My objectives were to determine if nutritional benefits occur when animals are offered foods with compounds -- alkaloids, saponins, and tannins - that are potentially complementary. I hypothesized that food intake and digestibility increase when lambs consume plants such as alfalfa ALF that contain saponins or birdsfoot trefoil (BFT) that contain tannins when the basal diet is endophyte-infected tall fescue (TF) or reed canarygrass (RCG) both of which contain alkaloids. I predicted that the nutritional status of lambs would be enhanced if basal diets of alkaloid-containing grasses were supplemented with ALF or BFT. Lambs fed a basal diet of either endophyte-infected TF or RCG ate more food and consequently digested more dry matter, energy and nitrogen when supplemented with ALF or BFT. Lambs ingested more dry matter and digested more nutrients when fed a basal diet of RCG than one of TF, and supplementing with ALF and BFT was more beneficial for lambs fed TF than for lambs fed RCG. Increased intake of digestible nutrients was due to greater intake when lambs were offered more than one food, not due to an increase in digestibility. In pen trials meant to complement the field trials, lambs were offered an alkaloid-containing (either gramine or 5-methoxy-N,N-dimethyltryptamine) total mixed ration and supplemented with a food that contained saponins or tannins. All rations were isocaloric (3.3Mcal/kg) and isonitrogenous (14% CP). Lambs fed a ration with either alkaloid and offered a food containing saponin digested approximately the same amount of dry matter, energy, nitrogen, and NDF as lambs not offered saponin. When lambs were fed a ration with either alkaloid and supplemented with food that contained tannins, tannin consumption adversely affected dry matter, energy, and NDF digestibility, but lambs offered food with tannins increased dry matter intake, and as a result, they digested the same amount of dry matter, energy, and NDF as lambs not offered the food with tannins. Lambs offered tannin digested and retained more nitrogen than lambs not offered tannin. These findings indicate a nutritional advantage for sheep eating mixtures as opposed to monocultures of foods with different profiles of secondary compounds and nutrients.

A number of methods to isolate and quantify protein in Pinot noir wines were evaluated. The combination of precipitation by acetone containing 10% w/v trichloroacetic acid followed by quantification with the Bradford assay, reported in yeast invertase equivalents yielded the most accurate results when compared to micro-Kjeldahl analysis. The technique was validated by dialysis and proteolysis experiments and was used to assay protein in 57 Pinot noir wines. These wines were found to contain protein concentrations ranging from 49 to 102 mg/L. The mannan and tannin content of the wines was also measured, but no correlation between protein content and concentrations of these components was found. The presence of protein in red wines greater than 30 years old at concentrations typically found in white wines contradicts the notion that interactions with tannin severely reduce protein levels. / Graduation date: 2011

La substitution des composés carbonés d'origine fossile par des matières premières renouvelables représente un enjeu majeur et stratégique pour l'environnement, l'économie, et la santé publique. Nous nous sommes particulièrement intéressés au cas des dérivés du phénol, largement utilisés dans le domaine des matériaux synthétiques (résines, plastiques). Des travaux antérieurs ont démontré le potentiel des monomères de flavanols, sous-unités constitutives des chaines polymériques des tanins condensés comme substituts aux phénols issus de la pétrochimie, tels que le bisphénol A, l'objectif du présent travail a été de contribuer au développement d'une voie industrielle d'accès à de tels composés par dépolymérisation des tanins condensés (proanthocyanidines), une ressource végétale abondante mais actuellement peu exploitée pour ce type d'applications. Cette dépolymérisation peut être obtenue par rupture de la liaison interflavanique en milieu acide et piégeage des carbocations formés par un réactif nucléophile. Différentes stratégies et conditions ont été étudiées pour mieux comprendre le rôle de l'acide, du nucléophile, du solvant et l'impact de la température sur la réaction de dépolymérisation. Les stratégies sélectionnées, menées sur un dimère B2 pur servant de modèle et sur un extrait industriel de tanins de pépins de raisins blancs issus de marcs à l'échelle du gramme, ont été comparées en termes de rendement, de cinétique, de stabilité des produits, et de facilité de mise en œuvre et de traitement dans la perspective d'une production à plus grande échelle respectant au mieux les objectifs du développement durable et les contraintes de l'industrialisation. / The substitution of fossil carbon by renewable raw materials is a major strategic challenge for the environment, economy and public health. Our thesis focuses on the utilisation of phenol derivatives, which are widely used in the field of synthetic materials (resins, plastics). Previous studies have demonstrated the potential of plant flavanol monomers as substitutes for petrochemical phenols such as bisphenol A. The objective of this work was to contribute to the development of an industrial access to such compounds by depolymerization of condensed tannins (proanthocyanidins), an abundant plant resource currently untapped for such applications. Depolymerization can be performed by breaking the interflavan bonds in acidic medium and scavenging the released carbocations by a nucleophilic reagent. Various strategies and conditions were studied and compared to better understand the role of the acid, the nucleophile and the solvent and temperature in the depolymerisation reaction. The selected strategies, applied on a pure B2 dimer used as a model and an industrial seed tannins extract from white grape pomace at the gram scale, were compared in terms of performance, kinetics, product stability, ease of implementation and work-up in the context of a larger scale production complying with the objectives of sustainable development and the constraints of industrialization.

A aplicação de sais de alumínio para tratamento de efluentes é questionada devido a possíveis impactos nocivos aos seres humanos e organismos vivos, em decorrência de residuais de alumínio remanescentes na água tratada e das quantidades de lodo sedimentado que contém o metal. Portanto, o uso combinado de sais metálicos e taninos vegetais, a fim de reduzir as concentrações do primeiro, aplicadas na coagulação-floculação de contaminantes dos efluentes é importante, inclusive pelas vantagens do uso de taninos, como polímeros orgânicos biodegradáveis. Assim, este trabalho visa aplicar sulfato de alumínio e taninos, em uso individual e em combinação, para remoção de contaminantes por meio de coagulação-floculação. Os ensaios foram realizados com três efluentes, um com elevada carga orgânica, um com baixa carga orgânica e um efluente de acabamento, todos de um mesmo curtume que realiza operações de acabamento molhado a acabamento final de couro wet-blue. No efluente de alta carga orgânica, foram testados 5 tipos de taninos em seis dosagens, e os taninos Tanfloc SM e Tanfloc SH, com melhor eficiência, também foram testados no efluente de menor carga orgânica, assim como o sulfato de alumínio, nas mesmas concentrações utilizadas inicialmente a fim de apresentar os resultados atingidos em efluentes com características de altas e baixas dosagens de químicos Após, foram realizadas combinações de sulfato de alumínio com Tanfloc SM e Tanfloc SH, em diferentes concentrações, e realizados ensaios nos três efluentes, com o intuito de apresentar a eficiência do uso combinado destes produtos em diferentes características de efluentes e verificar a redução das dosagens de sulfato de alumínio. Os melhores resultados obtidos na aplicação combinada de sulfato de alumínio e taninos, mostraram remoção de cor, turbidez e COT estatisticamente iguais à aplicação do uso individual destes, porém utilizando menores dosagens de sulfato de alumínio na composição. Assim, conclui-se que é possível realizar, de forma eficiente e satisfatória, o uso de misturas de sulfato de alumínio com taninos de forma a reduzir as dosagens de sulfato de alumínio, obtendo bons resultados de remoção de cor, turbidez e remoções superiores de COT quando comparadas com a aplicação de todos os coagulantes/floculantes individualmente. / The use of aluminum salts for the treatment of effluents is questioned due to possible harmful impacts on humans and living organisms with aluminum residuals remaining in the treated water and the quantities of sedimented sludge containing the metal. Therefore, the combined use of metal salts and vegetable tannins, in order to reduce the concentrations of the former, applied in the coagulation-flocculation of effluent contaminants is important, including the advantages of the use of tannins, such as biodegradable organic polymers. Thus, this work aims to apply aluminum sulfate and tannins, in individual use and in combination, to remove contaminants by means of coagulation-flocculation. The tests were carried out with three effluents, one with high organic load, one with low organic load and one finishing effluent, all from the same tannery that performs wet finishing operations with the final wet-blue leather finish. In the high organic matter effluent, five types of tannins were tested in six dosages, and Tanfloc SM and Tanfloc SH tannins with better efficiency were also tested in the less organic effluent as well as aluminum sulfate in the same concentrations used in order to present the results achieved in effluents with characteristics of high and low chemical dosages Afterwards, combinations of aluminum sulphate with Tanfloc SM and Tanfloc SH were carried out in different concentrations, and tests were carried out on the three effluents, in order to show the efficiency of the combined use of these products in different effluent characteristics and verify the reduction of the dosages of aluminum sulfate. The best results obtained in the combined application of aluminum sulphate and tannins showed color removal, turbidity and TOC statistically equal to the application of the individual use of these, but using lower dosages of aluminum sulphate in the composition. Thus, it is concluded that it is possible to efficiently and satisfactorily carry out the use of aluminum sulphate mixtures with tannins in order to reduce the dosages of aluminum sulphate, obtaining good results of color removal, turbidity and higher removals of COT when compared to the application of all coagulants/flocculants individually.

As pastagens que cobrem uma importante área no território mundial apresentam elevado potencial de produtividade e suas características bioquímicas podem gerar relevante impacto na produção de ruminantes. Porém, poucos trabalhos relatam a concentração de compostos bioquímicos em pastagens tropicais comumente usadas na produção animal. Diante deste fato, o capítulo II desta tese teve como objetivo elucidar e determinar a concentração de taninos condensados e tocoferol, bem como avaliar a produção e os valores nutritivos de espécies forrageiras tropicais normalmente usadas em sistemas de pastejo. Com este estudo foi possível constatar que algumas espécies de gramíneas e leguminosas se destacam não apenas pela sua capacidade de produção de biomassa e qualidade nutricional, mas também pela concentração de compostos bioquímicos, como a gramínea tifton que teve elevada concentração de α-tocoferol (202.3 ± 116.5 mg/kg matéria verde, MV). As leguminosas amendoim forrageiro (15.7 ± 5.2 g/kg matéria seca, MS) e feijão guandu (8.7 ± 0.8 g/kg MS) apresentaram boa concentração de taninos condensados, mas o grande destaque foi para a leguminosa nativa pega-pega (66.5 ± 13.8 g/kg MS) que além da alta concentração de taninos, esses apresentaram potencial para atividade biológica (PPF = 60.1 g/kg MS) Aliado as características bioquímicas, as espécies que irão compor o sistema de produção podem influenciar na biologia de vida livre dos nematoides parasitas do trato gastrintestinal (NGI) e no comportamento ingestivo dos animais. O capítulo III e IV avaliam três diferentes sistemas de alimentação de cordeiros em pastagens tropicais. O capítulo III traz como objetivo avaliar a distribuição de larvas infectantes (L3) em diferentes perfis de pastagem tropical (gramíneas e leguminosas) e o impacto da contaminação da pastagem na carga parasitária e desempenho de cordeiros. Onde, a inclusão da leguminosa tropical alterou a concentração de larvas infectantes na pastagem e a contaminação dos animais. No capítulo IV é apresentado o trabalho que teve como objetivo avaliar o comportamento ingestivo de cordeiros em condições de pastejo contínuo submetidos a diferentes sistemas de alimentação com a presença de leguminosa tropical contendo taninos condensados. Apesar da diferença estrutural e concentração de taninos condensados, de modo geral essas características da pastagem não alteraram o comportamento ingestivo dos cordeiros. / Pastures covering an important area in the world territory present high production potential and their biochemical characteristics can generate a significant impact on the production of ruminants. However, few studies report the concentration of biochemical compounds in tropical pastures commonly used in animal production. Facing this fact, chapter II of this thesis had as objective to elucidate and to determine the concentration of condensed tannins and tocopherol, as well as to evaluate the production and nutritional values of tropical forage species normally used in grazing systems. In this study, it was possible to verify that some species of grasses and legumes stand out not only for their mass production capacity and nutritional quality, but also for the concentration of secondary compounds, such as tifton grass, which had a high α-tocopherol concentration (202.3 ± 116.5 mg / kg green matter, GM). The forage peanut legumes (15.7 ± 5.2 g / kg dry matter, DM) and pigeon pea (8.7 ± 0.8 g / kg DM) had an excellent concentration of condensed tannins, but the main highlight was the native legume Desmodium incunum (66.5 ± 13.8 g / kg DM) that in addition to the high concentration of tannins, these had potential for biological activity (PPP = 60.1 g / kg DM) In addition to the biochemical characteristics, the species that will make up the production system can influence the ecology of the free-living stages of endoparasite of the gastrointestinal tract (NGI) and the ingestive behavior of the animals. Chapter III and IV evaluate three different feeding systems of lambs in tropical pastures. Chapter III aims to evaluate L3 distribution in different tropical pasture (grass and legume) profiles and the impact of pasture contamination on lamb parasitic loads and production performance. Where the inclusion of the tropical legume changed the concentration of infective larvae in the pasture and the contamination of the animals. Chapter IV presents the work that aimed to evaluate the ingestive behavior of lambs under continuous grazing conditions submitted to different feeding systems with the presence of tropical legume containing condensed tannins. Despite the structural difference and concentration of condensed tannins, in general these pasture characteristics did not alter the ingestive behavior of the lambs.

Une alternative aux produits industriels de type phénol ou résorcinol peut être des tanins ou de la lignine. Les deux sont des polyphénols naturels, le tanin est extrait de différentes parties de plantes, tandis que la lignine est habituellement obtenue comme sous-produit dans les industries papetières. Ces deux produits sont la base principale sur laquelle j’ai travaillé pendant le développement de cette thèse. Dans une première partie, une étude de caractérisation et de différenciation entre différents tannins ayant la même origine mais que présentent un comportement différent lorsqu'ils sont utilisés dans la même application dans les mêmes conditions a été effectuée. Cette étude met en évidence la GPC comme technique fondamentale pour la différenciation des tanins de quebracho sulfités. D'autre part, les interactions entre différentes substances avec du tanin et de la lignine ont été étudiées. Comme l’étude de la réaction entre les diamines (telles que l'hexaméthylènediamine) avec du tanin et de la lignine pour obtenir des résines polycondensées. En outre, dans cette section ont été obtenus des polyuréthanes avec au moins 70% de substances naturelles dans leur préparation sans utiliser d'isocyanate dans le procédé. De plus, des aldéhydes dérivés de la lignine, comme la vanilline, ont été utilisés avec le tanin de pin pour la fabrication d'adhésifs dans la préparation de panneaux de particulaires, obtenant des résultats satisfaisants selon les normes européennes et des substances complètement naturelles. Enfin, dans le cadre d'un projet industriel les étapes initiales pour le développement d'une mousse de tanin rigide applicable par projection pour l'isolation thermique des bâtiments ont été réalisées. Lorsqu'un nouveau système de moussage mécanique a été développé pour des mousses de tanin basées sur des mousses de lutte contre incendie à base de tanin ou dans les mousses des opérations d’ouverture du tunnel, ce nouveau système de moussage évite les problèmes de retrait lors de la formation de la mousse / An alternative to industrial phenol or resorcinol industrial products may be tannins or lignin. Both are natural polyphenols, the tannin is extracted from different parts of plants, while lignin is usually obtained as a secondary product in the pulp and paper mill. These two products are the main basis on which I have worked during the development of this thesis. In a first part, a study of characterization and differentiation between different tannins with the same origin and that present a different behavior when used in the same application under the same conditions has been done. Highlighting the GPC as a fundamental technique for the differentiation between sulphited quebracho tannins. On the other hand, the interactions between different substances with tannin and with lignin have been studied. As the study of the reaction between diamines (such as hexamethylenediamine) with tannin and lignin to obtain a polycondensed resins. Also, in this section have been obtained polyurethanes with at least 70% of natural substances in their preparation without using any isocyanate in the process. In addition, aldehydes derived from lignin, such as vanillin, have been used next to pine tannin for the manufacture of adhesives in the preparation of particleboards, obtaining satisfactory results according to European standards and from completely natural substances. Finally, within an industrial project the initial steps have been carried out for the development of a rigid tannin foam applicable by projection for the thermal insulation of buildings. Where a new mechanical foaming system has been developed for tannin foams based in fire-fighting foams or in the foams of the tunneling operations, this new system of foaming avoids the problems of shrinkage during the formation of the foam

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study aimed to evaluate the effect of tannin extract from Acacia mearnsii in the reduction of total and urinary nitrogen (N) excretion, in optimizing nutritional and productive performance of lactating cows grazing on temperate or tropical pastures, and also aimed to evaluate its effects on the digestive process, N excretion as well as the flow of metabolites through the portal system and liver of sheep fed temperate grass or tropical grass based diets. Four assays were carried out, two with sheep and two with lactating cows. In assay 1, six sheep were used in a crossover design for two 21-day periods to evaluate the intake, digestibility and N excretion. The diets were composed of Tifton hay 85 and concentrate either without the inclusion of tannin extract (control) or with the addition of 1% tannin extract (dry matter (DM) basis). In assay 3, five sheep were used in a crossover design for two 21-day periods to evaluate the intake, digestibility, N excretion and the flow of blood metabolites through the portal system and liver. The diets were a mixture of oats and ryegrass hay and concentrate either without the addition of tannin extract (control) or with the addition of 2% tannin extract. In assays 2 and 4 were used 14 lactating cows in each assay through a random block design. The experiments lasted for 49 days, and were divided into two periods. In the first 21 days all cows received, for standardization, the same diet and were later randomly assigned, within each block, one of the treatments. In experiment 2, cows were grazing on Tifton 85 pasture and supplemented with concentrate containing 1%, or not (control), of tannin extract. In experiment 4, the cows were kept in mixed oats and ryegrass pasture, and supplemented with concentrate either with the addition of 2% tannin extract or without (control) the addition of tannin extract. For the sheep assays were collected food, scraps, feces, urine and samples as well as arterial, liver and portal blood samples, for assay 3. For assays with cows were collected food scraps, feces, urine and milk samples as well as blood samples from the coccygeal vein. The data were submitted to variance analysis and the effect of treatment compared by F test using the SAS statistical program. P≤0.05 values were considered significant and 0.05<P≤0.10 were considered trend. In assay 1 the inclusion of tannin in the diet promoted a reduction in the true digestibility of N and endogenous N excretion (P≤0.05), without affecting consumption, fecal and urinary excretion of N and digestibility of other dietary fractions (P>0.05). In assay 2 the tannin extract did not cause any changes (P>0.05) in consumption, and milk yield or composition, or the N use efficiency for synthesis of milk proteins, as well as in plasma urea concentrations. There was, however, an increase in N excretion via urine and hence reduction in the overall N use efficiency. In assay 3 there was a reduction (P≤0.05) of the true and apparent N digestibility and urea excretion by urine without affecting the parameters of intake, digestibility of organic matter, neutral detergent fiber and synthesis of microbial rumen nitrogenous compounds. The N-urea concentrations in arterial, portal and hepatic blood samples reduced (P≤0.05) and hepatic glucose concentration tended to decrease (P=0.065) due to the intake of the tannin extract. However, there was a reduction in N-urea flow only in total visceral tissue (P=0.053), and neither concentrations nor the N-NH3 flow changed (P>0.05). In assay 4 the intake of tannins did not affect any milk yield and composition parameters, neither plasma concentrations of urea. It did, however, promote increase (P≤0.05) pasture intake and fecal N excretion and tended to decrease (P≤0.10) N excretion through urine without altering the N use efficiency. The inclusion of 2% tannin extract of Acacia mearnsii in the concentrate fed to dairy cows in the proportion of approximately 25% of the diet based on temperate grasses promotes increased fodder consumption and has the potential to reduce the environmental impact due to the reduction of urinary N excretion, without short term interference in milk yield and composition. Furthermore, based on the study with sheep, offer of up to 40% of concentrate in the diet promotes a more marked reduction in urinary N excretion and may have positive effects on the concentrations of urea in milk and plasma. In assays with tropical grass the inclusion of tannin in the diet did not show results that justify the use of this additive in the assessed dietary conditions. / O objetivo deste estudo foi avaliar o potencial do uso dietético do extrato tanífero de Acacia mearnsii em reduzir a excreção de nitrogênio (N), melhorar a eficiência nutricional e o desempenho produtivo de vacas em lactação recebendo dietas à base de gramínea temperada ou gramínea tropical, e avaliar o seu efeito sobre os processos de digestão, excreção de N, e o fluxo de metabólitos através do sistema portal e fígado de ovinos recebendo dietas à base de feno de gramínea temperada ou gramínea tropical. Foram conduzidos dois ensaios com ovinos e dois ensaios com vacas em lactação. No ensaio 1, foram utilizados seis ovinos em um delineamento inteiramente casualizado (DIC) em esquema de reversão simples, em dois períodos de 21 dias, para avaliar o consumo, a digestibilidade e a excreção de N. As dietas foram constituídas de feno de Tifton 85 e concentrado sem inclusão de extrato tanífero ou adição de 1% de extrato tanífero (base MS). No ensaio 3, cinco ovinos foram utilizados em um DIC em esquema de reversão simples, em dois períodos de 21 dias, para avaliar o consumo, a digestibilidade, a excreção de N e o fluxo de metabólitos sanguíneos através do sistema portal e fígado. As dietas foram constituídas de feno misto de aveia e azevém e concentrado sem inclusão de extrato tanífero ou adição de 2% de extrato tanífero. Nos ensaios 2 e 4 foram utilizadas 14 vacas em lactação em cada um dos ensaios através de um delineamento em blocos ao acaso. Os experimentos tiveram duração de 49 dias, divididos em dois períodos. Nos primeiros 21 dias todas as vacas receberam a mesma dieta para padronização e, posteriormente, foi atribuído aleatoriamente às vacas, dentro de cada bloco, um dos tratamentos. No experimento 2, as vacas foram mantidas em pastagem de Tifton 85 e suplementadas com concentrado contendo 1% ou não (controle) de extrato tanífero. No experimento 4, as vacas foram mantidas em pastagem mista de aveia e azevém, e suplementadas com concentrado contendo 2% ou não (controle) de extrato tanífero. Nos ensaios com ovinos foram coletadas amostras de alimentos, sobras, fezes, urina, e também amostras de sangue arterial, portal e hepático no ensaio 3. Nos ensaios com vacas foram coletadas amostras de alimentos, sobras, fezes, urina, leite e sangue através da veia coccígea. Os dados foram submetidos à análise de variância e o efeito de tratamento comparado pelo teste F através do programa estatístico SAS. Valores de P≤0,05 foram considerados significativos e 0,05<P≤0,10 foram considerados tendência. No ensaio 1 a inclusão de tanino na dieta promoveu redução na digestibilidade verdadeira do N e na excreção de N endógeno (P≤0,05), sem influenciar no consumo, excreção fecal e urinária de N e digestibilidade das demais frações da dieta (P>0,05). No ensaio 2 o extrato tanífero não promoveu nenhuma alteração (P>0,05) no consumo, produção e composição do leite, eficiência de utilização do N para síntese das proteínas do leite, bem como nas concentrações de ureia plasmática. No entanto, houve aumento na excreção de N através da urina e, consequentemente, redução na eficiência de uso geral do N. No ensaio 3 houve redução (P≤0,05) das digestibilidades aparente e verdadeira do N e da excreção de ureia através da urina, sem afetar os parâmetros de consumo, digestibilidade da matéria orgânica, fibra em detergente neutro e síntese de compostos nitrogenados microbianos ruminais. As concentrações de N-ureia nas amostras de sangue arterial, portal e hepático reduziram (P≤0,05) e a concentração de glicose hepática tendeu a reduzir (P=0,065) devido à ingestão do extrato tanífero. Entretanto, houve redução no fluxo de N-ureia apenas nos tecidos viscerais totais (P=0,053) e, nem as concentrações, nem os fluxos de N-NH3 foram alterados (P>0,05). No ensaio 4 a ingestão de taninos pelos animais não afetou nenhum dos parâmetros de produção e composição do leite, assim como as concentrações plasmáticas de ureia. Entretanto, promoveu aumento (P≤0,05) no consumo de pasto e na excreção de N fecal pelos animais e tendeu a reduzir (P≤0,10) a excreção de N através da urina, sem alterar a eficiência de uso deste nutriente. A inclusão de 2% de extrato tanífero de Acacia mearnsii no concentrado fornecido a vacas em lactação na proporção de aproximadamente 25% da dieta à base de gramíneas temperadas promove aumento do consumo de forragem e tem o potencial de reduzir o impacto ambiental pela menor proporção de N excretado através da urina, sem interferir na produção e composição do leite em curto prazo. Além disso, com base no estudo com ovinos, o fornecimento de até aproximadamente 40% deste concentrado na dieta promove uma redução mais acentuada na excreção de N urinário e pode apresentar reflexos positivos sobre as concentrações de ureia no leite e no plasma. Nos ensaios com gramínea tropical a inclusão de tanino na dieta não apresentou resultados que justificam o uso deste aditivo nas condições dietéticas avaliadas.

Master of Science / Apparel, Textiles, and Interior Design / Sherry J. Haar / This study compared the colorfastness of potassium aluminum sulfate (PAS) mordanted and nonmordanted 30/2 wool yarn, dyed with black walnut (Juglans Nigra), Osage orange (Maclura pomifera), and eastern redcedar (Juniperus virginiana) sawdust. Information from this study is intended to inform natural dye artisans and to increase the profitability of sawdust for farmers, ranchers, and mill owners who would otherwise find little use for this byproduct of timber manufacturing. Pre-testing ensured dyeings of visually comparable color depth and dye concentrations were pre-tested to find a standard depth of shade between the same dye on PAS mordanted and nonmordanted wool yarns. Tests for colorfastness to light, laundering and staining were performed in accordance to AATCC test methods. Resulting colors for exposed and unexposed specimens were rated using CIE L* a* b* values and AATCC gray scale for color change. GLM Anovas and two-sample t-tests were used to statistically analyze CIE L* a* b* values. As expected, findings indicated that dye absorption was improved with the use of a PAS mordant, especially for black walnut and eastern redcedar. For yarns premordanted with PAS the dyewoods became yellower. A PAS mordant slightly improved colorfastness to light for black walnut and eastern redcedar, but did not influence Osage orange which had an unexpected color change from bright yellow to warm brown after exposure to light. Colorfastness to laundering was slightly improved with PAS for Osage orange, while black walnut and eastern red cedar had slightly less color change without the mordant. This research was supported by the Agricultural Research Experiment Station and Kansas State University.

Made available in DSpace on 2015-05-14T13:21:51Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3041446 bytes, checksum: ababcafc4806728e34bf8d0bd8ea021e (MD5) Previous issue date: 2010-09-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This study proposed a miniaturized flow-batch system for chemical analysis. The technique used microfabricated urethane-acrylate, a commercial polymer. The microsystem was evaluated and optimized by analysis of synthetic dye samples. Afterwards, it was employed for the determination of tannins in tea samples. The tannins are a group of polyphenols of significant relevance in the food industry and pharmaceuticals. The samples used were green and black tea, obtained from the local market. The determinations were performed by turbidimetric methods using copper (II) in an acetate medium, with photometric methods and ferrous tartrate as a reference. Miniaturization in urethane-acrylate implies low cost and low maintenance, rapid prototyping and includes the satisfactory physicochemical properties of polymer. These characteristics combined with the general advantages of miniaturization in analytical devices, such as high frequency analysis and low waste generation, make the system a great source in academic research. For analysis of tannins in tea samples, the system had precise and accurate results, and high speeds. This flow-batch microsystem was able to perform up to 300 tests per hour, for the photometric method of reference and up to 200 tests per hour for the turbidimetric method. Each analysis performed generated waste volumes lower than 70 μL. Data validation of statistical models obtained have proved very satisfactory and promising for new optical applications. / Neste trabalho de pesquisa foi proposto o uso da técnica de microfabricação em polímero comercial uretana-acrilato para a miniaturização de um sistema automático de análises químicas em fluxobatelada, o flow-batch. O microssistema desenvolvido foi avaliado e otimizado pela análise de amostras sintéticas de corantes. Posteriormente, o microssistema, foi empregado para a determinação de taninos, grupo de polifenóis de expressiva relevância industrial, em amostras de chá verde e preto, por dois métodos ópticos distintos, fotométrico e turbidimétrico. A técnica de microfabricação em uretana-acrilato se caracteriza pelos baixos custos de implementação e manutenção, satisfatórias propriedades físicoquímicas do polímero e a rápida prototipagem de sistemas microfluídicos. Tais características aliadas às vantagens inerentes da miniaturização de dispositivos analíticos, como a elevada frequência de análise e a baixa geração de resíduos, conferem a esse sistema de análise uma ótima fonte de pesquisa acadêmica. Para análise dos taninos em amostras de chá, o sistema apresentou resultados precisos e exatos, além de uma alta velocidade analítica para ambos os métodos ópticos, sendo capaz de executar até 300 análises por hora, no método fotométrico e 200 análises por hora pelo método turbidimétrico. Cada análise efetuada gerou resíduos cujos volumes foram inferiores a 70 μL. Os dados de validação estatística dos modelos obtidos se mostraram bastante satisfatórios e promissores para novas aplicações ópticas.

A aplicação de sais de alumínio para tratamento de efluentes é questionada devido a possíveis impactos nocivos aos seres humanos e organismos vivos, em decorrência de residuais de alumínio remanescentes na água tratada e das quantidades de lodo sedimentado que contém o metal. Portanto, o uso combinado de sais metálicos e taninos vegetais, a fim de reduzir as concentrações do primeiro, aplicadas na coagulação-floculação de contaminantes dos efluentes é importante, inclusive pelas vantagens do uso de taninos, como polímeros orgânicos biodegradáveis. Assim, este trabalho visa aplicar sulfato de alumínio e taninos, em uso individual e em combinação, para remoção de contaminantes por meio de coagulação-floculação. Os ensaios foram realizados com três efluentes, um com elevada carga orgânica, um com baixa carga orgânica e um efluente de acabamento, todos de um mesmo curtume que realiza operações de acabamento molhado a acabamento final de couro wet-blue. No efluente de alta carga orgânica, foram testados 5 tipos de taninos em seis dosagens, e os taninos Tanfloc SM e Tanfloc SH, com melhor eficiência, também foram testados no efluente de menor carga orgânica, assim como o sulfato de alumínio, nas mesmas concentrações utilizadas inicialmente a fim de apresentar os resultados atingidos em efluentes com características de altas e baixas dosagens de químicos Após, foram realizadas combinações de sulfato de alumínio com Tanfloc SM e Tanfloc SH, em diferentes concentrações, e realizados ensaios nos três efluentes, com o intuito de apresentar a eficiência do uso combinado destes produtos em diferentes características de efluentes e verificar a redução das dosagens de sulfato de alumínio. Os melhores resultados obtidos na aplicação combinada de sulfato de alumínio e taninos, mostraram remoção de cor, turbidez e COT estatisticamente iguais à aplicação do uso individual destes, porém utilizando menores dosagens de sulfato de alumínio na composição. Assim, conclui-se que é possível realizar, de forma eficiente e satisfatória, o uso de misturas de sulfato de alumínio com taninos de forma a reduzir as dosagens de sulfato de alumínio, obtendo bons resultados de remoção de cor, turbidez e remoções superiores de COT quando comparadas com a aplicação de todos os coagulantes/floculantes individualmente. / The use of aluminum salts for the treatment of effluents is questioned due to possible harmful impacts on humans and living organisms with aluminum residuals remaining in the treated water and the quantities of sedimented sludge containing the metal. Therefore, the combined use of metal salts and vegetable tannins, in order to reduce the concentrations of the former, applied in the coagulation-flocculation of effluent contaminants is important, including the advantages of the use of tannins, such as biodegradable organic polymers. Thus, this work aims to apply aluminum sulfate and tannins, in individual use and in combination, to remove contaminants by means of coagulation-flocculation. The tests were carried out with three effluents, one with high organic load, one with low organic load and one finishing effluent, all from the same tannery that performs wet finishing operations with the final wet-blue leather finish. In the high organic matter effluent, five types of tannins were tested in six dosages, and Tanfloc SM and Tanfloc SH tannins with better efficiency were also tested in the less organic effluent as well as aluminum sulfate in the same concentrations used in order to present the results achieved in effluents with characteristics of high and low chemical dosages Afterwards, combinations of aluminum sulphate with Tanfloc SM and Tanfloc SH were carried out in different concentrations, and tests were carried out on the three effluents, in order to show the efficiency of the combined use of these products in different effluent characteristics and verify the reduction of the dosages of aluminum sulfate. The best results obtained in the combined application of aluminum sulphate and tannins showed color removal, turbidity and TOC statistically equal to the application of the individual use of these, but using lower dosages of aluminum sulphate in the composition. Thus, it is concluded that it is possible to efficiently and satisfactorily carry out the use of aluminum sulphate mixtures with tannins in order to reduce the dosages of aluminum sulphate, obtaining good results of color removal, turbidity and higher removals of COT when compared to the application of all coagulants/flocculants individually.