphénoliques de sa nourriture. Des travaux similaires ont été conduits à l’aide de tannins extraits de feuillage d’épinette blanche. Dans le cas du sapin baumier, les résultats montrent que l’insecte possède une panoplie de mécanismes de compensation dans ces processus alimentaires pour limiter les impacts des tannins. Toutefois, des effets négatifs sur les performances de l’insecte sont détectés à mesure que les contenus en tannins de sapin baumier augmentent dans le substrat alimentaire. En ce qui concerne l’épinette blanche, l’insecte possède aussi une panoplie de mécanismes de compensation. Contrairement au sapin baumier, l’épinette blanche semble contenir un niveau optimal de tannins dans son feuillage au delà duquel la plante n’obtient pas de gain supplémentaire en terme d’effets létaux sur l’insecte. Une expérience a aussi été conduite sur le système d’interaction Tannins d’épinette blanche - Bacillus thuringiensis var. kurstaki (Btk) – TBE à l’aide d’extraits polyphénoliques de feuillage et de toxines de Btk incorporés seuls et/ou en combinaison à diverses concentrations dans un substrat alimentaire artificiel. Les résultats de ces travaux ont montré qu’individuellement ces deux types de composés (tannins et Btk) ont de sérieux effets délétères sur l’insecte. Cependant, lorsqu’ils sont présents ensemble dans la nourriture, ces derniers ont des effets antagonistes mutuels réduisant ainsi leurs effets létaux respectifs envers l’insecte. / Host plant nutritive and allelochemical characteristics are important factors of forest insect defoliator population dynamics. The spruce budworm (Choristoneura fumiferana (Clem.)) (Lepidoptera : Tortricidae) is one of the most important lepidopteran forest pests of North America attacking especially balsam fir (Abies balsamea (L.)) and white spruce (Picea glauca (Moench) Voss) trees, two host tree species that contains polyphelonics which are believed to act as defensive chemicals against herbivores. Certain sylvicultural treatments such as stand thinning are among the variables that affect host tree foliar polyphenolics. Stand thinning of young balsam fir tree stands is known to decrease, the year following the treatment, host content in foliar tannin and to increase foliar nitrogen. These short term changes in host chemistry have already been related shown to increases in spruce budworm larval survival and development rates in field studies. However, the cause-effect relationship remains to be established. In the current study, effects of variations in balsam fir foliar tannin and nitrogen related to stand thinning were investigated on spruce budworm survival, growth, development and food utilization using purified tannins from host tree foliage and various sources of proteins incorporated into artificial diet. Results from this study support the hypothesis that changes in host tree tannin and nitrogen following thinning of young balsam fir stands are responsible for increases budworm survival and defoliation. Food utilization studies were also conducted using balsam fir foliage purified tannin extract incorporated into artificial diet in order to document the level of tolerance and plasticity of budworm larvae to foliar polyphenolic variations. Similar studies were conducted using white spruce foliage. In the case of balsam fir foliar tannins, it appears that the spruce budworm is negatively affected by these compounds as their concentration increases in host trees. The insect exhibited various types of compensatory feeding mechanisms that allowed it to partially deal with both balsam fir and white spruce tannins. Contrary to balsam fir, white spruce trees appear to contain an optimal amount of tannins above which the host tree does not produce any more gain more deleterious effect on the insect. An additional study that investigated the system of interactions white spruce tree tannin - Bacillus thuringiensis var. kurstaki (Btk) - spruce budworm was conducted using artificial diet supplemented with various concentrations of tannin and Btk purified toxin. Results indicate that alone in the diet, tannin and Btk toxin have deleterious effects on spruce budworm larvae. However, when these compounds are both present in the diet they antagonize each other such that their respective potency against the insect is reduced.

L'objectif de ce travail de thèse a été de produire des matériaux expansés à partir de produits d'origine naturelle, en particulier à partir de tanins. Au moment où cette thèse a débuté, des études étaient publiées sur la possibilité d'élaborer ce type de matériaux avec des formulations qui comportaient du formaldéhyde. Cela allait à l'encontre du caractère naturel recherché puisqu'en fait, on utilisait des produits naturels et les faisait réagir avec un produit cancérogène. Il n'était donc pas possible de les présenter comme des matériaux « verts ». Aussi, nous avons voulu au cours de ce travail, élaborer des matériaux expansés uniquement à partir de produits naturels ou en découlant. Les tanins sont des substances naturelles chimiquement actives qui peuvent être utilisées afin de remplacer des produits homologues dérivés du pétrole comme le phénol par exemple qui présente des caractéristiques de réactivité chimique très similaires à celles des tanins condensés. Des formulations comportant des tanins condensés ont d'ailleurs déjà été étudiées pour élaborer des matériaux expansés. En considérant cela, ce travail de thèse s'est déroulé sous la forme de différents projets convergents vers un objectif commun: la production de mousses aux tanins plus naturelles et plus intéressantes pour l'industrie. Cinq projets ont ainsi été menés : 1. analyses de différents tanins, condensés, hydrolysables et synthétiques ; 2. production de mousses aux tanins sans utilisation de formaldéhyde ; 3. production de mousses aux tanins sans solvants ; 4. production de mousses aux tanins rigides ou élastiques ; 5. production de mousses aux tanins, sans acides, mais avec une catalyse alcaline / The aim of this thesis was to produce foamed materials from natural products, especially from tannins. At the time this thesis began, studies were published on the possibility of doing this type of materials with formaldehyde containing formulations. This was contrary to the desired natural character because in fact, were used natural products reacted with carcinogenic product. It was not possible to present them as "green" materials. During this thesis our aim was to develop expanded materials only from natural or bio-derived raw materials. Tannins are chemically active natural substances that can be used to replace homologous oil derivatives such as phenol which has characteristics of chemical reactivity very similar to those of condensed tannins. Formulations containing condensed tannins have already been studied to develop expanded materials. Considering this argument, this thesis takes place in the form of various projects converging towards a common goal: production of foams with more natural impact and interesting for tannins industry. Five projects have been completed: 1. analysis of various tannins, condensed, hydrolysable and synthetic ; 2. tannin foams production without the use of formaldehyde ; 3. tannin foams production without solvents ; 4. tannin foams production with rigid or elastic behavior ; 5. tannin foams production without acids, but with an alkaline catalysis

Master of Science / Department of Animal Sciences and Industry / KC Olson / Condensed tannins (CT) in plants are phenolic compounds with relatively high binding affinities for proteins. In ruminants, dietary CT limit DM intake and digestibility, and ruminal protein degradation by forming CT-protein complexes. Effects of dietary CT, animal species, prior dietary CT exposure, and antimicrobial inclusion on 48-h rate and extent of digestion were measured in two in vitro experiments. Cattle, sheep, and goats (n = 3 / species) were used in a 2-period, randomized complete-block experiment with a 2 × 3 × 2 × 3 factorial arrangement of treatments. Factor 1 was substrate: tannin-free or high-CT. Factor 2 was source of ruminal fluid inoculum: cattle, sheep, or goat. Factor 3 was prior animal exposure to a high-CT diet: non-exposed or exposed. Factor 4 was inclusion of antimicrobials: no antimicrobial, penicillin + streptomycin to suppress bacterial activity, or cycloheximide to suppress fungal activity in the fermentation. Tannin-free or high-CT substrates were incubated in vitro using ruminal fluid from animals either not exposed (period 1) or exposed to dietary CT (period 2). Periods consisted of an adaptation to tannin-free (10 d) or high-CT diets (21 d) and a 15-d period of ruminal-fluid collection via stomach tube. The presence of CT or penicillin + streptomycin in in vitro fermentation reduced (P < 0.001) total gas pressure, DM disappearance, and total VFA, acetate, propionate, butyrate, valerate, and branched-chain VFA concentrations. We concluded that: 1) CT had negative effects on fermentation, 2) prior exposure to dietary CT attenuated some but not all negative effects, and 3) CT effects were similar to the effects of penicillin + streptomycin.

Thesis (MSc)--University of Stellenbosch, 2011. / ENGLISH ABSTRACT: High molar mass tannin extracts are complex mixtures which are distributed in both molar mass and chemical composition. Condensed tannins from quebracho and mimosa and hydrolysable tannins of tara, chestnut wood and turkey gall were studied. Application of a single analytical technique is not sufficient to elucidate the complete structures present in the extracts. 13C Nuclear Magnetic Resonance (NMR) spectroscopy and Matrix Assisted Laser Desorption/Ionisation Time-of-Flight (MALDI-TOF) mass spectrometry were applied in order to determine the chemical composition and molar mass, respectively. A new mass spectrometric method that can uniquely determine the oligomer microstructure was developed using Collision Induced Dissociation (CID) experiments. Bulk analysis only showed the average composition of the extracts, in order to obtain specific information on the molar mass and chemical composition distributions. Hydrophilic Interaction Liquid Chromatography (HILIC) was used for analysis of the condensed tannins and for the hydrolysable tannins Normal Phase Liquid Chromatography (NP-LC) was utilised. The HILIC separation was up-scaled and the fractions were collected and analysed by MALDI-TOF, and this coupling revealed that separation occurs by molar and chemical composition. For separation of the molecules only by size, Size Exclusion Chromatography (SEC) analyses were carried out; this allowed for relative comparison of the tannin molecules. In conclusion, for characterisation of high molar mass tannins a multi-dimensional approach was necessary since the various distributions present in these extracts are superimposed. / AFRIKAANSE OPSOMMING: Hoë molekulêre massa tannienekstrakte is komplekse mengsels, in terme van beide molekulêre massa en chemiese samestelling. Gekondenseerde tanniene vanaf quebracho en mimosa, en hidroliseerbare tanniene vanaf tara, kastaaiinghout en Turksegal is bestudeer. Die gebruik van ‘n enkele analitiese tegniek is nie voldoende om die volledige struktuur van komponente teenwoordig in die ekstrakte te analiseer nie. 13C KMR-spektroskopie en MALDI-TOF-massaspektroskopie is gebruik om die chemiese samestelling en molekulêre massa, onderskeidelik, te bepaal. ‘n Nuwe metode is ontwikkel vir die bepaling van die oligomeer-mikrostruktuur deur gebruik te maak van botsings-geïnduseerde dissosiasie eksperimente. Grootmaat analise het net die gemiddelde samestelling van die ekstrak bepaal. Hidrofiliese-interaksie-vloeistofchromatografie (HILIC) is gebruik vir die analise van gekondenseerde tanniene en gewone fase-vloeistofchromatografie is gebruik vir die hidroliseerbare tanniene. Die HILIC-skeiding is op groter skaal uitgevoer en die fraksies is versamel en gebruik vir MALDI-TOF analise. Hierdie koppeling het getoon dat skeiding plaasvind op grond van molekulêre massa en chemiese samestelling. Grootte-uitsluitingschromatografie is gebruik vir die skeiding van molekules alleenlik op grootte. Hierdeur kon ‘n relatiewe vergelyking van die tannienmolekules gemaak word. Vir die karakterisering van hoë molekulêre massa tanniene is ‘n multi-dimensionele benadering nodig aangesien die verskeie verspreidings teenwoording in hierdie ekstrakte supergeponeerd is.